Symposium Organizers
Swadeshmukul Santra, University of Central Florida
Michael Molinari, Universite de Reims Champagne Ardenne
Nicole Labbe, University of Tennessee
Loukas Petridis, Oak Ridge National Laboratory
BI02.01: Non-Traditional Plant and Soil Treatments
Session Chairs
Ashok Mulchandani
Swadeshmukul Santra
Monday PM, November 27, 2017
Sheraton, 3rd Floor, Gardner AB
8:30 AM - *BI02.01.01
Novel Copper Composites and Magnesium Oxide Nanomaterials against Copper-Tolerant Strains of Xanthomonas Perforans and Bacterial Spot of Tomato
Mathews Paret 1
1 Department of Plant Pathology, University of Florida, Gainsville, Florida, United States
Show AbstractBacterial spot of tomato caused by Xanthomonas spp. is the leading bacterial disease of tomatoes in the U.S and worldwide. Studies were undertaken from 2015-2016 to evaluate the antibacterial activity of three novel copper composites, core-shell copper (CS-Cu), multi-valent copper (MV-Cu), and fixed quaternary ammonium copper (FQ-Cu), and magnesium oxide nanomaterials as potential alternatives to commercially available copper bactericides for controlling copper-tolerant X. perforans. This is highly relevant as currently all strains in Florida are copper-tolerant, and also in many other places, and there are only a few effective materials available in the market against the bacterium. Thus, finding alternatives to conventional copper bactericides is critical for the U.S tomato industry. In vitro studies showed that 100 μg/ml of metallic copper from CS-Cu and FQ-Cu killed the copper-tolerant X. perforans stain within 1 h of exposure. In contrast, none of the micron-sized copper rates (100-1000 μg/ml) from Kocide 3000 significantly reduced copper-tolerant X. perforans populations after 48 h of exposure compared to the water control (P= 0.05). Greenhouse studies demonstrated that all copper composites significantly reduced bacterial spot disease severity when compared to copper-mancozeb and water controls (P= 0.05). Although there was no significant impact on yield, copper composites significantly reduced disease severity when compared to water controls using 80% less metallic copper in comparison to the grower’s standard in field studies (P= 0.05). In vitro studies demonstrated that MgO had high antibacterial activity against copper-tolerant X. perforans compared to the equivalent concentration of a standard Cu-based bactericide. Two greenhouse experiments with the copper-tolerant strain demonstrated that disease severity was significantly reduced by MgO at 200 µg/ml compared to copper-mancozeb, the grower standard, and the untreated control (P = 0.05). In three field experiments conducted at NFREC, Quincy and GCREC, Wimauma, non-formulated MgO at 200 µg/ml significantly reduced disease severity compared to the untreated control (P = 0.05). There was no negative impact on the yield due to MgO treatments. These studies demonstrated the antibacterial potential of novel copper composites and MgO nanomaterials against X. perforans and its potential use against bacterial spot of tomato. Most recent findings on studies on elemental accumulation of metals in tomatoes due to MgO nanomaterial application and review of prior studies on photocatalytic nanomaterials (TiO2/Zn, TiO2/Ag) and bio-nanomaterials (Ag-dsDNA-GO) will be presented.
9:00 AM - BI02.01.02
T-SOL a Non-Nano Copper Alternative Antimicrobial for the Management of Citrus Canker and HLB
Tyler Maxwell 2 1 , Smruti Das 2 , Parthiban Rajasekaran 2 , Mikhael Soliman 2 3 , Ziyang Huang 2 1 , Ali Ozcan 2 1 , Mikaeel Young 2 4 , Laurene Tetard 2 3 5 , Swadeshmukul Santra 2 1 4
2 NanoScience Technology Center, University of Central Florida, Orlando, Florida, United States, 1 Chemistry, University of Central Florida, Winter Haven, Florida, United States, 3 Materials Science and Engineering, University of Central Florida, Orlando, Florida, United States, 4 Burnett School of Biomedical Science, University of Central Florida, Orlando, Florida, United States, 5 Physics, University of Central Florida, Orlando, Florida, United States
Show AbstractTo combat the rise of drug and copper resistant pests and address the issue of toxic copper build up in soils, new agricultural formulations are needed. It is necessary that the pesticides of the future have improved availability of metallic active ingredients with overall less metal usage per acre of crops protected. We have developed a ternary solution (TSOL) as a copper alternative pesticide where zinc ions are the primary active ingredient. TSOL technology encompasses multiple variants that utilized three different Zn chelating agents; urea, sodium salicylate, and sodium gluconate. Spectroscopic material analysis showed that metal ions are interacting with the chelate functional groups (such as carboxyls, hydroxyls and amines). Phytotoxicity studies conducted with citrus plants (Sp. Cleopatra) at a field spray (800ppm metal content) rate with all TSOL variants considered showed no toxicity. Plant uptake and rainfastness studies conducted using atomic absorption and X-Ray fluorescence depicted the influence of chelating agent in the differences in permeability and systemic movement of zinc. Systemic antimicrobial studies suggested that between 50-100 ppm of metallic Zn, all TSOL variants exhibited significantly improved killing efficacy against Escherichia coli and Xanthomonas alfalfae compared against Zn ions alone. TSOL variants made from either reagent grade or agriculture grade chemicals appear to have similar antimicrobial and plant compatibility characteristics suggesting the feasibility of this material for industrial scale production.
9:15 AM - BI02.01.03
Nanoscale Nutrients Suppress Plant Disease and Increase Crop Yield
Jason White 1 , Roberto De La Torre Roche 1 , Jorge Gardea-Torresdey 2 , Christian Dimkpa 3 , Wade Elmer 1 , Nubia Zuverza Mena 1
1 , Connecticut Agricultural Experiment Station, New Haven, Connecticut, United States, 2 , University of Texas at El Paso, El Paso, Texas, United States, 3 , IFDC, Muscle Shoals, Alabama, United States
Show AbstractSoil-borne pathogens significantly limit agricultural production, reducing crop yields by 10-20% and resulting in billions of dollars in losses. Such inefficiencies have a significant impact on global food insecurity and will be exacerbated by a changing climate and increasing population. Micronutrients, such as Cu, Mn and Zn are known to protect plants from root disease, but traditional foliar applications of these elements are not basipetally translocated to roots. Furthermore, soil treatments are usually ineffective due to poor nutrient availability in soils. Although there may be great potential for using nanoparticles (NP) of micronutrients to nourish roots in disease infested soils, little information exists on mechanisms of action, efficacy and application. A series of studies have been investigating if foliar applications of metallic oxides of micronutrients in NP form could affect plant health when grown in soil with known plant pathogens. Using greenhouse and field studies, we are growing tomato, eggplant, watermelon and sorghum in pathogen (Fusarium, Verticillium) infested soils. In the greenhouse, NP of AlO, CuO, FeO, MnO, NiO, and ZnO were sprayed on tomatoes grown in soilless medium infested with the Fusarium wilt fungus. NP of CuO, MnO, or ZnO reduced disease estimates by 31%, 28%, or 28%, respectively, when compared to controls. When NP of CuO, MnO, or ZnO, their bulked equivalents, or their sulfate salts were compared to untreated eggplants in the greenhouse in soilless medium infested with the Verticillium wilt fungus, NP of CuO increased fresh weights by 64%, reduced disease by 69%, and had 32% more Cu in the roots. These same amendments were sprayed onto the foliage of tomato and eggplant transplants and set in field plots in soil heavily infested with the Verticillium wilt fungus. Compared to untreated controls, yields of tomato were 33% or 31% greater with NP of CuO or the bulked MnO, respectively. NP of CuO or ZnSO4 increased eggplant yields by 34% or 41% when compared to controls, respectively. Importantly, in vitro studies found that nanoscale micronutrients were not inhibitory to the Fusarium wilt fungus, suggesting that host defence was being modified. Ongoing studies that may also be discussed involve the importance of cultivar type and innate resistance to infection on the efficacy of nanoscale micronutrient amendments and disease suppression. In addition, greenhouse and field experiments are assessing binary combinations of NP CeO2, CuO, MnO, and ZnO on eggplant growth upon infection with Verticillium wilt. Last, ongoing studies are evaluating the impact of ZnO NP exposure on sorghum growth and macronutrient utilization efficiency. Collectively, our findings show that providing required micronutrients in nanoscale form is a cost-effective means to enhance foliar nutrient accumulation, increase element transfer to the roots, and improve overall plant health and yield in the presence of disease.
9:30 AM - BI02.01.04
Targeted Delivery of Antibiotics in Plants through Silk-Based Materials
Yunteng Cao 1 , Benedetto Marelli 1
1 , MIT, Cambridge, Massachusetts, United States
Show AbstractGlobal food security has been a critical issue for decades and the imbalance between crop yield and food demanding will worsen due to the rapidly increasing population and limited potential of crop increment. Despite the struggle of agriculture to meet food security, plant disease has a detrimental effect on crop production and significant losses, 20-40% of global crop productivity at a conservative estimate, are caused. Effective management of plant disease thus is of great importance. Although spraying pesticide/fungicide is a widely used effective method in agriculture, it has limited effect on diseases associated with phloem and xylem-restricted bacteria, such as citrus greening and zebra chip, because bacteria can spread unimpededly in plants via the vascular system. Indeed, management of citrus greening and zebra chip is primarily achieved by frequent application of pesticides for vector control and immediately removal of infected plants. In addition, abuse of pesticide may cause side effects on the ecosystem and result in pesticide resistance. Although treatment to the bacteria via antibiotics is a potential approach, there are several challenges, including difficulty to target pathogens and short lifetime of antibiotics. Therefore, an effective targeted therapy to treat phloem and xylem-restricted bacteria is highly desirable.
Targeted drug delivery has gained much attention due to its superior capacity to maximum therapeutic efficacy and minimum side effects of drugs and has been achieved by many methods, including nanoparticles and microneedles. Silk fibroin, derived from domesticated silkworms is an FDA and EPA approved natural biomaterial that has been largely investigated in drug delivery. Silk fibroin possesses, in fact, many compelling properties, including biocompatibility, tunable degradation rate, ease of fabrication in various forms with nano- and micro-scale features, and the capability to stabilize heat-labile therapeutics. In particular, silk fibroin fabricated into microneedles loaded with several antibiotics has shown the possibility to precisely deliver and stabilize drugs. Despite extensive studies on microneedles and silk fibroin in medical applications, they are rarely used in plants.
In this work, microneedles composed of silk and loaded with oxytetracycline were proposed as a therapy to treat phloem-restricted disease and used effectively in a tunable manner. Tomato plants infected with Candidatus Liberibacter solanacearum were used as a model. Microneedle dimensions were investigated from 500 micros to 2mm. Degradation rates of microneedles treated with different post-treatments as well as drug release rates were monitored for 30 days upon injection on plants, and their effects were assessed. This opens the door to new and targeted treatments for plants infected by phloem and xylem-restricted pathogens.
9:45 AM - BI02.01.05
Fixed-Quat—A Non-Metal Alternative to Copper Biocides
Mikaeel Young 2 5 , Ali Ozcan 2 3 , Parthiban Rajasekaran 2 , Preeti Kumrah 5 , Monty Myers 1 , Evan Johnson 1 4 , James Graham 1 4 , Swadeshmukul Santra 2 3 5
2 NSTC, University of Central Florida, Orlando, Florida, United States, 5 Burnett School of Biomedical Sciences, University of Central Florida, Orlando, Florida, United States, 3 Chemistry, University of Central Florida, Orlando, Florida, United States, 1 IFAS, University of Florida, Ft. Pierce, Florida, United States, 4 Plant Pathology, University of Florida, Lake Alfred, Florida, United States
Show AbstractCopper (Cu) based biocides have been extensively used as crop protectants in agriculture. Protracted use of Cu biocides however increases the risk of Cu accumulation in fertile soil and development of bacterial Cu resistance. Therefore a reliable alternative to Cu, preferably non-metal based with comparable or improved antimicrobial efficacy is desired. Quaternary Ammonium Compounds (Quats, a class of positively charged compounds) are used as powerful disinfectants. Quat cannot be however directly applied to plant systems as bactericides as it causes severe phytotoxicity. In this study, we are reporting for the first time a novel strategy for mitigating Quat phytotoxicity while maintaining antimicrobial efficacy using silica gel as the Quat delivery system (called hereafter Fixed-Quat gel, FQ-G). FQ-G composite material was synthesized using a sol-gel method and characterized using Scanning Electron Microscopy (SEM) for structure and morphology. Quat interaction with silica was investigated using Fourier Transform Infra-Red spectroscopy (FTIR). Phytotoxicity testing of FQ-G was conducted on two model species, ornamental Vinca and tomato. Results showed that the FQ-G is completely non-phytotoxic. In-vitro antimicrobial efficacy of FQ-G was evaluated against Xanthomonas alfalfae subsp. citrumelonis, Pseudomonas syringae pv. syringae and Clavibacter michiganensis subsp. michiganensis using various assays including determination of the Minimum Inhibitory Concentration (MIC) and Minimum Biofilm Eradication Concentration (MBEC). In-vitro assays confirmed that FQ-G did not lose activity compared to Quat alone. Field efficacy of FQ-G was evaluated for control of bacterial citrus canker caused by Xanthomonas citri subsp. citri and two fungal diseases, citrus scab caused by Elsinoe fawcettii and melanose caused by Diaporthe citri on ‘Ray Ruby’ red grapefruit trees over three seasons (2014, 2015 and 2016). FQ-G reduced incidence of canker infected fruit to 15% (2014), 26% (2015) and 55% (2016) compared to the untreated with 62%, 60% and 93%, respectively. Commercial cuprous oxide bactericide/fungicide reduced infected fruit to 16% (2014), 29% (2015) and 56% (2016). This demonstrated that FQ-G provided comparable control of bacterial and fungal diseases to a copper standard with no metal actives, confirming strong potential for crop protection.
Keywords: Fixed-Quat, Quat, Silica Gel, Agriculture, Biocide, Copper, Phytotoxicity, citrus
10:30 AM - *BI02.01.06
Aquatic and Cellular Toxicity Assessment for Commercially Viable Agriculture Biocide—ZinkicideTM
Parthiban Rajasekaran 1 , Mikaeel Young 1 , Mitsushita Doomra 1 , Tyler Maxwell 1 , Swadeshmukul Santra 1
1 , NanoScience Technology Center/UCF, Orlando, Florida, United States
Show AbstractZinkicideTM is a promising agriculture biocide that has shown effectiveness against microbial diseases that affect various vegetable and fruit crops in controlled field trials. While effectiveness against microbes is primary attribute for any agricultural biocide, assessment of any potential toxicity to humans via occupational or accidental exposure is mandatory for passing regulatory hurdles. Additionally, unintentional exposure of local water bodies where the biocide is sprayed also could affect the fish and other aquatic living organisms. Modeling hypothetical yet very possible condition of human exposure, toxicity assessment was performed in lung epithelial cell line (A549) (simulating pulmonary exposure), human dermal fibroblasts (simulating topic exposure) and macrophages (systemic exposure). To assess any unintended toxic effect on the aquatic systems, model fish exposure studies using fathead minnows (Pimephales promelas) were performed. These toxicity studies suggest that the ZinkicideTM material is no different than the currently available commercial products such as Kocide and Nordox in terms of toxicity to cellular systems and fish model systems. Since the individual components of ZinkicideTM material were not known to cause any significant damage to plant systems, any toxicity arising out of the final material was unexpected. These studies suggest that ZinkicideTM usage in agricultural crop protection would not be detrimental to surrounding ecosystem and the humans that come in contact with the material.
11:00 AM - BI02.01.07
Stabilization and Delivery of Rhizobacteria to Mitigate Soil Salinity
Augustine Zvinavashe 1 , Benedetto Marelli 1
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Show AbstractHow will we provide food to an estimated 9.6 billion people by 2050? In spite of the gains in agricultural productivity of the past decades, the Food and Agricultural Organization of the United Nations reports over 800 million people in the world, or one in nine, currently suffer from hunger. One of the leading factors is that there is a significant gap between crop yields’ and yield potential. By 2050 food demand is estimated to have increased by 50 to 100% . However, this will add stress to our soils. Therefore ways to protect and alleviate soil degradation are a must to increase productivity for now and the future. Improper farming techniques, misuse or excess use of fertilizers and pesticides are one of many factors that lead to soil degradation. However, growth-promoting bacteria are known to alleviate soil degradation by providing plants with required nutrients, combating pathogens and/or absorbing excessive salts that cause degradation in a symbiotic relationship. With biological means of combating and enhancing food production the use of fertilizers, pesticides and chemicals can be significantly reduced and lead to less soil degradation. Currently, this is of great importance in developing countries were there is a significant gap between crop yields and yield potential. With such a tool remote areas in Africa and India were fertilizers are expensive and difficult to obtain, production can be significantly increased. Increasing crop yields alone will not solve this problem, but a cocktail of solutions. It is critical to increase output by reducing inputs such as water, fertilizers and pesticides and Rhizobacteria are a key tool. However, our biggest challenge is that they are very difficult to grow. Leveraging our expertise in biopolymers we plan to develop a bacteria technology encapsulating and controlling delivery for soil salinity control, which is easily transferable for other uses. Our, project focuses on stabilizing and controlling degradation for delivery of Rhizobacteria in structural biopolymers. The ability to stabilize bacteria will not only be beneficial to the agricultural world, but the scientific community at large. Our studies are exploring EPA approved biopolymers such as zein, chitosan, alginate, silk and trehalose biopolymers. Embedding bacteria in silk fibroin materials or trehalose materials has stabilized bacteria for up to a week in standard conditions, this result provides the mean. Currently, experiments are looking at stabilizing for longer periods and different temperatures. Silk fibroin has been shown to preserve perishables through the modulation of gases by membrane. In addition, trehalose is implicated in anhydrobiosis. This is the ability to withstand dessication and Tardigrades rely on this mechanism. We relied on such mechanisms to mimic nature.
11:15 AM - BI02.01.08
Programmable Ecosystems—Engineered Environments for the Study of Field Conditions
Ludovico Cademartiri 1 , Oskar Siemianowski 1 , Kara Lind 1 , Xinchun Tian 1
1 , Iowa State University, Ames, Iowa, United States
Show AbstractThe necessity of understanding the role of the abiotic and biotic environment on the development of plants and ecosystems is challenged by a lack of tools capable of providing simple and controllable model systems with which to test hypotheses. While biology has made great strides in the implementation of sophisticated methods for the characterization of the various -omics, relatively little has been done to improve and standardize the tools available for the growing of plants in controlled environments.
Our group is interested in creating a set of integrated tools to allow the scientific community to create completely customizable environments with which to conduct plant biology and plant ecology experiments.
In this talk I will describe a strategy for the design of model ecosystems for plants and their microbiome in which the ecosystem composition, connectivity, and stimulation can be programmed and dynamically controlled.
We will show how engineered flows in these systems allow for the quantitative and dynamic control of the effective signaling distances between organisms (down to the μm scale) in cm-scale networks of cm-scale habitats that combine the control, modularity, and connectivity of microfluidics with the simplicity and low cost of Petri dishes.
11:30 AM - BI02.01.09
Enhancing the Efficiency of Agricultural Sprays through In Situ Precipitation
Maher Damak 1 , Seyed Reza Mahmoudi 1 , Nasim Hyder 1 , Kripa Varanasi 1
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Show AbstractLow retention of chemicals due to poor application of agricultural sprays on plants is an important issue, as large quantities of toxic chemicals end up in soils and groundwater after sprayed droplets bounce off leaves. One of the most important causes of the problem is that leaves are hydrophobic, which makes impinging droplets bounce or roll-off the surface. Here we propose to enhance the amount of liquid that remains on hydrophobic surfaces by in-situ formation of hydrophilic surface precipitates that pin the impacting drops during the retraction phase and prevent them from bouncing. We use two solutions containing oppositely charged polyelectrolytes and we spray them simultaneously on the surface. As droplets from both sprays coalesce on the surface, the charged polymers attract to each other and a precipitation reaction takes place, forming microscopic defects. We study individual drop-on-drop impact dynamics of the various possible interactions using a high-speed camera and we image the surface after impact. Based on this data, we elucidate the mechanism of precipitate formation and droplet retention. We measure the precipitation timescale, derive a physical model to estimate the energy dissipation by the formed defects and compare it to the kinetic energy to predict the transition from bouncing to sticking, which can be used to build a design map for effective sprays. Using our model, we make solutions that exhibit large macroscopic enhancements in retention of sprays on superhydrophobic synthetic surfaces as well as various leaves. We demonstrate the results with various charged polymers, including natural and biodegradable ones that would be excellent candidates for application in agricultural sprays.
BI02.02: Tools and Sensors for Plant and Soil Characterization
Session Chairs
Michael Molinari
Swadeshmukul Santra
Monday PM, November 27, 2017
Sheraton, 3rd Floor, Gardner AB
2:00 PM - BI02.02.01
Rapid Detection of Pesticide Concentrations in Citrus Leaf Tissue
Charles Edmunds 1 , Mikhael Soliman 2 , Laurene Tetard 2 , Swadeshmukul Santra 2 , Nicole Labbe 1
1 Center for Renewable Carbon, The University of Tennessee, Knoxville, Tennessee, United States, 2 Nanoscience Technology Center, University of Central Florida, Orlando, Florida, United States
Show AbstractThe citrus greening disease known as Haunglongbing (HLB) has had a detrimental impact on the citrus industry in Florida. We have applied analytical tools such as infrared spectroscopy (near and mid-infrared), X-ray fluorescence (XRF), and high-performance liquid chromatography (HPLC) for the rapid detection of the concentration of multifunctional surface/subsurface/systemic therapeutic (MS3T), a newly developed pesticide, in citrus leaf tissue. Infrared spectroscopy has several advantageous qualities such as rapid data acquisition time, little or no samples preparation, as well as being relatively low cost, non-destructive, and field deployable. By utilizing a multivariate statistical approach called partial least squares (PLS) regression, spectroscopic data was correlated to reference measurements for many leaf tissue samples in order to build robust predictive models. Once the models are properly calibrated, the easily acquired spectra of the leaf tissue can be used to predict the MS3T concentration in the same.
In order to establish reference values for MS3T content in leaf tissue, we targeted zinc (Zn) and nitrogen (N), as these are major components of MS3T. These reference measurements for leaf tissue samples were collected using XRF and HPLC for Zn and N-containing compounds, respectively. The spectroscopic and reference data were used to develop robust prediction models. For example, a near-infrared partial least squared (NIR-PLS) model was constructed with a range of 26 to 830 ppm Zn (in leaf tissue), a correlation coefficient (reference vs. predicted value) of R2 = 0.98, and root mean square error (RMSE) of 44 ppm. This methodology has been applied to recent MS3T field trials, and results demonstrate that after an initial foliar spray application of MS3T, the pesticide persisted in leaf tissue over the testing period of 2-weeks. Longer term field trials are currently underway, and the findings of MS3T accumulation and persistence over time will be discussed. Ultimately this technology can be deployed in the field and be used to inform optimum pesticide application schedules on an individual farm plot basis. The ability to accurately and quickly detect the concentration of the MS3T pesticide in citrus plant biomass is essential to combat the Haunglongbing disease.
2:15 PM - BI02.02.02
In Situ Zn2+ Detection Using a Novel Two Step Square Wave Anodic Stripping Voltammetry-Based Needle-Type Microsensor for Citrus Plant Applications
Jared Church 1 , Woo Hyoung Lee 1
1 , University of Central Florida, Orlando, Florida, United States
Show AbstractIn the span of 10 years, Huanglongbing (HLB) has devastated Florida’s over 10-billion-dollar citrus industry. Recent works on greenhouse canker infiltration assays showed local systemic activity of Zn-chelate (e.g. Zinkicide); however, there is no clear understanding of how the Zn-chelate moves in citrus trees. Although there are many analytical methods available for detecting Zn2+ in aqueous solutions, in situ monitoring of the movement of Zn-chelate in citrus trees is quite challenging. There is an urgent need to develop a reliable Zn2+ monitoring tool, capable of tracking its systemic activity directly in planta and successful in situ Zn2+ detection will lead to better understanding of its potential fate in planta for effective HLB management. In this study, a potential use of square wave anodic stripping voltammetry (SWASV) was evaluated for the detection of zinc in citrus plants. Two novel concepts were explored to overcome challenges of in situ measurement of Zn2+ in planta. First, a low melting point bismuth alloy (Belmont Alloy 2451: 44.7% bismuth, 22.6% lead, 19.1% indium, 8.3% tin, and 5.3% cadmium, melting point 47°C) was tested as a way to eliminate the need for co-deposition of bismuth traditionally used in SWASV detection of zinc. Second, a novel concept of separating deposition and stripping steps was evaluated as a way to minimize the invasiveness of the measurement by eliminating the need for inserting a counter and reference electrode into the citrus plant. The bismuth microelectrode was fabricated by heating the bismuth alloy and pushing the melted alloy through a borosilicate micropipette with a tip diameter of 6 µm. To test the sensor, the bismuth electrode was inserted into a solution of 0.1 M Tris buffer at pH 6.5 (to represent conditions found in the vascular bundle of citrus plants using a pH microsensor) with varying concentrations of Zn2+ (1– 200 ppm). Zn2+ was then deposited on the bismuth by applying a -1.4 V potential for 180 seconds. Next, the electrode was transferred to a separate solution of 0.1 M acetate buffer at pH 4.5 for striping (Scan: -1.4V to -0.4 V; Step: 10mV; Amplitude: 40mV; Frequency; 5 Hz). Findings of this research showed that the developed bismuth alloy microelectrode can be used for the detection of zinc without the need for pre-deposition or co-deposition of bismuth. A linear response (R=0.982) to zinc from 1 to 200 ppm Zn2+ was observed at -1.1 V under controlled conditions (deposition and stripping in 0.1 M acetate buffer at pH 4.5). When deposition and striping steps were separated, the linear range was only slightly decreased; but still with a good relationship. Overall, this research demonstrates the possibility of using a SWASV microsensor as a direct and rapid method for monitoring of Zn2+ concentration in phloem tissue in a minimally invasive way.
2:30 PM - BI02.02.03
Understanding the Uptake and Translocation of Zinc-Based Treatments in Citrus Plants to Combat Citrus Greening Disease
Mikhael Soliman 5 1 , Warren Edmunds 2 , Parthiban Rajasekaran 5 , Mikaeel Young 5 , Nicole Labbe 2 , Swadeshmukul Santra 5 1 3 , Laurene Tetard 5 1 4
5 Nanoscience Technology Center, University of Central Florida, Orlando, Florida, United States, 1 Materials Science and Engineering, University of Central Florida, Orlando, Florida, United States, 2 Center for Renewable Carbon, University of Tennessee, Knoxville, Knoxville, Tennessee, United States, 3 Chemistry, University of Central Florida, Orlando, Florida, United States, 4 Physics, University of Central Florida, Orlando, Florida, United States
Show AbstractCitrus Greening disease has devastated citrus crops in Florida and threatens to destroy groves in other regions of the United States, South America, and Asia for several years, No known effective disease management plan is available to date despite massive research and industrial interests in preventing infections and treat infected trees. With mostly failed efforts to manage the disease to save infected groves in the near or long term, growers are experiencing a severe decline in production and quality. Recently, two important criteria have been considered as a new attempt to tackle this disease: 1) the mode of action of the active used should differ from conventional Copper treatments to circumvent bacterial resistance, and 2) the treatment should be designed to interact with bacteria causing the greening directly in the phloem, where they prevent normal flow of plant resources (sugar, water, nutrients).
Here, we study the uptake and transport of different Zinc-based treatments in leaves and seedlings. Nanoparticles that are sufficiently small to cross the natural pores and membranes of the tree are designed to penetrate the vascular system and target bacteria inside the phloem. Whole seedling uptake assays are developed to compare root and foliar uptake of the formulations. The dynamic of treatment uptake and the distribution in the seedling at different time points is determined using a combination of analytical techniques. The presence of the treatment in the leaves is first established by obtaining the Raman signature of the leaf extract obtained from various regions of the seedling. Once the treatment uptake is confirmed, Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy and functional Atomic Force Microscopy are used to pinpoint the local regions of the tissues (cellular level) with high concentration of treatments and to identify potential variations in plant tissue properties. Lastly, X-ray Fluorescence Spectroscopy is carried out on the plant tissues in powder form to quantify the average Zinc content in different levels of the plants. Overall, the distribution of the treatment from plant to subcellular level is considered to inform potential refinement requirements of the formulation actives to increase the efficacy of disease management for greening.
3:15 PM - *BI02.02.04
A Nanoscale View of Plant Tissues and Their Response to External Stresses
Laurene Tetard 1
1 NanoScience Technology Center, University of Central Florida, Orlando, Florida, United States
Show AbstractThe emergence of applications of nanotechnologies into agriculture raises new questions with respect to the plant tissues and cells properties, as well as their evolution in presence of external stresses. To tackle these rather fundamental questions, a multiscale approach that eventually reaches high sensitivity and nanoscale spatial resolution is of great interest. Novel platforms involving functional atomic force microscopy (AFM), in particular those equipped with infrared spectroscopy (IR), may offer a paradigm shift in the field of plant science. The chemical maps with spatial resolution up to 10 nm recently reported shall be exploited to explore the variations in chemical content of plant cell walls both in their native states and in response to external stresses, including chemical treatments for deconstruction of the cell wall or for disease management.
In this talk, we will discuss promising approaches that are being developed to probe chemical, mechanical and structural properties of features and assemblies in the cell wall layers. To illustrate the potential of such technologies, we will present our findings of local variations in composition of plant cell walls treated with various solvents and chemicals. We will consider the current limitations and perspectives of such approach. In particular, we will highlight the importance of statistical tools to establish connections between the observations made at the nanoscale and at larger scales to better take into account the complexity of natural variations associated with plant systems for applications in pesticides and material design related to biorefinering lignocellulosic feedstock.
3:45 PM - *BI02.02.05
Scalable Manufacturing of Graphene-Based Biosensors for In-Field Fertilizer and Pesticide Sensing
Jonathan Claussen 1 , John Hondred 1 , Suprem Das 1 , Igor Medintz 2 , Joyce Breger 2 , Nathaniel Garland 1
1 , Iowa State University, Ames, Iowa, United States, 2 , U.S. Naval Research Laboratory, Washington, District of Columbia, United States
Show AbstractHigh resolution inkjet printed nanomaterials have shown tremendous promise towards the fabrication of low-cost, flexible electrical circuits. However, the utility of these inkjet printed nanomaterials have limited biosensing applications. This presentation demonstrates how the utility of inkjet printed graphene and biorecognition agents (e.g., enzymes and ionophores) can be converged to enable low-cost and sensitive in field monitoring of pesticides and fertilizer ions in soil samples. Inkjet printed graphene uses low-cost exfoliated graphene/graphene oxide flakes (in lieu of high-cost chemical vapor deposition synthesized graphene) to form carbon-based electrical circuits. Inkjet printed graphene applications have been constrained due in part to post-print annealing steps, low electrochemical reactivity, and relatively smooth, planar surfaces. In this work, we expand the utility of inkjet printed graphene by welding/stitching the printed graphene flakes and nanostructuring the flakes into 3D nanopetals via a pulsed laser annealing process. The laser processing and/or thermal annealing techniques change the electrically conductivity of the printed graphene from highly resistive (> 100 MΩ) to highly conductive (< 1 kΩ sheet resistance)—a conductivity higher than previously published reports; the hydrophobicity of the graphene from hydrophilic (water contact angle ~ 45°C) to superhydrophobic (water contact angle ~ 155°C); the graphene electrochemical reactivity from a surface with slow, irreversible charge transport to fast, reversible charge transport; and finally a graphene surface roughness that changes from 2D planer to 3D nano/microstructured with stitched/welded graphene flakes. We demonstrate how these improvements in material properties enable highly sensitive and selective ion selective electrodes and enzymatic biosensors for in-field fertilizer and pesticide sensing respectively in soil samples. We also demonstrate how the graphene can be printed and post processed on the microscale with 20 µm resolution via a scalable inkjet maskless lithography technique without the need for photolithograpy or stencil patterning. These results show significant promise for use in rapid, low-cost, and disposable biosensors for soil management in the farm field with potential use for biosensing applications that require low-cost, disposable/recyclable, and flexible electrodes.
4:15 PM - BI02.02.06
Application of Calixarene Grafted Magnetite Nanomaterials in Removal of Paraquat and Diquat Herbicides
Pratibha Kumari 1
1 , Deshbandhu College, University of Delhi, Delhi India
Show AbstractParaquat and diquat are the most widely used herbicides. They are quick-acting and non-selective, killing green plant tissue on contact. However, they are toxic to human beings and animals. Paraquat is linked to development of Parkinson's disease. If ingested, it can cause acute respiratory distress syndrome in humans. Diquat may also be fatal to humans if swallowed, inhaled, or absorbed through the skin in large quantities. The removal of these herbicides from water is a worldwide challenge. To address this problem, we synthesized water soluble sulphonated calix[n]arenes (n=4,6,8) derivatives and grafted them onto magnetite nanoparticles via covalent bonding. The adsorption studies of paraquat and diquat were carried out under different conditions such as different temperature, pH, dosage amount, and time of contact. Excellent results and highest extraction efficiency was observed with calix[8]arene modified magnetite nanoparticles
4:30 PM - BI02.02.07
Fertilizer Based on Nanocomposites Urea-Mineral Phosphates for Efficient Supply of Phosphorus in Acid Soils
Amanda Giroto 1 2 , Gelton Guimarães 2 , Caue Ribeiro de Oliveira 2
1 , Univ Federal-Sao Carlos, Sao Carlos Brazil, 2 LNNA, Embrapa Instrumentation, Sao Carlos, Sao Paulo, Brazil
Show AbstractThe interaction between urea and mineral phosphates has been used as a strategy to increase N and P supply efficiency, reduce losses and increase the availability of these nutrients in the soil. Thus, a new fertilizer (UrHap) based on nanoparticles of hydroxyapatite (Hap - the model source of mineral phosphates) dispersed in a urea matrix in the proportion 1:1 wt-1 was processed by an extrusion process. Through microscopy using a scanning electron microscope, it was possible to observe the formation of a homogeneous composite as confirmed by the X-ray microtomography analysis. A dense material, without the presence of pores, was formed by the dispersion of Hap particles in the matrix of Urea, without agglomerations. The dispersion of the particles was the key factor for the control of the release of phosphorus in solution or in the soil. In previous studies involving this same material, urea release retention was observed, followed by decreased NH3 volatilization and higher NH4+ retention in the soil. It can also be observed a rapid reduction of the P fraction in the soil extracted with Hap and MAP ( commercial fertilizer) resin after incorporation of the sources to the soil. This reduction can be attributed to the adsorption of P by the soil colloids. The Red-Yellow Oxisol used in the incubation has characteristics that are indicative of high adsorption of P in the soil, such as low pH, low available P concentration, low remaining P value and high potential acidity. In addition, the presence of Fe and Al oxides in the Red-Yellow Oxisol makes it more susceptible to P. adsorption. On the other hand, the UrHap composite presented a higher availability of P from the third week of incubation, with a decrease of adsorption of P to soil colloids compared to Hap and MAP. This result can be explained by the increase in soil pH around the particles provided by the hydrolysis of urea. Our results support the development of a new class of smart fertilizers, with release tailored by nanostructure.
Symposium Organizers
Swadeshmukul Santra, University of Central Florida
Michael Molinari, Universite de Reims Champagne Ardenne
Nicole Labbe, University of Tennessee
Loukas Petridis, Oak Ridge National Laboratory
BI02.03: Biomass Processing and Modeling
Session Chairs
Nicole Labbe
Loukas Petridis
Tuesday AM, November 28, 2017
Sheraton, 3rd Floor, Gardner AB
8:45 AM - *BI02.03.01
Real-Time SANS Visualization of Hierarchical Structural Changes During Thermochemical Reactions
Sai Venkatesh Pingali 1
1 , Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States
Show AbstractKnowledge of structural changes to biomass during pretreatment will enable an informed approach to improving biomass conversion efficiencies. We developed a pressure reaction cell to monitor morphological changes in biomass using small-angle neutron scattering (SANS) during thermochemical pretreatment in real-time. This approach takes advantage of the non-destructive and high penetration properties of neutrons to perform in-situ studies. Recently, we have extended the capabilities of the Bio-SANS instrument at the High Flux Isotope Reactor at Oak Ridge National Laboratory by installation of an additional detector array. The upgrade makes it possible to capture neutrons scattered at higher angles simultaneously to the neutrons captured at smaller scattering angles by the main detector. As a result, data collection times are dramatically reduced and it is possible to obtain structural information at much shorter length scales than was previously possible. Here, we report on real-time SANS studies of native poplar and variant that is deficient in lignin synthesis, during dilute acid and alkali pretreatments. We observe significant differences in lignin aggregation patterns in the native and mutant poplar comparing the two pretreatment regimes. On the other hand, the scattering signature assigned to the cellulose microfibrils remains relatively unchanged in both pretreatments. A quantitative analysis of the structural changes in the native and mutant plants will be presented. Using this approach, it is possible to obtain molecular level insights into structural rearrangements of biomass polymers during pretreatment to better understand the consequences of genetic mutations on the overall digestability of biomass.
http://www.ornl.gov/science-discovery/clean-energy/research-areas/systems-biology/bioenergy/dynamic-visualization-of-lignocellulose
9:15 AM - BI02.03.02
Co-Production of Cellulosic Nanocrystals and Biofuel Precursors with Cellulase Enzymes
Peter Ciesielski 1 , John Yarbrough 1 , Ruoran Zhang 1 , Yannick Bomble 1 , Stephen Decker 1 , Michael Himmel 1
1 , National Renewable Energy Lab, Golden, Colorado, United States
Show AbstractNanocellulose represents an emergent class of renewable nanobiomaterials with impressive properties and useful functionality for many applications including nanocomposites, green electronics, and biomedical. One form of nanocellulose, termed cellulose nanocrystals (CNCs) is produced by controlled hydrolysis of cellulosic feedstocks. While most CNC production methods have employed strong mineral acids, the use of cellulolytic enzymes enables the co-production of CNCs and monomeric sugars as precursors for biofuels and biochemicals. I will describe the capacity for coproduction of nanocellulose products and monomeric sugars of two vastly different cellulase systems: a classic “free enzyme” system of the saprophytic fungus, Trichoderma reesei (T. reesei) and the complexed, multifunctional enzymes produced by the bacterial system of Caldicellulosiruptor bescii (C. bescii). Comparative digestions reveal that the C. bescii system outperforms the fungal enzyme system in terms of total cellulose conversion, sugar production, and nanocellulose production. Surprisingly, we also find that that the nanocellulose produced by the C. bescii cellulase system is substantially more uniform than that produced by the T. reesei system as evidenced by multimodal imaging and dynamic light scattering. These disparities in the yields and characteristics of the nanocellulose produced by these two enzyme systems are attributed to the differences in the modality of hydrolysis performed by the dominant enzymes in each system.
9:30 AM - BI02.03.03
Multi-Scale Modeling of Materials Derived from Hydrothermal Processing of Biomass
Diego López Barreiro 1 , Francisco Martin-Martinez 1 , Markus Buehler 1
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Show AbstractHydrothermal processing (HTP) transforms any type of wet biomass into solid and liquid carbon-rich materials by applying high pressure and high temperature. This process takes advantage of the water present in the feedstock, while circumventing the highly energy-demanding process of drying the biomass. The carbon-rich materials produced by means of HTP can be used for several applications. This work focuses on the use of the liquid products for asphalt binder, while the solid products are tested for gas cleaning applications.
Experimental data has been used to develop a multi-scale model of solid and liquid HTP products, computing different conceptual Density functional theory (DFT) descriptors, i.e., Fukui Function and chemical hardness, to characterize the reactivity of representative molecules of those materials. Molecular dynamics (MD) simulations are also performed to understand the mechanisms governing the behavior of these materials under the aforementioned applications. In the case of asphalt binder, particular focus is placed on the aggregation patterns of diverse classes of molecules in biocrude oil. In the case of solid materials for gas cleaning applications, the effect of the different types of functionalities (pyrroles, pyridines, amines) is studied to understand how to maximize the CO2 capture by maximizing the chemical interaction of those groups with the CO2 molecules.
9:45 AM - BI02.03.04
Development Progress in Constructing Atomic Scale Models of Diverse Lignins
Josh Vermaas 1 , Loukas Petridis 2 , Gregg Beckham 1 , Michael Crowley 1
1 , National Renewable Energy Laboratory, Golden, Colorado, United States, 2 , Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States
Show AbstractLignin is a recalcitrant, aromatic heteropolymer, one of the 3 primary components of biomass. Lignin provides structure to plants, water and nutrient transport through plant tissues, and a highly effective defense against pathogens. As the largest reserve of aromatics in the biosphere, lignin has a great potential as a feedstock for industrial processes, if only if its native recalcitrance could be addressed. To better understand the origins of lignin’s recalcitrance, it is imperative to know its 3D structure as it relates to lignin composition and linkage. However, computational modeling all of lignin’s diversity to this point has been limited by the available lignin forcefields, which lack explicit parameterization for emerging lignin structures both from natural variants and engineered lignin structures. Since polymerization of lignin occurs via radical intermediates, multiple C-O and C-C linkages have been isolated, and the current force field only represents a small subset of lignin the diverse lignin structures found in plants.
In order to take into account the wide range of lignin polymerization chemistries, monomers and dimer combinations of C-, H-, G-, and S-lignins as well as with hydroxycinnamic acid linkages were subjected to extensive quantum mechanical calculations to establish target data from which to build a complete molecular mechanics force field tuned specifically for diverse lignins. By parameterizing lignin specifically, we are able to more accurately represent the interactions and conformations of lignin monomers and dimers relative to a general force field. Coupled with structure building advances also presented, this new force field will enables computational researchers to study the effects of different linkages on the structure of lignin, as well as construct more accurate plant cell wall models based on observed statistical distributions of lignin that differ between disparate feedstocks, and guide further lignin engineering efforts.
BI02.04: Cellulosic and Lignocellulosic Materials
Session Chairs
Nicole Labbe
Michael Molinari
Tuesday PM, November 28, 2017
Sheraton, 3rd Floor, Gardner AB
10:30 AM - *BI02.04.01
Lignocellulosic Bioinspired Assemblies as Templates for Characterizing Plant Cell Walls and Designing Nano-Biocomposite Materials
Brigitte Chabbert 1 2 , Michael Molinari 3 , Véronique Aguié-Béghin 1 2
1 , INRA, Reims France, 2 , University of Reims Champagne Ardenne, Reims France, 3 Laboratoire de Recherches en Nanosciences, University of Reims Champagne Ardenne, Reims France
Show AbstractLignocellulosic bioinspired assemblies as templates for characterizing plant cell walls and designing nano-biocomposite materialsChabbert B
a, Molinari M
b, Aguié-Béghin V
aaFARE laboratory, INRA, UMR614 Fractionnement des AgroRessources et Environnement,
F-51100 Reims, France
bLaboratoire de Recherches en Nanosciences,University of Reims-Chamapgne Ardenne, F-51100 Reims, France
[email protected]Lignocellulosic biomass (LB) represent abundant and renewable resources and a sustainable alternative to fossil carbon. LB is composed of various polymers such as cellulose, hemicellulose and lignin. These polymers are interconnected through a variety of covalent and noncovalent interactions in plant cell walls thus forming a highly complex organized network that vary according to plant species and development, and growing conditions. Such an organization plays a key role in plants growth, mechanical properties, and biological recalcitrance but can be a bottleneck to the development of sustainable and cost-efficient biorefineries.
Given the increasing interest in LB it has become critical to characterize LB architecture at multiscale levels and to understand structural parameters that control the LB properties and its susceptibility to transformation into chemicals, materials and biofuels. Notably, understanding the effect of the interactions between individual polymers on the cell wall structure and subsequent impact on the their properties is still challenging considering the hierarchical organization of the lignified cell walls. In this context, bioinspired systems based on lignocellulosic polymers can be a valuable tool to adress the role of interactions between cell wall polymers in plant cell walls properties and to provide rationale for designing lignin-based nanomaterials.
11:00 AM - BI02.04.02
Quality and Biorenewable Carbon Fiber from Fractionated Lignin
Qiang Li 1 , Shangxian Xie 1 , Wilson Serem 1 , Joshua Yuan 1
1 , Texas A&M University, College Station, Texas, United States
Show AbstractCarbon fiber is a lightweight material with excellent mechanical properties and broad applications in a variety of industries, such as automotive, sports equipments, wind turbine blade, and aerospace. Traditionally, commercial carbon fibers are mostly made of polyacrylonitrile (PAN), yet the major limitation for carbon fiber applications is the high cost of PAN, which is at ~$15/lb and accounts for more than 50 % of carbon fiber production cost. Currently, a good candidate to displace PAN as a cheap carbon fiber precursor is lignin. Lignin is not only bio-renewable, abundant, and low-cost as a biorefinery waste, but also a unique biopolymer with high carbon content (up to 60%) and aromatic moieties. However, the application of lignin carbon fiber in composite is still unrealistic due to the low mechanical performance, introduced by the high heterogeneity and structural complexity of lignin. In this research, we hereby address this challenge by developing a new biological approach to fractionate and modify lignin to produce quality carbon fibers. A laccase-mediator system and dialysis method have been designed to fractionate lignin with different molecular weights, and to modify lignin functional groups and interunitery linkages. The fractionated high molecular weight lignin in general improves the miscibility and spinnability of lignin. The mechanical test surprised us that carbon fiber made of this lignin fraction showed the same elastic modulus to pure PAN based carbon fiber. Lignin structural characterization revealed that lignin functional groups and interunitary linkages are critical for a pre-graphitic turbostratic carbon structure in carbon fiber, which significantly improved the crystallization and mechanical performance of lignin carbon fiber. Moreover, we found that both molecular weight and molecular uniformity (polydispersity index) could affect the elastic modulus of lignin-based carbon fiber; in particular, the elastic modulus has linear correlation with molecular uniformity. On the other side, although the fractionated low molecular weight lignin fraction was found not to be suitable for carbon fiber, it can be used as a superior asphalt binder modifier. Both high and low temperature performances of asphalt binder were improved by adding the low molecular lignin fraction. The carbon fiber and asphalt binder thereby enabled a multi-stream integrated biorefinery towards multiple high-value bioproducts. This research is the first to use biological system to tailor lignin and the first in addressing the effects of lignin structure and molecular uniformity on lignin-based carbon fiber mechanical strength. This technical breakthrough produces lignin-based carbon fiber with similar elastic modulus to pure PAN carbon fiber, and could guide the development of lignin processing for quality carbon fibers to serve as bio-renewable and cost-effective alternative for the present petroleum-based carbon fiber.
11:15 AM - BI02.04.03
Lignin Based Thermally Conductive Materials for 3D-Printing Applications
Ngoc Nguyen 1 , Sietske H. Barnes 1 , Kelly M. Meek 1 , Jong Keum 2 , Amit Naskar 1
1 Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States, 2 Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States
Show AbstractPolymers are the most widely-used materials in electronic packaging. Thermal dissipation of electronic devices plays a decisive role in the electronic packaging. However, the thermal conductivity window of these materials is very narrow. In this study, we employed lignins as a polymer domain to develop novel functional 3D-printing materials: green, cheap, and thermally-conductive lignin-carbon fiber based composites. Lignins are renewable materials having limited uses due to their naturally complicated structures. Herein, the determined structures of these investigated lignins revealed highly heterogeneous and branching aromatic functional units exhibiting rigid structures with less flexible macromolecular chains causing difficulties for melt-processing. We introduced a polymer as a lubricant phase to improve the lignin macromolecular mobility, thus flow characteristics. Loading of lignin composites indicated favorable 3D-printing characteristics. The measured electron-microscopy and small angle neutron scattering data indicated the formation of phase separation within the composites. The effects of two selected lignins’ molecular structure on the composites’ properties and their corresponding printability will be discussed.
11:30 AM - BI02.04.04
Single Molecule Force Spectroscopy as a Tool to Analyze Intermolecular Interactions between Lignocellulosic Polymers for Agromaterial Applications
Carlos Marcuello 1 2 , Brigitte Chabbert 1 , Michael Molinari 2 , Véronique Aguié-Béghin 1
1 , Institute National de la Recherche Agronomique (INRA), Reims France, 2 , Laboratoire de Recherche en Nanosciences (LRN), Reims France
Show AbstractAt the present, there is a global demand for societies that are more environmentally friendly, relying less on fossil resources. In this regard, lignocellulose biomass provides a panoply of excellent opportunities for refineries to produce biomolecules, agromaterials or bioenergy [1]. Among them, lignocellulosic polymers are a potential target to be analysed due its applications in food packaging, bionanocomposites or new biosensors with specific polymer-polymer interactions for biomedical applications. For example, cellulose nanocrystals (CNCs) are used in novel nanomaterials with high added-value. The external coverage of hydroxyl groups is an interesting target to be chemically modified and thus, exerting their function as scaffold for polymer nanocomposites. Lignin is a constituent of cell walls being the biomass source with an aromatic functionality. This aspect allows lignin to be a bio-based alternative to the use of fossil fuels. Although huge volume of research has been carried out in this area [2], the interaction between lignocellulosic polymers is poorly understood at molecular levels. Atomic Force Microscopy (AFM) is being established as a versatile tool to address the morphology and properties of biological systems. Additionally, Single Molecule Force Spectroscopy (SMFS) measures the interaction forces between both biopolymers attached on flat substrate and cantilever, respectively. Due to it, AFM becomes an attractive technique to reveal the adhesion properties of different materials at nanoscale level.
It exists a lack of information of the intermolecular forces between those polymers (cellulose, lignin and hemicellulose). For this purpose, cohesion forces not only for several substrates were determined (CNCs, glucomannan, xylan, lignin and then, several combinations of them in different ratios), but also obtained by different techniques (Langmuir-Blodgett, casting or spin coating) using functionalized AFM levers with CNCs or lignin. The functionalization strategy is novel and we expect the present protocol opens new gates in the bioconjugation field. Relevant parameters such as loading rate, tip-sample interaction time and relative humidity were analyzed. The understanding gained will promote more efficiently the properties control of high added-value biobased products. Thus, the main aim of the present work is to increase the knowledge of intermolecular forces govern lignocellulosic polymers based systems. We expect our methodologies will substantially aid in the understanding of this topic.
[1] Aguié V, Paës G, Chabbert B, Molinari M. (2016). “Films and Coatings from Lignocellulosic Polymers”. Chapter 8. Edible Films and Coatings: Fundamentals and Applications. M.P Montero, M.C Gomez-Guillen, M.E Lopez-Caballero, G.V. Barbosa-Canovas. Eds. CRC.
[2] Moon R.J, Martini A, Nairn J, Simonsen J, Youngblood J. (2011). “Cellulose nanomaterials review: structure, properties and nanocomposites”. Chem. Soc. Rev. 40, 3941-3994.
11:45 AM - BI02.04.05
Study of the Hydrophobic and Mechanical Properties of Cellulose from Soybean Hulls and Paper Fiber Based on Kraft Type Cellulose
Oxana Kharissova 1 , Blanca Montes Mejia 1
1 , UANL, Monterrey Mexico
Show AbstractHusk soy is a byproduct of the process of obtaining soybean oil which contains about 40% fiber in order to develop polymeric materials with applications in the paper industry. In this research, the results for the production of micro and nanocellulose from soy husk by ultrasound treatment are presented, using methods of alkaline treatment applying basic solution (NaOH 10% w/w) and breeding method acid using acidic solution of HNO3 at 65% w/w, washing, filtering and drying. This research refers to the hydrophobic elements for the coating of materials with the use of nanotechnology, in this case specific for the production of a hydrophobic paper based on Kraft cellulose fibers containing SiO2 silicon oxide nanoparticles linked in size 20 nm, resulting in an increase up to 86% in its mechanical properties, avoiding the absorption of moisture in the paper, forming water contact angles of 120° to 150°. The obtained samples were characterized and analyzed by contact angle, infrared spectroscopy (IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM). The offered method has a potential capacity to replace the cellulose from trees and reducing their use thus contributing to the environmental impact.
BI02.05: Crop Protection and Food Safety
Session Chairs
Philip Demokritou
Swadeshmukul Santra
Tuesday PM, November 28, 2017
Sheraton, 3rd Floor, Gardner AB
1:30 PM - *BI02.05.01
Silk Fibroin-Based Edible Coatings to Control Crops’ Post-Harvest Physiology
Benedetto Marelli 1 , Fiorenzo Omenetto 2
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States, 2 Biomedical Engineering, Tufts University, Medford, Massachusetts, United States
Show AbstractThe reinvention of structural biopolymers into technical materials has enabled the design of biomedical and optoelectronics devices with unique and compelling properties that can serve at the interface between the biotic and the abiotic worlds. For example, we have previously shown the use of silk fibroin bioinks as detector for E.coli contamination to enhance food security. Silk fibroin, in fact, is an edible and biodegradable protein extracted from
B. mori cocoons that can be engineered in several formats ranging from films to particles, foams and gels. By exploiting silk fibroin essential properties (i.e. polymorphism, conformability and hydrophobicity) it is possible to design a water-based protein suspension that self-assembles in nano- to micro-meter thick membranes upon dip coating. The so formed thin films modulate mass transport (e.g. O
2 and CO
2 diffusion and water vapor permeability). This is possible by controlling protein polymorphism (i.e. formation of random or beta-sheet structures) during and post material assembly. Here, we show how silk materials can be used as an edible coating to preserve food freshness and mitigate spoilage. In particular, silk fibroin coatings with an increased beta-sheet content decrease O
2 and CO
2 diffusion in crops, effectively reducing oxidative stresses and cell metabolism. The control of silk fibroin polymorphism also allows to reduce loss of weight due to dehydration in several crops, including cassava roots, grapes, berries, bananas and tomatoes. The water-based processing and edible nature of silk fibroin makes this approach a promising alternative for food preservation with a naturally derived material. In the context of this presentation, we will also compare silk fibroin coatings with other natural alternatives as shellac, chitosan and zein based coatings.
* Benedetto Marelli
Paul M. Cook Career Development Assistant Professor
Laboratory for Advanced Biopolymers (L.A.B.)
Department of Civil and Environmental Engineering
Massachusetts Institute of Technology
77 Massachusetts Avenue, Room 1-348, Cambridge, MA, 02139-4307, USA
Email:
[email protected]Website: https://www.marelli.mit.edu
2:00 PM - BI02.05.02
Aptamer Based Biosensors for Real-Time Detection of Foodborne Pathogens Using pH-Responsive Polymer Nanobrushes and Platinum Nanoparticles Platforms
Suleiman Althawab 1 , Daniela Oliveira 1 , Lucas Rua 1 , Nicholas Cavallaro 3 , Eric McLamore 3 , Carmen Gomes 1 2
1 Biological and Agricultural Engineering, Texas A&M University, College Station, Texas, United States, 3 Agricultural and Biological Engineering , University of Florida, Gainesville, Florida, United States, 2 Mechanical Engineering, Iowa State University, Ames, Iowa, United States
Show AbstractTo meet the need of supplying fresh, high quality, and safe food to a growing world population, rapid and sensitive monitoring techniques are needed which can determine foodborne pathogen presence. Conventional methods for detecting foodborne pathogens are time-consuming and required highly trained personnel and certified laboratories. Recent recalls related to Listeria monocytogenes contamination highlight the importance of rapid tools that could be used to monitor pathogens such as Listeria. Therefore, a highly sensitive and easy to use biosensor as a rapid detection method for foodborne pathogen is required to ensure food safety and public health. The objective of this project was to design electrochemical biosensors based on the combination of platinum nanoparticles (n-Pt), pH-responsive polymer nanobrushes including, chitosan (CHI), alginate (ALG) and polyacrylic acid (PAA)), and aptamers for improved detection of L. monocytogenes. n-Pt was deposited on electrodes using a pulsed sonoelectrodeposition (pulSED) method, which increased (P < 0.05) the electroactive surface area (ESA) from 0.018 ± 0.0004 cm2 to 0.0807 ± 0.0179 cm2. Then, pH-responsive polymer brushes were electrodeposited onto the n-Pt. The optimized nanobrushes deposition increased (P<0.05) ESA to 0.101 ± 0.004 cm2, 0.111 ± 0.012 cm2, and 0.108 ± 0.022 cm2 for CHI, ALG and PAA/n-Pt modified electrodes, respectively. Aptamers selective to L. monocytogenes were loaded onto the nanobrushes at 1000 nM, 400 nM, and 800 nM for CHI/n-Pt, PAA/n-Pt, and ALG/n-Pt electrodes, respectively. Loading aptamers onto the pH-responsive nanobrushes improved (P < 0.05) the biosensors performance, as they were actuated to extend during the bacteria capturing step and contract during the sensing process. The developed biosensors were tested in buffer and a food matrix against another gram-positive bacteria (Staphylococcus aureus) and showed a wide detection range of 101-108 CFU/mL of L. monocytogenes in 17 min. The 1000-nM-aptamer/CHI/n-Pt biosensors provided the lowest average of limits of detection (LODs), 1.37 ± 1.50 CFU/mL with a sensitivity of 7.27 ± 1.10 (1/log(CFU/mL)) based on charge transfer resistance (Rct) changes. Conversely, the 400-nM-aptamer/ALG/n-Pt biosensors provided the most consistent results with LODs of 6.10 ± 1.95 CFU/mL and sensitivity of 5.97 ± 0.90 (1/log(CFU/mL)) based on Rct data, respectively. The combination of aptamers and pH-responsive nanobrushes on n-Pt provided enhanced sensing performance over other published biosensors, covering the relevant levels for food safety analysis, without requiring addition of reagents or sample pre-incubation.
2:15 PM - BI02.05.03
Absorption of Ethylene on Membranes Containing Potassium Permanganate Loaded into Nanofibers of Alumina or Carbon with Alumina Nanoparticles
Ashkan Tirgar 1 , Daewoo Han 1 , Andrew Steckl 1
1 Nanoelectronics Laboratory, Electrical Engineering and Computing Systems, University of Cincinnati, Cincinnati, Ohio, United States
Show AbstractPremature ripening of fruit and flowers during packing, transport and storage results in significant wastage and costs, especially for high value products. The ripening is caused by ethylene (C2H4), which is emitted by certain climacteric or non-climacteric1 fruits and it affects others nearby. A widely-used method is to utilize oxidants containing permanganate ions, such as potassium permanganate (PPM), loaded on inorganic carriers, to neutralize the ethylene produced from fruits.2 Alumina (Al2O3) has been used for this purpose only in the form of small porous beads that accommodate PPM on their large surface area. Because alumina beads are not self-standing, they cannot be used as a packing material and require to be contained in individual pouches.
We report on the fabrication of electrospun membrane carriers for PPM and show the effectivity in absorbing ethylene. PPM is a strong oxidizing agent and cannot remain active on organic membranes. Hence, we fabricated inorganic fibers using alumina nanofibers (ANF) and carbon nanofibers (CNF), and developed absorber fiber membranes that can be used to control atmospheric ethylene level. Moreover, we incorporated alumina nanoparticles (ANPs) into ANFs using blend electrospinning and improved the efficiency of the ANF carrier.
Electrospinning is a versatile technique for fabrication of light and flexible free-standing fibrous membranes made of a wide range of polymers. The diameter of fibers produced using electrospinning ranges from 10s of nanometers to µm’s depending on solution viscosity, conductivity, etc.
The results demonstrate improved ethylene absorption kinetics from fiber membranes compared to alumina beads. ANP incorporated ANFs and CNFs, and alumina NFs presented ethylene concentration drop of 58%, 40%, and 27% in 13 min with initial reaction rate of 5.1, 1.4, and 2.2 ppm/min, respectively, while alumina beads presented with only 17% drop with the rate of 5.2 ppm/min. In particular, ANP incorporated ANFs presented the highest initial absorption followed by gradual absorption of ethylene. Further, fiber membranes have the advantage of flexibility and ease of handling that make them ideal for being used inside packaging materials. We also investigated the relationship between the amount of ANPs in CNF membranes and the ethylene absorption kinetics. The weight ratio of 2.5:1 provided the highest absorption ~ 40% while other weight ratios of 0.5:1 and 4.7:1 only provided 4% and 35%, respectively. This indicates that the absorption kinetics of our membranes can be tuned by varying the weight ratio between ANPs and inorganic fiber material (carbon or alumina). This property can be exploited to match the ethylene absorption rate by membranes to the rate of ethylene release from a fruit of interest.
1. Chervin, C., A. El-Kereamy, J.-P. Roustan, A. Latché, J. Lamon and M. Bouzayen, Plant Sci. 167 (2004): 1301-1305.
2. Wills, R. B. H., and M. A. Warton, J. Am. Soc. Hortic. Sci. 129 (2004): 433-438.
3:15 PM - *BI02.05.05
An Antimicrobial Targeted and Precision Delivery Platform Using Engineered Water Nanostructures (EWNS) for Food Safety Applications
Nachiket Vaze 1 , Georgios Pyrgiotakis 1 , Mary Eleftheriadou 1 , Philip Demokritou 1
1 Center for Nanotechnology and Nanotoxicology, Harvard University, T.H. Chan School of Public Health, Boston, Massachusetts, United States
Show AbstractFood must be appealing and nutritious to the consumer, but it must also be safe. The constant occurrence of foodborne disease is a major public health problem, worldwide. WHO estimates that 600 million people get sick and 420,000 die every year from contaminated food. In addition to safety, microbial food contaminants bring about food spoilage contributing to food waste, a big problem in the modern world. Further, in recent years, consumers are driving the market towards healthier food choices, consuming more fruits and vegetables, demanding green approaches to food production, minimal processing, organic produce and the use of less chemicals. Food produced under these conditions can be, however, of higher microbiological risk. To this end, traditional thermal and chemical approaches to food safety assurance must be replaced or supplemented with new, more efficient ones, which can provide the level of safety, required across the farm to the fork continuum in a more sustainable way. In this study, a ‘dry’ nanotechnology-based platform was developed and utilized for the targeted and precision delivery of various antimicrobial agents for the reduction of microbial foodborne contaminants on the surface of fresh produce (berries). This emerging method utilizes Engineered Water Nanostructures (EWNS), synthesized by combining electrospraying and ionization of an aqueous solution of any antimicrobial active ingredient (AI). It was shown that EWNS nanoparticles possess unique physico-chemical properties, have extensive surface per mass, are highly mobile due to their nanoscale size and can interact with microorganisms on the food surface, delivering the encapsulated active ingredient and reactive oxygen species (ROS), bringing about inactivation. What is interesting is that the food surface, treated by these EWNS, stays dry due to the minute quantities of AIs delivered (nanograms). As a result, sensory characteristics of the produce are not affected while the method maintains a green approach. Antimicrobials used in this study include H2O2, ROS generated by the electrolysis of deionized water and citric acid. The results demonstrate the precision and efficacy of the method in terms of delivery in a targeted way of the active ingredient taking advantage of the electric charge of the EWNS. For example in the case of 1% w/v of H2O2, there was a 5 log reduction in the concentration of E. coli inoculated onto stainless steel coupons just after 5 minutes of treatment, whereas the actual dose of H2O2 delivered to the E. coli was in the orders of picograms. These breakthrough results are pointing to a game changing platform, a disinfection method that is safer for products, consumers and the environment, with potential applications at a number of critical control points across the farm-to-fork chain; mainly post-harvest, to reduce microbial food contaminants with significant public health and economic outcomes.
3:45 PM - BI02.05.06
Bacteria-Repellent Self-Cleaning Food-Contact Surfaces for Improved Food Safety
Jun Kyun Oh 1 , Luis Cisneros-Zevallos 1 , Mustafa Akbulut 1
1 , Texas A&M University, College Station, Texas, United States
Show AbstractIn the context of food safety, contamination of food-contact surfaces with pathogenic bacteria is a global concern. Exogenous cross-contamination is one of the main mechanisms contributing to such infections. In this study, we report a surface modification approach involving “fluorinated silica nanoparticles” (FSNs) to improve the protective ability against bacterial contamination of common metal food-contact surfaces (i.e., aluminum and steel) and disposable glove surfaces (i.e., latex, nitrile, and polyethylene). The bacterial antiadhesive properties of the modified surfaces were evaluated with Salmonella Typhimurium LT2 and Staphylococcus aureus at bacterial concentrations of 8.6-9.0 log CFU/mL through the dip-inoculation approach. Bacterial attachment to food-contact surfaces were enumerated by the pour plating method as well as direct counting via scanning electron microscopy. The bacterial populations of S. Typhimurium LT2 and S. aureus on FSN-coated surfaces was reduced by 1-2 log units in comparison to bare surfaces, which already reduce the bacterial attachment to some extent. These results suggest that the use of FSN-coated surfaces that come into contact with bacterial pathogens in the food systems can improve bacterial hygiene, and therefore may reduce the rate of foodborne diseases.
4:00 PM - BI02.05.07
Non-Natural DNA Barcodes Encapsulated with Silica Nanoparticles as Track&Trace Tools in Food Technologies
Robert Grass 1 , Wendelin Stark 1 , Michela Puddu 1 , Daniela Paunescu 1
1 , ETH Zurich, Zurich Switzerland
Show AbstractDNA barcoding is an established technology in food sciences, by which the natural (genetic) DNA sequence of the food product is utilized to gain insights of the natural origin of the product (e.g. discriminating yellow-fin tuna from other tuna species). Due to the limited amount of discriminating features in natural DNA, only very well defined differences can be identified. There is, however, a current need to further understand the value chain of food products (from farm to fork) and a resulting need for novel tracer technologies for the tagging of food products.
As such food tracers should be absolutely non-toxic, it is only possible to utilize additives, which are already used/present within food products. Using DNA with non-natural sequences (or nature expired sequences) would be a logic choice and would extend the scope of the basic DNA barcoding technology. However outside of a cellular organism, DNA is prone to enzymatic degradation by nucleases and has to be appropriately protected to guarantee adequate barcode read-out throughout the life cycle of the food products. For this reason we have developed a technology for the encapsulation of DNA within silica nanoparticles (1), which by themselves are also already approved as a food additive (E551 in European food additive regulation). In this system, short (ca. 100 basepair) non-natural DNA barcodes are encapsulated within silicate glass using sol-gel chemistry forming nanoparticles of ~100 nm diameter and DNA loadings between 0.1 and 1 wt% (2). Within these encapsulates the DNA molecules are protected from enzymatic and hydrolytic cleavage under a wide range of environmental storage conditions.
In first studies, we show that such artificial DNA barcode tracers can be utilized to trace the origin of milk derived products (cheese and yogurt) (3), as well as extra virgin olive oil (4) at tracer loadings below 10 µg / kg. We have also shown that this barcoding technology can be extended for the application of pesticide tracing in an agricultural field setting and we will discuss the next steps and hurdles in implementing this technology on the market.
(1) Paunescu et al. Powder Technol. 291, 344 (2016)
(2) Paunescu et al. Nat. Protoc. 8, 2440 (2013)
(3) Bloch et al. J. Agric. Food. Chem. 62, 10615 (2014)
(4) Puddu et al. ACS Nano 8, 2677 (2014)
(5) Mora et al. ES&T Lett. 3, 19 (2016)
4:15 PM - BI02.05.08
The Supercapacitor Performance Evaluation of Modified Tungsten Oxide-Based Nanostructures and Their Biosensing Applications
Pankaj Kumar 1 , Prashant Sarswat 1 , Michael Free 1
1 , Univ of Utah, Salt Lake City, Utah, United States
Show AbstractNanostructured WOx has attracted significant attention for electrochemical supercapacitor applications due to high rate capability and excellent capacitance. In recent years, different structures of tungsten oxide or their 2-D integrated structure with other functional nanomaterials or layer modifications to core structure have been examined to improve the electrochemical performance. In order to investigate the effect of surface modifications on the electrochemical capacitance behavior of nanostructured tungsten oxide, the layered structure of functional materials over nanorods of tungsten oxide was prepared and systematically studied using three electrode electrochemical measurements. The end goal of surface modifications was to improve the adhesion or robustness of WO3 grown over the tungsten substrate, apart from any improvement in supercapacitor performance. These WO3 based sensors were utilized for biosensing and safety applications based on electrochemical detection of the hazardous chemicals in the food. The systematic electrochemical behavior for each model organic compound can be utilized to quantitatively characterize the quality of food to facilitate distinguishing between healthy (clean) and unhealthy (contaminated) food.
4:30 PM - *BI02.05.09
Nanosensors for Onsite Detection of Citrus Greening Disease (Huanglongbing)
Thien-Toan Tran 1 , Hui Wang 5 , Pankaj Ramnani 2 , Tung Pham 2 , Claudia Villarreal 3 , Kelley Clark 4 , Gang Liu 5 , Wenbo Ma 4 , Ashok Mulchandani 2 3
1 Department of Bioengineering, University of California, Riverside, Riverside, California, United States, 5 Key Laboratory of Modern Precision Agriculture System Integration Research, Ministry of Education and Key Laboratory of Agricultural Information Acquisition Technology, Ministry of Agriculture, China Agricultural University, Beijing China, 2 Department of Chemical and Environmental Engineering, University of California, Riverside, Riverside, California, United States, 3 Materials Science and Engineering Program, University of California, Riverside, Riverside, California, United States, 4 Department of Plant Pathology and Micribiology, University of California, Riverside, Riverside, California, United States
Show AbstractCitrus greening disease, also known as Huanglongbing (HLB), is posing a worldwide threat to the multi-billion dollars citrus industry. Containment of the disease is heavily dependent on early detection of infected hosts for quarantine. One of the major pathogens responsible is the bacteria Candidatus Liberibacter asiaticus (CLas). Current methods for detection of HLB are based on qualitative assessment of disease symptoms and nucleic acid assays which are susceptible to error and inaccuracies and suffer from lack of portability and ease-of-use making them unsuitable for onsite applications due to variable latent time and sporadic distribution of the pathogens in infected plants.
We report two nanosensors for the rapid, facile, low cost onsite detection of HLB infection in citrus. In the first sensor, we detect the signature blend of volatile organic carbons released by the infected plant. The sensor consists of single-walled carbon nanotubes (SWNTs) non-covalently functionalized with metalloporphyrins (MPs). The adsorption of the VOCs on the sensor causes change in the electrical properties of carbon nanotubes. By monitoring the change in device resistance as a function of VOC concentration, combined with enhancement of selectivity achieved by using different central metal ions in MPs, we can selectively detect low concentrations of VOCs in a simple, cost-effective manner. We report the detection of the five most discriminating VOCs associated with the asymptomatic stage of HLB including tetradecene, linalool, nonadecane, phenylacetaldehyde and ethylhexanol.
In the second sensor we detect an antigen secreted by the bacteria pathogen in the tissue phloem. This sensor uses semiconducting single-walled carbon nanotubes (sSWNTs) functionalize with antibodies specific to the secreted antigen. Antigen-antibody binding at the surface of sSWNTs lead to changes in the local electrostatic environment and consequently leads to proportionate modulation of electrical resistance of the nanomaterials and the sensing device. The immunosensor was successfully applied to detect HLB biomarkers at nanomolar concentration with high selectivity against other biological compounds in phloem extract of different citrus trees.
BI02.06: Poster Session
Session Chairs
Wednesday AM, November 29, 2017
Hynes, Level 1, Hall B
8:00 PM - BI02.06.02
Green Synthesis of Silver Nanoparticles Using a Melissa Officinalis Leaf Extract with Antibacterial Properties
Alvaro de Jesús Baltazar 1 , Ramiro Pérez 1
1 Nanotechnology, Universidad Nacional Autónoma de México, Querétaro, Querétaro, Mexico
Show AbstractIn this investigation, silver nanoparticles were obtained by green synthesis route. Melissa officinalis leaf extract was employed to reduce the silver ions in aqueous solution. A simple an efficient methodology at room temperature is presented. Also, the antibacterial activity of the silver nanoparticles against Staphylococcus aureus and Escherichia coli was confirmed. The silver nanoparticles were characterized by scanning electron microscopy, X-ray diffraction, UV-vis, and FT-IR spectroscopy.
Keywords
Green synthesis, Nanoparticles and Antibacterial effect
8:00 PM - BI02.06.03
Thermal and Magnetic Field Path Dependence of Large Magnetoresistance and Magnetocaloric Effect in Off-Stoichiometric Ni45Mn44Sn11 Heusler Alloy
Tanmay Chabri 1 , Venimadhav Adyam 1 , Tapan Nath 1
1 , Indian Institute of Technology Kharagpur, Kharagpur India
Show AbstractIn the recent years ferromagnetic shape-memory alloys (FSMAs) with a coupled magneto-structural first order phase transition have attracted a lot of interest due to the presence of latent heat of the structural transformation. In these alloys metastable states are formed due to the competition between thermal and magnetic energies. The strong coupling between the magnetism and structure in these kinds of materials results an entropy change when magnetic field is applied. The first order martensitic transition (MT) has been observed through magnetization and electronic- and magneto-transport measurements in Ni45Mn44Sn11 disordered Heusler alloy. The sharp change of magnetization from ferromagnetic austenite phase (AP) to weak magnetic martensitic phase (MP) in the vicinity of MT leads to both large magnetic entropy change and negative magnetoresistance (MR). The alloy also shows a second order ferromagnetic (FM) to paramagnetic (PM) phase transition above MT. The maximum magnetic entropy change at 275 K for the application of 5 T magnetic field are 24 Jkg-1K-1 and 15 Jkg-1K-1, estimated from field decreasing M-H protocol and field increasing M-H protocol, respectively. The maximum MR of -16 % and -43% for the field change of 8 T is observed at 275 K, when the temperature is reached by cooling from 320 K and by warming from 150 K, respectively. The difference in AP and MP phase fractions, originated from different thermal path and magnetic field path, is the most possible reason to observe different values of entropy change and MR in Ni45Mn44Sn11 Huesler alloy. First order MT in Ni45Mn44Sn11 also shows field induced effect. The field induced MT has been confirmed from the magnetic measurements and electronic transport measurements under high magnetic field. Arrest of AP in the MP by the application of magnetic field has been observed from both magnetization and electronic transport behaviors. It is also clearly seen that tuning of metastability due to the coexistence of AP and MP can be done by external parameters like magnetic field and temperature.
8:00 PM - BI02.06.04
Evaluating the Diffusion and Translocation of Antibacterial Treatment in Plant Systems with Infrared Spectroscopy
Nicholas Ciaffone 1 , Briana Lee 1 , Laurene Tetard 1
1 , University of Central Florida, Orlando, Florida, United States
Show AbstractBacterial diseases in plants can decimate groves and plantations by rapidly reducing production yields. An endemic infection can have devastating economic consequences at large, as seen in Florida due to Huanglongbing (HLB) – or citrus greening disease. HLB is a phloem-restricted bacterial infection spread by Asian Citrus Psyllids (ACPs) as they feed from the leaves phloem. The presence of the bacteria in the plant can affect the natural delivery of nutrients by clogging the vascular system, leading to early fruit drop with poor juice quality. With decimated groves and low fruit yield, the multibillion dollar citrus industry is facing severe economic hardship.
All disease management methods considered to date have failed to stop the progression of the disease or to improve the health of infected trees. Hence, based on their previous success in the treatment of fireblight disease in apple and pear trees, antibiotics including streptomycin and oxytetracycline combined with adjuvants are currently being evaluated. Their diffusion and translocation in Valencia Orange trees (Citrus sinensis) is the focus on this work. To model the processes, single leaf and seedling assays and whole plant spray simulations have been designed to quantify the uptake and translocation rate. We present results showing that Raman spectroscopy can be used to evaluate the presence of Streptomycin based on its fingerprint in the 900-1600 cm-1 range. We discuss important considerations including the protocols developed to ensure that surface residues are removed during the cleaning process to avoid interferences with the measurements on leaf sections. Finally, we consider the time evolution of the diffusion and translocation processes in the presence of adjuvants in the treatment. Overall, our results present a multi-scale approach to map pesticide-plant interactions at the tissue level.
8:00 PM - BI02.06.05
g-C3N4/Nb2O5 Heterostructures Tailored by Sonochemical Synthesis—Enhanced Photocatalytic Performance in Degradation of Emerging Pollutants Driven by Visible Radiation
Gelson Tiago da Silva 1 3 , Kele Carvalho 3 , Osmando Lopes 2 3 , Caue Ribeiro 3
1 Department of Chemistry, Federal University of São Carlos, São Carlos, São Paulo, Brazil, 3 , Brazilian Agricultural Research Corporation/Embrapa Instrumentation , São Carlos, São Paulo, Brazil, 2 Department of Chemistry, Institute of Chemistry of São Carlos, São Carlos, São Paulo, Brazil
Show AbstractThe presence of organic contaminants such as pesticides, pharmaceuticals, and dyes in rivers and lakes, even at low concentrations, can seriously affect human health and the environment1. There is therefore a need for the development of efficient treatment technologies for the removal of these compounds from wastewater. Advanced oxidation processes (AOPs) such as heterogeneous photocatalysis have attracted great interest for this purpose, especially using semiconductors that can be actived under visible irradiation. Graphitic carbon nitride (g-C3N4) is gaining attention in photocatalysis due to its semiconducting properties, which allow its activation by visible radiation. This material is of particular interest because of the increasing use of solar energy in many applications, but previous studies have found that g-C3N4 is more useful when associated with another semiconductor in a heterostructured system such as AgVO3/g-C3N42, g-C3N4/TiO23 . Among several materials with high potential to form heterostructures with g-C3N4, Nb2O5 is an especially interesting material due to its electronic properties. Nb2O5 is also well known for its strong surface acidity, which is useful for the adsorption and subsequent degradation of organic pollutants. Therefore, we propose a synthesis route for the production of suitable heterostructures using a sonochemical method based on surface charge-induced heteroaggregation. In this work we was focus shown that the g-C3N4/Nb2O5 heterojunctions with different weight ratios between g-C3N4 and Nb2O5, enhanced the photocatalytic performance for degradation of emerging pollutants (drug amiloride and rhodamine B dye) under visible irradiation, compared to the pure semiconductors. The photodegradation performances were mainly associated with increased lifetimes of the charge carriers, due to the formation of heterojunctions between Nb2O5 and g-C3N4. Formation of the type II heterostructure was confirmed by time-resolved photoluminescence, with the 3CN:1Nb heterostructure showing the longest electron/hole pair lifetime. Studies of the photodegradation mechanism confirmed that the hole (i.e., direct oxidation) was the main active species for dye photodegradation catalyzed by the g-C3N4/Nb2O5 heterostructures under visible irradiation. Additionally, it was demonstrated that the g-C3N4/Nb2O5 heterostructures exhibited satisfactory photostability, even after four successive reuses. Therefore, our work demonstrates the possibility of achieving significant improvements in the catalytic performance of two different semiconductors, g-C3N4 and Nb2O5, by means of their association.
Keywords: Graphitic carbon nitride; Sonochemical method; Heterojunction; Photooxidation;
Water treatmen
Work supported by Fapesp, LNNano, MCTI/SisNANO, CNPq and CAPES.
Ahmed, M.B. et al. J. Hazard. Mater., 325 (2016) 274-298.
Zhao, W. et al. App. Catal., A 501 (2015) 74–82.
Hung, Z. et al. Appl. Catal., B 164 (2015) 420–427.
8:00 PM - BI02.06.06
Hybrid Power Scavenging Systems Using Solar Panel and Piezoelectric Materials
Hassan Elahi 1
1 , La Sapienza University of Rome, Rome Italy
Show AbstractThis paper implements an efficient way to power generation system, using solar power. Solar energy system is used to collect maximum power from sun. This proposal is to use the solar panels implemented in this project more efficiently and to carry out a realistic experimental approach to enhance the solar output power to a significant level and piezoelectric energy harvesting circuit. In this paper, piezoelectric-based energy harvesting technology is applied to generate electricity from mechanical stress (vibrations). Using piezoelectric material to harvest vibration energy from humans walking, machinery vibrating, or cars moving on a roadway is an area of great interest, because this vibration energy is otherwise untapped. Since movement is everywhere, the ability to capture this energy cheaply would be a significant advancement toward greater efficiency and cleaner energy production. The goal of this experiment is to investigate whether piezoelectricity would be able to provide sufficient source of voltage to charge the parent battery in case of rainy or cloudy days. . This configuration allows the two sources to supply the load separately or simultaneously depending on the availability of the energy sources. This paper implements an efficient way to electrify or generate electricity using solar power and piezoelectric energy harvesting circuit. A prototype of the system having a track of 2x3.5 ft2 having a solar panel on its top and piezo-system below it on the sides is required.
8:00 PM - BI02.06.08
Development of X-Ray Shield Concrete for Secure Safety against the Impact of the Fukushima Accident
Ippei Sato 2 , Toshio Hatakeyama 2 , Yasuyuki Sato 2 , Yasuyuki Mori 3 , Yaoki Yamashita 3 , Satoru Hashimoto 4 , Ichiro Hatsumura 1 , Yhuki Katakami 1 , Tsukuru Nishitsunoi 1 , Teruyoshi Hirano 1
2 , TAIHAKU Co., Ltd., Natori-city, Miyagi, Japan, 3 , REMIKKUMSRUHACHI Co., Ltd., Senbiki-city, Gifu, Japan, 4 , HYOUKAKEN Co., Ltd., Chiyoda-ku, Tokyo, Japan, 1 , GGK Inc, Tokyo Japan
Show AbstractThe TEPCO Fukushima Daiichi Nuclear Power Plant has meltdown due to the huge earthquake and tsunami that occurred on March 11, 2011. As a result, radioactive materials were dissipated into the environment. Those materials caused continuous concern to the Fukushima area.
We developed efficient shielding concrete as a building material to shield the influence against radioactive materials. This concrete is a material blended with the Anti-Sievert® (high density ceramics material). Conventionally, when the Anti-Sievert® is compounded, concrete requires a high concentration of water. Therefore, lots of water added, sufficient concrete strength could not be realized. Moreover, it was not able to give liquidity corresponding to construction materials.
We developed the Anti-Sievert® concrete containing high performance water reducing material and optimized blending of cement, water, aggregate, sand material, the Anti-Sievert® 210 and the Anti-Sievert® 216 as materials for composing the concrete. As a result, we realized the shielding concrete with high fluidity to realize construction suitability by concrete pump machine. Anti-Sievert® concrete has a shielding function of about 3 times as compared with ordinary concrete with respect to X-ray (200 kV), and shows strength exceeding 40 N / mm2.
In this presentation, the correlation between the shielding effect of Anti-Sievert® concrete and the energy of X-rays is shown and discussed. In addition, the evaluation results of strength and durability of Anti-Sievert® concrete are shown in this presentation. These conclusions show that Anti-Sievert® concrete is an excellent X-ray shielding material and is a practical material having extremely high durability and strength.
8:00 PM - BI02.06.09
Development of High Performance Additives for the X-Ray Shield Concrete against the Fukushima Accident
Satoru Hashimoto 4 , Yhuki Katakami 1 , Tsukuru Nishitsunoi 1 , Ichiro Hatsumura 1 , Yaoki Yamashita 3 , Yasuyuki Mori 3 , Toshio Hatakeyama 2 , Ippei Sato 2 , Yasuyuki Sato 2 , Teruyoshi Hirano 1
4 , HYOUKAKEN Co., Ltd., Chiyoda-ku, Tokyo, Japan, 1 , GGK Inc, Tokyo Japan, 3 , REMIKKUMSRUHACHI Co., Ltd., Seki-city, Gifu, Japan, 2 , TAIHAKU Co., Ltd., Natori-city, Miyagi, Japan
Show AbstractThe TEPCO Fukushima Daiichi Nuclear Power Plant has meltdown due to the huge earthquake and tsunami that occurred on March 11, 2011. As a result, radioactive substances were dissipated into the environment, which caused concern about continuous radioactive substances. In the future, it will be required to shield the influence from radioactive materials and radiation for a long time. In particular, concrete with enhanced radiation shielding function is required as building materials.
We have developed an additive for concrete that effectively shields radiation such as X-rays. The concrete having an excellent shielding effect has been realized by adding high density oxides, slag, tungsten and the like. Existing X-ray shielding concrete is deficient in strength and fluidity, and there was a big problem in construction situations. This shielding concrete additive can realize concrete blended with Anti-Sievert® (high density ceramic material). X-ray shielding concrete with high strength and excellent durability could be realized by blending Anti-Sievert® additives and Anti-Sievert® shielding materials.
In this presentation, we will show and discuss the properties of Anti-Sievert® additives and the properties of the concrete optimized for blending. These results show that Anti-Sievert® concrete is an excellent X-ray shielding material and is a practical material having extremely high durability and strength.
8:00 PM - BI02.06.10
In-Field, Disposable Soil Sensor for Monitoring Pesticides Levels via Laser Annealed Graphene Electrodes
John Hondred 2 , Joyce Breger 1 , Suprem Das 2 , Scott Walper 1 , Igor Medintz 1 , Jonathan Claussen 2
2 Mechanical Engineering, Iowa State University, Ames, Iowa, United States, 1 Bio/Molecular Science and Engineering, U.S. Naval Research Laboratory, Washington, District of Columbia, United States
Show AbstractWhile the use of pesticides (organophosphates) are critically important to meet the current and future food demands, their overuse has shown long-term detrimental impacts on the environment. Current pesticide soil measurement methods (chromatography) are costly, require trained technicians, and take days to analyze; thus, farmers are taking an “over-application approach” which is pollution the environment and waterways. A disposable, in-field soil sensor would provide farmers the opportunity of precisely regulating the application of pesticides in an independent and economical fashion. Electrochemical biosensors provide the unique ability to quickly detect analytes with disposable sensors; however, the detection limit and sensitivity of these biosensors are inadequate for current applications. Three approaches are simultaneously performed to address this issue: 1) Increasing the enzymatic efficiency of organophosphate hydrolase by strategically functionalizing to nanomaterials [e.g., 17-fold increase in Vmax when functionalized to gold nanoparticles vs free enzyme]. 2) Improving the electroactive transduction material of the biosensor by laser annealing graphene which facilitates reduced resistance [sheet resistance ~ 0.7 kΩ/sq], high-surface electroactive surface area [3D petal-like nanostructuring], and fast heterogenous charge transport. 3) Performing enhanced electrochemical measurement techniques by use of complex geometries (e.g. interdigitated electrodes fabricated using IML technique, line resolution below 25 microns). This disposable, direct application biosensor will be a platform technology that could be amenable to other applications such as healthcare screening, drinking water monitoring, and even bioterror agent detection. This work demonstrates the manufacturing of a simple, low-cost electrochemical biosensor suitable for rapid in-field detection of organophosphates that has low detection limits, high linear sensing range, and ultra-low detection limits.
8:00 PM - BI02.06.11
Synthesis of Antimicrobial Magnesium Hydroxide Particle for Agricultural Application
Ziyang Huang 1 , Parthiban Rajasekaran 1 , Ali Ozcan 1 , Swadeshmukul Santra 1
1 , UCF NanoScience Technology Center, Orlando, Florida, United States
Show AbstractExcessive use of heavy metals such as copper in agriculture biocides have raised environmental concerns thus warranting alternative strategies. Magnesium serves as one macronutrient for plants. Employing magnesium based biocidal material can act as a dual-purpose strategy to act both as a nutrient supplement and as a plants disease controlling agent. The low cost and environmental friendly magnesium hydroxide has been widely applied in wastewater purification, fire retardant material and in neutralizing stomach acidity. Recent studies suggest magnesium hydroxide as an effective antibacterial agent. This study focuses on synthesizing surface charge-tunable magnesium hydroxide particles and their potential application in agriculture. Magnesium hydroxide was synthesized by coprecipitation method. Various organic capping agents were used to control particle size. Positive and negative charged particle may have a different interaction preference towards negative charged bacteria surface. Different capping agent could change particle surface charge from negative to positive. The binding between capping agent and particles were confirmed by FT-IR. Zeta potential measurement was used to confirm the particle surface charge and the particle surface charge was variable with different capping agents. The hydrodynamic size was confirmed by DLS, the diameter of synthesized Mg(OH)2 with different capping agents were 200-300 nm. XRD was applied to study the crystal structure of as-synthesized Mg(OH)2. The morphology of synthesized material and the relationship between morphology and antibacterial effects are further studied by SEM. The antimicrobial activity was determined by performing a 96-well plate based MIC and CFU assays. The results showed that the minimum inhibitory concentration for Pseudomonas syringae and Xanthomonas alfalfae was about 250 μg/mL of metallic magnesium. This study introduces synthesis of a magnesium hydroxide based biocide that can be applied for plant disease control.
8:00 PM - BI02.06.13
Magnetic Slippery Extreme Icephobic Surfaces
Peyman Irajizad 1 , Abdullah Al-Bayati 1 , Nazanin Farokhnia 1 , Hadi Ghasemi 1
1 , University of Houston, Houston, Texas, United States
Show AbstractAnti-icing surfaces have a critical footprint on daily lives of humans ranging from transportation systems and infrastructure to energy systems, but creation of these surfaces for low temperatures remains elusive. Non-wetting surfaces and liquid-infused surfaces have inspired routes for the development of icephobic surfaces. However, high freezing temperature, high ice adhesion strength, and high cost have restricted their practical applications. Here we report new magnetic slippery surfaces outperforming state-of-the-art icephobic surfaces with an ice formation temperature of -34oC, 2–3 orders of magnitude higher delay time in ice formation, extremely low ice adhesion strength (≈2 Pa) and stability in shear flows up to Reynolds number of 105. In these surfaces, we exploit the magnetic volumetric force to exclude the role of solid–liquid interface in ice formation. We show that these inexpensive surfaces are universal and can be applied to all types of solids (no required micro/nano structuring) with no compromise to their unprecedented properties.
8:00 PM - BI02.06.14
Cellulose Assisted Combustion Synthesis of Nanoparticles for Sustainable Hydrogen Production
Anand Kumar 1 , Anchu Ashok 1 , Rahul Bhosale 1
1 , Qatar University, Doha Qatar
Show AbstractCatalyst nanoparticles were synthesized using a novel “Cellulose Assisted Combustion Synthesis” technique. In this technique, an aqueous solution of metal nitrate and a reducing agent is impregnated on a thin cellulose paper. The paper is dried and locally ignited at one end to start combustion reaction that is self-sustained under optimum loading of reactive solution, continuously producing nanoparticles. The thin film helps in generating a quenching effect and limits nanoparticles sintering in post-combustion stages. This paper describes the synthesis of Cu, Ni and Co based nanomaterials that are found to be active for sustainable hydrogen production from bioethanol, that can further be produced from agricultural biomass. A detailed mechanistic study of nanoparticle evolution during synthesis process was conducted along with the reaction pathway analysis for hydrogen production from bioethanol. In-situ FTIR (DRIFTS) studies on the metal surfaces reveal the differences in their catalytic performance and help in explaining the observed product distribution.
8:00 PM - BI02.06.15
Spring-Assisted Triboelectric Nanogenerator for Efficiently Harvesting Water Wave Energy
Tao Jiang 1 , Yanyan Yao 1 , Zhong Lin Wang 1 2
1 , Beijing Institute of Nanoenergy and Nanosystems, Chinese Academy of Sciences, Beijing China, 2 , Georgia Institute of Technology, Atlanta, Georgia, United States
Show AbstractOcean waves are one of the most promising renewable energy sources for large-scope applications. Triboelectric nanogenerator (TENG) has been demonstrated to effectively harvest water wave energy possibly toward large-scale blue energy. In this work, a kind of spring-assisted TENG was designed and investigated for harvesting water wave energy. The idea of introducing spring is to store the potential energy built during mechanical triggering for multiple cycles of conversion into electricity afterward, and transform a low frequency motion into a high frequency oscillation for improving the energy harvesting efficiency. The output performance of the basic unit was optimized by adjusting the motor acceleration and spring parameters including the rigidity and length. There exists an optimized spring rigidity or spring length to produce the highest performance. By using the spring, the accumulated charge of the TENG can be increased by 113.0%, and the translated electric energy or efficiency can be improved by 150.3%. Then four optimized basic units were connected in parallel and packaged into a sealed box to harvest the water wave energy. The present work could provide an approach to improving the output performance and efficiency of TENGs in harvesting low-frequency water wave energy.
8:00 PM - BI02.06.16
Modifications of Copper Catalysts for CO2 Reduction via Overlayer Addition and Electrochemically Induced Phase Transitions
Roman Kazantsev 1 2 , Alberto Riccardis 1 , Sean Fackler 1 , Maryam Farmand 1 , Aya Buckley 1 , David Larson 1 , Guiji Liu 1 , Paul Burroughs 1 , Walter Drisdell 1 , F. Toste 2 , Francesca Maria Toma 1
1 , Lawrence Berkeley National Laboratory, Berkeley, California, United States, 2 Chemistry, University of California, Berkeley, California, United States
Show AbstractModification of copper (Cu) catalysts for enhanced carbon dioxide reduction (CO2R) is a long-standing challenge in the field of artificial photosynthesis. Altering Cu’s surface chemistry and material properties has been suggested as a route to alter the binding energies of CO2–° and CO* intermediates important for CO2 activation and reduction. However, producing materials that promote C-C bond coupling while limiting parasitic formation of H2 is a non-trivial matter. To address these challenges, we target a two-pronged approach. The first prong involves modification of Cu’s surface via interfacing with oxide overlayers. Synthesized via hydrothermal techniques directly onto Cu electrodes, the oxides investigated include porous aluminosilicate zeolites, tungsten oxide, and vanadium oxide, all of which impact copper’s ability to reduce CO2. The second prong involves Cu catalyst synthesis via electrochemically induced phase transition from Cu(II)-based nanostructured precursors. Results suggest that the initial morphology of the Cu precursors before electroreduction impacts the selectivity of products produced from CO2R. In all cases, materials were thoroughly characterized by X-ray and microscopy techniques and CO2R was conducted in a custom-built electrochemical, two-chamber compression cell. Further understanding of the structural and electronic properties of these materials will enable selectivity tuning in future CO2R electrocatalysts.
8:00 PM - BI02.06.17
The One-Step Fabrication of Triboelectric Nanogenerator Based on the Nano Imprinting and Poling Process
Do Wan Kim 1 , Dongwhi Choi 1 , Dong Sung Kim 1
1 , POSTECH, Pohang Korea (the Republic of)
Show AbstractEnergy harvester called triboelectric nanogenerator that convert mechanical energy from an ambient environment to electrical energy has been growing topic of interest as promising means of generatring electrical power for mobile system applications and micro devices without using wiring from an external power source. After the first report in 2012 due to high accessibility from the ubiquitous characteristics of contact electrification. With the help of a simple configuration and high accessibility, lots of TENGs have been developed for various applications, such as biomechanical energy harvesters, micro devices, and optoelectronic devices. With the exception of functional characteristics, another topic of interest is improvement of electrical output performance of TENG. As the generation of the electrical output is dependent on the surface contact, the surface morphology of the contact layer of the TENG plays an important role in enhancing the electrical output performance. Another factor is the increase of the surface charge by applying external electric field called poling process. Due to the poling process, the surface charge of contact layer is enhanced, especially, as the ferroelectric material is subjected to the external electric field, the surface potential difference increases. However, the process of surface modification is expensive and complex and poling process is time-consuming task. To overcome the limitation, we introduced the developed process in combination with nano imprinting and poling process. The thermoplastic and ferroelectric polymer which is PVDF is suitable for the nano imprinting and poling process in terms of characteristics. By applying the external electric field during the nano imprinting, the surface modification and the enhancement of surface charge and surface potential difference can be obtained. Also the shorten of the process can obtain the feasibility of mass production. From the results, we believe the research suggests a developed process can be applicable in energy industry.
8:00 PM - BI02.06.18
Materials Innovation for Sustainable Agriculture and Its Application for Bacterial Diseases
Briana Lee 1 , Ali Ozcan 1 2 , Parthiban Rajasekaran 1 , Swadeshmukul Santra 1 2 , Laurene Tetard 1 3
1 NanoScience Technology Center, University of Central Florida, Orlando, Florida, United States, 2 Chemistry, University of Central Florida, Orlando, Florida, United States, 3 Physics, University of Central Florida, Orlando, Florida, United States
Show AbstractThe chemical, physical, and biological properties of bacteria developing resistance, in both humans and plants, are mostly unknown at the single cell level. However biomechanical properties have been shown to contribute to bacteria becoming infectious. Thus the ability to probe changes in stiffness, adhesion, binding interactions and molecular traits of individual bacteria is of great interest to develop a new generation of more potent, yet sustainable, pesticides.
Our study aims to investigate the mechanical and chemical properties of bacterial systems and their cell walls. Building upon this fundamental understanding of the cells, we also investigate the biophysicochemical responses associated to multivalent nanoparticle-based bactericide treatments on bacterial systems identified as pathogens in plant diseases. Here we focus on developing a novel protocol to support the design and accelerate the development of pesticides and treatments against Xanthomonas perforans, a strain known for causing bacterial spot in tomatoes and causing close to 50% losses in production. By comparing bacteria pre- and post-treatment with a multivalent silica core shell nanoparticle using a combination of Raman spectroscopy and atomic force microscopy (AFM)-based techniques, we identify attributes that can potentially serve as markers to track the bacterial response to the treatment. By exploring the local bacterial responses to treatment and correlating the results to conventional bioassays, we propose a new approach with exciting implications, such as potential clues for the development of more potent treatments for resistant bacteria.
8:00 PM - BI02.06.19
Solar Photo-Thermal Water Splitting at 140 °C with Cu-Loaded TiO2
Do Son 1
1 , Sogang University, Seoul Korea (the Republic of)
Show AbstractMetal oxide based solar thermal water splitting is a promising approach for using solar energy to produce H2 and O2. The normal protocol employed for this process involves thermal reduction of a metal oxide (MOx) at around 1500 °C to produce the reduced form (MOx-d) and O2. This step is followed by steam treatment of MOx-d at around 1000 °C to yield MOx and H2. Owing to the need to use high temperatures, the traditional approach has several important drawbacks. In a study designed to improve this process, we found that Cu-loaded TiO2 (Cu/TiO2) effectively expels O2 upon irradiation with an AM 1.5 1 SUN solar simulated light and that treatment of the reduced form of the reduction product Cu/TiO2-d with steam at 140 °C generates H2. This new approach, termed solar photo-thermal water splitting, has the potential of becoming an important method for converting solar energy into chemical energy.
8:00 PM - BI02.06.20
Thiol-Alkene Click Chemistry Approach for Enhanced Energy Density Required for SEA-FARM
Kanun Pokharel 1 , Zhe wang 2 , Christopher Green 3 , Greg Lutz 3 , Bryan Bilyeu 2 , Douglas Chrisey 1
1 , Tulane University, New Orleans, Louisiana, United States, 2 , Xavier University, New Orleans, Louisiana, United States, 3 , Louisiana State University, Baton Rouge, Louisiana, United States
Show AbstractGlobal production of farmed fish has more than doubled in the past 15 years. The United States today imports about 70% of its fish food consumption resulting in large economic deficit. Aquaculture systems could be a possible solution to it and for that, we propose a modern approach “Sustainable Economic Aquaculture From Autonomously Real-time Monitoring (SEA-FARM) System” that can be deployed to high diversity aquaculture farm with freshwater or marine. SEA- FARM will be a multi-disciplinary effort from concept to operation, towards minimizing the energy consumption and maximizing the efficiency of the operation for a desirable precision of aquaculture assessment. To accomplish the goal, we plan to store energy capacitively as the cost must be amortized over the storage unit’s lifetime, including continuous operation, making our capacitive approach economically advantageous.
Dielectric capacitive storage provides the necessary power density and lifetime properties required for SEA-FARM, but falls short when it comes to gravimetric energy storage. Energy density is depended on two factors; dielectric constant and breakdown field. Efforts have been made to increase the energy density through nanocomposites by mixing high dielectric ferroelectric nanopowders with known high breakdown polymers through surface initiated polymerization assuming that overall energy density is enhanced. However, the interface of the nanoparticle and polymer matrix creates a void that acts as a charge concentrator, greatly reducing the breakdown field. We use an approach called thiol-alkene click chemistry to overcome this issue. By designing a thermally and electronically stable polymer that is cured through UV processing, functionalized high dielectric constant nanoparticles can be directly bonded into a high breakdown polymer matrix that enhances energy density. To achieve this, we need novel materials that will both withstand high electric fields (≥1 MV/cm) and maintain an extremely high dielectric constant (~30,000). The energy thus obtained is then used in SEA-FARM.
8:00 PM - BI02.06.21
Density Functional Theory Study of Cu Doped (0001) and (012) Surfaces of Hematite for Photoelectrochemical Water Splitting
Joseph Simfukwe 1 , Edwin Refilwe Mapasha 1 , Mmantsae Diale 1 , Artur Braun 2
1 Department of Physics, University of Pretoria, Pretoria, Gauteng, South Africa, 2 , Empa–Swiss Federal Laboratories for Materials Science and Technology, Zurich Switzerland
Show AbstractDensity Functional Theory study of Cu doped (0001) and (012) surfaces of hematite for photoelectrochemical water splitting.J. Simfukwe
1,2*, R. E. Mapasha
1, A. Braun
3 and M. Diale
11Physics Department, University of Pretoria, Pretoria 0002, South Africa.2Physics Department, Copperbelt University. Riverside, Kitwe 10101, Zambia3Empa, Zurich, SwitzerlandAbstract:The production of energy from fossil fuels and nuclear materials has a number of environmental draw backs. These draw backs include the creation of nuclear waste and the pollution associated with fossil fuels which lead to global warming and climate change. Increasing demand for sustainable, carbon free energy is the motivation behind the development of solar energy conversion and storage technologies. In Photoelectrochemical (PEC) water splitting, we need suitable semiconductors to directly dissociate water molecules into hydrogen and oxygen. Hematite (α-Fe
2O
3) possesses several advantages over other semiconductor materials for water splitting technique. Its band gap of ~ 2.1 eV makes it possible to absorb about 40 % of the incident solar spectrum. In addition, it is a very stable material in a broad pH range, non-toxic and abundant in the Earth’s crust. These advantages have attracted a lot of research on hematite as a photoanode material for PEC. However, hematite also presents a number of challenges for its full applications in PEC water splitting. Hematite as an n-type oxide, its conduction band which lies below that of H
+/H
2 redox potential, does not favour the self reduction of hydrogen. This means an external bias is needed to drive this reaction. Poor carrier mobilities and short hole diffusion length are other challenges for hematite. In this study, we have carried out Density Functional Theory calculations to study the Cu doped (0001) and (012) surfaces of hematite for enhanced water splitting. It is envisaged that surface doping is more beneficial than bulk doping because it reduces the distance moved by the charge carriers and further reduce quick recombination resulting in efficient use of the charges. Our results show that the (0001) and (012) surfaces are more stable. Furthermore, our preliminary results indicate that the band gap of hematite can be reduced by surface doping with Cu which leads to increased absorption of incident solar light.
Keywords: hematite (α-Fe
2O
3); surfaces; copper (Cu); Photoelectrochemical and density functional theory
*[email protected] 8:00 PM - BI02.06.22
Enhancing Performance of Microbial Fuel Cell Treating Distillery Wastewater Using Carbon Supported Nickel-Phthalocyanine/MnOx as Novel Cathode Catalyst
Bikash Tiwari 1 , Md Tabish Noori 2 , M.M. Ghangrekar 1
1 Department of Civil Engineering, Indian Institute of Technology, Kharagpur India, 2 Department of Agricultural and Food Engineering, Indian Institute of Technology, Kharagpur India
Show AbstractMicrobial fuel cell (MFC) is an upcoming technology which integrates the dual attribute of anodophillic microbiota capable of donating electrons to a solid electrode in addition to degrading organic matter present in wastewater. MFCs can bridge the gap in the existing waste treatment facilities as well as provide a clean and green solution to the imminent energy crisis. The most commonly used separator, i.e. Nafion and cathode catalyst, i.e. platinum, together account for around 85 % of the total fabrication cost of MFC. A decrease in the total cost of MFC by incorporation of low cost materials can induce their field scale application. Recently, transition metal based organometallic complexes (TMO) have been found to be suitable low cost cathode catalyst for enhancing MFC performance, but synthesis at high temperature is imperative for the activation of metal centre. Incorporating transition metal based oxides like MnO2 to the TMO can be an alternative to the high temperature synthesis procedure. In this study, nickel phthalocyanine incorporated with MnO2 was evaluated as cathode catalyst for MFC. Three MFCs with different catalyst incorporated on carbon felt cathode, viz. nickel phthalocyanine-MnOx (NiPc-MnOx) composite (MFC-1), platinum (MFC-2), control MFC with only carbon felt (MFC-3) were used for treating distillery wastewater. Raw distillery wastewater was found to have a high chemical oxygen demand of 57 gL-1 and acidic pH of 3.5. PVA-Nafion borosilicate membrane, having comparable performance as Nafion but 11-fold less costly was utilized as separator for all the MFCs. Various crystallographic phases of manganese dioxide (Mn3O4, MnO2 and MnO), NiPc and carbon were detected in the X-ray diffraction peaks of NiPc-MnOx/C. Growth of rod shaped MnOx along with circular NiPc/C were obtained from Field emission scanning electronmicroscopy of synthesized NiPc-MnOx/C. The linear sweep voltammetry studies revealed that a maximum current density of 3.7 Am-2 was achieved for NiPc-MnOx/C catalysed cathode which is 13-folds higher than that for control cathode (0.27 Am-2). Consequently, MFC-1 demonstrated a power density of 48.9 mWm-2 which was around 3.3 folds higher than the control MFC (14.9 mWm-2) owing to the improved oxidation reduction kinetics incase of NiPc-MnOx catalysed cathode. Coulombic efficiency (CE) was enhanced by a margin of about 11 % for MFC-1 (24.8 %) comparison to MFC-3 (13.4 %). MFC-1 successfully achieved a power density of around 79 % and CE around 83 % of that exhibited by MFC-2 (62 mWm-2, 29.8 %) having platinum cathode catalyst at 3-fold less cost as compared to platinum. Hence, NiPc-MnOx can be used as an alternative to platinum as cathode catalyst in MFC treating distillery wastewater. The implementation of low cost PVA-Nafion borosilicate membrane along with NiPc/MnOx cathode catalyst can lead to about 80 % reduction in cost of existing MFCs, thus making MFCs an economically feasible as well as sustainable technology.
8:00 PM - BI02.06.23
Improvement of TiO2 Photocatalytic Properties by Heterostructure Based on MgO/TiO2
Juliana Torres 1 , Andre Nogueira 1 , Gelson Tiago da Silva 2 1 , Caue Ribeiro 1
1 , Brazilian Agricultural Research Corporation/Embrapa Instrumentation, São Carlos Brazil, 2 Department of Chemistry, Federal University of São Carlos, São Carlos, São Paulo, Brazil
Show AbstractThe increase in energy consumption from the burning of fossil fuels coupled with the high emission of CO2 in the atmosphere has stimulated the search for solutions that reduce this emission of gases responsible for the greenhouse effect. An energetically favorable alternative is the photocatalytic reduction of CO2 since it aims to simultaneously use the emitted CO2 and the abundant solar energy to produce value-added chemical and fuel products [1]. Artificial photosynthesis uses solar power to convert raw materials like water and CO2 to useful chemicals, e.g., H2, CH4, CO, and hydrocarbons [2] Therefore, the success of this approach relies on two aspects; the eficiente utilization of solar power and the enhancement of the catalytic conversion of water and CO2 to fuels and chemical. Numerous heterostructures have been used for this proposal, among them MgO/TiO2 stands out due to the high adsorption capacity of CO2 molecules by MgO in the presence of H2O vapor, besides the easy desorption of the reaction products. In addition, TiO2 has the advantage of being low cost, chemically stable and non-toxic [3]. MgO on TiO2 photocatalysts can activated adsorbed CO2 molecules, which promotes the production of HCO3-, a possible intermediate for the production of hydrocarbon fuels or CO when the dissociative H atoms are available [3]. In this contexto, the objective of this study was to evalute the properties and the photocatalytic activity of heterostructures of MgO/TiO2 synthesized by co-precipitation method. In addition, the MgO semiconductor synthesized by the hydrothermal method was used to obtain higher superficial affinity for CO2 through its high adsorption capacity of this compound. The isolated semiconductors and the heterostructure were characterized by Xray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance UVVis spectroscopy (DRS), and nitrogen physical adsorption (BET method). The photocatalytic activity was evaluated using photoreduction CO2 in H2O vapor under ultravioleta irradiation using TiO2 and MgO/TiO2. The nanorods of TiO2 were successfully synthesized by the methodology used, being confirmed by the SEM. The band gap found for TiO2 through DRS confirms the stipulated in the literature (3,2 eV). The MgO/TiO2 heterostructure have been successfully synthesized by a facile co-precipitation method. The analysis of the gases after the photoreduction CO2 indicated the formation of CH4 mainly, being that after the synthesis of the heterostructure, the effect was more pronounced compared to the pure TiO2. This improvement can be attributed to the heterostructure between MgO and TiO2, which possibly facilitated charge transfer and the suppressed recombination of electron/hole pairs.
8:00 PM - BI02.06.24
Mesoscale Simulations of Confined Ionomer Membranes
Peter Vanya 1 , Jonathan Sharman 2 , James Elliott 1
1 Materials Science and Metallurgy, University of Cambridge, Cambridge United Kingdom, 2 , Johnson Matthey Technology Centre, Sonning Common United Kingdom
Show AbstractIonomer membranes are a class of materials promising to revolutionise transport industry via its use in fuel cells. Before they are capable of providing a serious alternative to batteries or combustion engines, several problems need to be addressed. Notable challenges include increased transport resistance at low platinum loadings, as measured by Weber et al. [1] and non-bulk morphology of the catalyst layer observed by the NIST group [2].
To gain insight into the behaviour of the fuel cell catalyst layer, we employed dissipative particle dynamics to simulate Nafion films of thickness of the order of tens of nanometres. Confining the thin film by carbon and quartz, two materials of opposing hydrophobicity, we investigated changes in water clustering, diffusivity and percolation channels for a wide range of water uptakes and film widths.
Our simulations show confinement-induced clustering of water perpendicular to the Nafion thin film, in agreement with neutron reflectometry. Near the film interface, hydrophobic carbon forms a water depletion zone, whereas hydrophilic quartz produces excess water. Diffusivity shows increasing anisotropy of up to 30% with decreasing film width, regardless of the confining material. Percolation analysis of water clustering and connectivity reveals significant differences with confining material. Water confined by carbon forms large disconnected clusters, whereas quartz induces well-interconnected channels.
All these findings suggest a fundamentally different nature of ionomer thin films compared with the bulk regime, with likely impact on fuel cell performance, and suggest avenues for exploration of a wider range of electrode materials, particularly platinum, or more complex shapes of the membrane-electrode interface.
[1] Weber and Kusoglu, J. Mat. Chem. A, 2014
[2] Dura et al., Macromolecules, 2009
8:00 PM - BI02.06.25
Antiscaling Magnetic Slippery Surfaces
Ali Masoudi 1 , Peyman Irajizad 1 , Nazanin Farokhnia 1 , Varun Kashyap 1 , Hadi Ghasemi 1
1 , University of Houston, Houston, Texas, United States
Show AbstractScale formation is a common problem in a wide range of industries such as oil and gas, water desalination and food processing. Conventional solutions for this problem including mechanical removal and chemical dissolution are inefficient, costly, and sometimes environmentally hazardous. Surface modification approaches have shown promises to address this challenge. However, these approaches suffer from intrinsic existence of solid-liquid interfaces leading to high rate of scale nucleation and high adhesion strength of the formed scale. Here, we report a new surface called magnetic slippery surface in two forms of Newtonian fluid (MAGSS) and gel structure (Gel-MAGSS). These surfaces provide a liquid-liquid interface to elevate the energy barrier for scale nucleation and minimize the adhesion strength of the formed scale on the surface. Performance of these new surfaces in both static and dynamic (under fluid flow) configurations is examined. These surfaces show superior anti-scaling properties with an order of magnitude lower scale accretion compared to the solid surfaces and offer longevity and stability under high shear flow conditions. We envision that these surfaces open a new path to address the scale problem in the relevant technologies.
8:00 PM - BI02.06.26
Synthesis and Characterization of CaO/ZSM5 Catalyst for the Study of Biodiesel Production
Jane Estephane 1 , Lena Chalouhi 1 , Safa Sammoury 1 , Bilal El Khoury 1 , Henri El Zakhem 1 , Cedric Gennequin 2 , Samer Aouad 1 , Edmond Abi Aad 2
1 , University of Balamand, El koura Lebanon, 2 , Université du Littoral Côte d'Opale , Dunkerque France
Show AbstractNowadays, fossil fuel resources are tremendously shrinking. Due to the huge demand for liquid fuels, especially for transportation purposes, it is necessary to find an alternate green source of energy. Production of biodiesel from vegetable oils and animal fats presents a promising solution since the oils and fats are readily available and renewable. Therefore, producing biodiesel from vegetable oils can help in enforcing energy security [1]. Biodiesel is nontoxic, biodegradable, and environmentally friendly. Moreover it has a high cetane number, no aromatics, virtually no sulphur content, and a high flash point [2-3]. Biodiesel is one of the prevalent choices to replace the conventional diesel.
ZSM5 zeolite support was used to prepare a series of CaO/ZSM5 catalysts with different CaO loadings (5 wt.%, 15 wt.% and 35 wt.%) using the wet impregnation method and the prepared catalysts were labeled 5CaO/ZSM5, 15CaO/ZSM5, and 35 CaO/ZSM5, respectively. The catalysts were calcined at 800°C in a muffle furnace for 3 hours (0.5°C/min), and then characterized by N2 adsorption-desorption, XRD and FTIR techniques. The catalytic activity of these catalysts was tested in the transesterification reaction of refined sunflower oil in a batch reactor at 60°C, using a fixed methanol to oil molar ratio (MOMR) of 12:1. Optimization of the reaction conditions was done by modifying the catalyst to oil mass ratio and reaction time.
Among the prepared catalysts, the 35CaO/ZSM5 catalyst exhibited the best catalytic performance at 60°C reaction temperature, 12:1 methanol to oil molar ratio, and 4 wt.% of catalyst loading. Optimization of the transesterification reaction conditions (reaction time, and catalyst to oil mass ratio) was done for the 35CaO/ZSM5. A methyl ester yield of 91.1 % was obtained for a reaction time of 6 h, at 60°C with 12:1 methanol to oil molar ratio and 10 wt.% of catalyst loading. The properties of produced biodiesel were studied and were found to be in good agreement with ASTM standard requirements.
References
[1] Zhang, X., & Huang, W. (2011). Biodiesel fuel Production through transesterification of chinese tallow kernel oil using KNO3/MgO catalyst. Procedia Environmental Sciences, 11, 757-762.
[2] J.M. Marchetti, “A summary of the available technologies for biodiesel production based on a comparison of different feedstock's properties”, Process Saf. Environ. Prot., vol. 90, no. 3, pp. 157–63, 2012.
[3] G. Knothe, “Improving biodiesel fuel properties by modifying fatty ester composition”, Energy Environ. Sci., vol. 2, no. 7, pp.759–766, 2009.
8:00 PM - BI02.06.27
Enhanced Electro-Kinetics of C-C Bond Splitting During Ethanol Oxidation Reaction Using Pt/Rh/Sn Catalyst with a Partially Oxidized Pt and Rh Core and a SnO2 Shell
Guangxing Yang 1 , Anatoly Frenkel 2 , Dong Su 3 , Xiaowei Teng 1
1 Department of Chemical Engineering, University of New Hampshire, Durham, New Hampshire, United States, 2 Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, New York, United States, 3 Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York, United States
Show AbstractDirect ethanol fuel cell (DEFC) is a promising technology for generating electricity via the electro-oxidation of liquid ethanol. Its implementation requires the development of anode catalysts capable of producing CO2 and yielding 12-electron transfer through breaking C-C bond of ethanol. Here we presented comprehensive studies of electro-kinetics of the CO2 generation on Pt/Rh/Sn ternary catalysts. Our studies showed that, for the first time, the tri–phase PtRhOx-SnO2 catalysts with a partially oxidized Pt and Rh core and a SnO2 shell, validated by X-ray absorption analyses and scanning transmission electron microscope-electron energy loss spectroscopy line scan, coincided with a 2.5-fold increase in the CO2 generation rate towards ethanol oxidation reaction, compared with the bi-phase PtRh-SnO2 catalysts with a metallic PtRh alloy core and commercial Pt. These studies provided insight on the design of a new genre of electro-catalysts with a partially oxidized noble metal.
8:00 PM - BI02.06.28
Reducing Sugar-Derived Mesoporous Graphene for High Energy and Ultra High Power Density Supercapacitor
SungHoon Jung 1 , HoSeok Lee 1 , Yusik Myung 1 , TaeYoung Kim 1
1 , Department of BionanoTechnology, Gachon University, Seongnam-si Korea (the Republic of)
Show AbstractWe present a scalable method to synthesize highly mesoporous graphene-based carbons derived from reducing sugar precursors. The process started with polymerization of mono- or disaccharide with amine-based compounds, releasing gas to produce a number of macropores and micropores. The polymers were converted into three dimensional macro- and microporous carbons frame with mono- or few-layered graphene at high temperature. We further attempted to activate reducing sugar-derived graphene to achieve large surface area and highly mesoporosity by physical- and chemical activation process. The resulting highly mesoporous activated graphene from reducing sugar were tested as electrode materials for supercapacitor with organic- and ionic liquid electrolytes. Performances of mesoporous graphene-based supercapacitor will be presented in terms of specific capacitance, energy- and power density on the physical- and chemical analysis of the electrode materials.
8:00 PM - BI02.06.29
Nanotechnology for Improving Local Systemic Activity of Copper (Cu) Pesticides and Measuring Sub-Surface Cu Bioavailability in Plant Tissue
Ali Ozcan 2 1 , Briana Lee 1 , Mikaeel Young 3 1 , Quirong Fan 4 , Amanda Strayer 4 , Ying-Yu Liao 4 , Stephen Smith 2 1 , Mitsushita Doomra 3 1 , Parthiban Rajasekaran 1 , Jeffrey Jones 4 , Mathews Paret 5 , Laurene Tetard 1 6 , Swadeshmukul Santra 2 1 3
2 Chemistry, University of Central Florida, Orlando, Florida, United States, 1 , Nanoscience Technology Center, Orlando, Florida, United States, 3 Burnett School of Biomedical Sciences, University of Central Florida, Orlando, Florida, United States, 4 Plant Pathology, University of Florida, Gainesville, Florida, United States, 5 Plant Pathology, University of Florida, Quincy, Florida, United States, 6 Physics, University of Central Florida, Orlando, Florida, United States
Show AbstractBacterial spot of tomato caused by Xanthomonas strains represents a major production challenge in Florida and many tropical and sub-tropical regions worldwide. Infection typically results in yield loss of marketable fruit, of up to 50% at peak conditions, negatively impacting US economy. Copper (Cu)-based bactericides constitute the only current choice available to growers for disease management. However, X. perforans, which is the dominant factor for bacterial spot of tomato species in Florida, exhibits Cu tolerance, making disease management with standard Cu pesticides extremely challenging.
This project aims at developing a novel Cu-based locally-systemic pesticide (LSP) material using nanotechnology to significantly increase the number of bactericidal mechanisms against X. perforans. We have successfully synthesized core-shell LSP particles. In a basic design, an inert silica core was coated with a layer of Cu loaded silica layer (shell). Cu is present in the silica gel in the form of hydroxide/oxide nanoparticle. HRTEM data reveals that Cu nanoparticles are ultra-small (~ 5.0 nm) and crystalline. Quaternary ammonium (Quat) compound was immobilized (fixed-Quat) in the silica shell layer during the synthesis process. Phytotoxicity studies were carried on tomato plants. It was observed that LSP formulation containing 300 µg Cu/mL and 75 µg Quat/mL was non-phytotoxic. However, Quat by itself at 75 µg Quat/mL is phytotoxic. Our results suggests that silica is an attractive host material to minimize phytotoxicity of Quat while maintaining its antimicrobial efficacy. At the 500 µg Cu/mL rate and above, we began to observe phytotoxicity of LSP product formulation. In-vitro antimicrobial studies demonstrated strong efficacy of LSP against both Cu susceptible and resistant strains of X. perforans in comparison to a standard film-forming Cu hydroxide based commercial product. SEM and EDS studies confirmed the distribution of LSP material on the leaf surface and aggregation around the stomata area observed. Metallic Cu uptake by tomato plant was quantified using XRF and AAS measurements, and high Cu uptake was observed indicating locally systemic activity of the LSP material.
Symposium Organizers
Swadeshmukul Santra, University of Central Florida
Michael Molinari, Universite de Reims Champagne Ardenne
Nicole Labbe, University of Tennessee
Loukas Petridis, Oak Ridge National Laboratory
BI02.07: Biomass and Biofuels
Session Chairs
Brigitte Chabert
Nicole Labbe
Wednesday AM, November 29, 2017
Sheraton, 3rd Floor, Gardner AB
9:00 AM - *BI02.07.01
Efficient Biomass Deconstruction and Conversion to Biofuel and Bioproducts in Future Biorefineries
Charles Cai 1 , Abhishek Patri 1 , Barmak Mostofian 2 , Bhogeswararao Seemala 1 , Ninad Kothari 1 , Priya Sengupta 1 , Thanh Yen Nguyen 3 , Yunqiao Pu 4 , Umesh Shrestha 5 , Yun-yan Wang 6 , Loukas Petridis 7 , Micholas Smith 7 , Xiaolin Cheng 7 , Jeremy Smith 7 , Arthur Ragauskas 4 6 , Phillip Christopher 8 , Mark Dadmun 5 , Rajeev Kumar 1 , Charles Wyman 1 8
1 Center for Environmental Research and Technology, University of California, Riverside, Riverside, California, United States, 2 , Oregon Health and Science University, Portland, Oregon, United States, 3 , Amyris, Emeryville, California, United States, 4 Biosciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States, 5 Department of Chemistry, University of Tennessee, Knoxville, Knoxville, Tennessee, United States, 6 Chemical and Biomolecular Engineering and Forestry, Wildlife, and Fisheries, University of Tennessee, Knoxville, Knoxville, Tennessee, United States, 7 Center for Molecular Biophysics, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States, 8 Department of Chemical and Environmental Engineering, University of California, Riverside, Riverside, California, United States
Show AbstractLignocellulosic biomass is the most abundant source of organic carbon on Earth and presents the only option with the potential to economically and sustainably replace fossil resources for large-scale production of renewable chemicals, materials, and liquid fuels. However, past methods to achieve the facile deconstruction of biomass has been challenged by processing difficulties, low product recovery, and excessive materials and energy costs. We highlight here the recent developments of novel CELF (Co-solvent Enhanced Lignocellulosic Fractionation) technology to achieve efficient fractionation of hemicellulose, cellulose, and lignin from biomass to enable their facile conversion to biofuels and biomaterials in future biorefineries. At lower reaction severities, we have recently applied CELF to solubilize lignin producing a cellulose-rich material from poplar wood that can be completely solubilized by thermophilic microbes without added enzymes in just two days culture. In another configuration, CELF treated corn stover paired with high solids ethanol fermentation achieved equivalent performance as compared to pure sugar fermentations while co-processing lignin to polyurethanes. At higher reaction severities, a pathway to high yield co-production of methylated furans from furfural and HMF was developed using a supported non-noble catalyst. We also demonstrate how atomic-level interactions simulated by supercomputers could help understand key chemical mechanisms responsible for biomass breakdown to help improve design of conversion processes. The central theme of this discussion will be towards maximizing total carbon utilization of biomass using CELF and a special focus on lignin valorization.
9:30 AM - BI02.07.03
Sustainable Bio-Diesel Production via Magnetic Induction Heating Assisted by Heterogenous Magnetic Catalyst
Arfa Nawaz 1 , May Lim 1
1 , University of New South Wales, Sydney, New South Wales, Australia
Show AbstractBio-diesel, a renewable green fuel, has been positioned as the future fuel for diesel engines owing to ever-increasing fuel demand and limiting oil reserves. Currently, biodiesel is produced via the transesterification process that is driven by homogenous catalysts such as sodium hydroxide or potassium hydroxide. The use of these homogeneous catalysts has been associated with costly downstream purification and wastewater production, which reduces the commercial viability of the bio-diesel as a renewable fuel. Moreover, the reaction is usually heated via conventional heat transfer where the power transmission is typically very low (~20 W cm-1). Magnetic induction heating is an alternative heating technology that can provide direct and localized heating with 1500 times higher power transmission than conventional heating method [1]. Heat is produced when magnetic susceptible materials are placed under an alternating current magnetic field; the magnetic material can therefore be used as a thermal source to drive a chemical reaction. Moreover, the development of magnetic heterogeneous catalyst can overcome the abovementioned issues related to downstream purification and wastewater production [2]. Herein, the use of iron sand (a natural occurring magnetic material), as well as micro and nano-sized magnetite (Fe3O4) particles as a thermal source in magnetic induction heating and as a magnetic catalyst support for bio-diesel production is reported. The effects of applied magnetic field strength and the particle size on heating efficiency, FAME yield and FAME composition were evaluated. The magnetite particles were shown to improve the FAME yield by constituting a bi-functional catalyst system where calcium oxide is Lewis base and magnetite is Lewis acid. The effectiveness of induction heating was also compared to conduction heating under comparable reaction and catalyst condition.
1. Benkowsky, G., Induktionserwärmung: Härten, Glühen, Schmelzen, Löten, Schweißen; Grundlagen und praktische Anleitungen für Induktionserwärmungsverfahren, insbesondere auf dem Gebiet der Hochfrequenzerwärmung. 1990: Verlag Technik.
2. Meher, L.C., D. Vidya Sagar, and S.N. Naik, Technical aspects of biodiesel production by transesterification—a review. Renewable and Sustainable Energy Reviews, 2006. 10(3): p. 248-268.
9:45 AM - BI02.07.04
Investigating the Impact of Blended Feedstocks on Vapor-Phase Pyrolysis Products and Pyrolytic Bio-Oil Properties
Charles Edmunds 1 , Choo Hamilton 1 , Timothy Rials 1 , Nicole Labbe 1
1 Center for Renewable Carbon, University of Tennessee, Knoxville, Tennessee, United States
Show AbstractProducing renewable and sustainable fuels and chemicals through biomass conversion is key for the future growth of the United States’ bioeconomy. Pyrolysis is the rapid heating of organic material in an anoxic environment, and has been identified as a leading biomass conversion technology for the production of liquid fuels and chemicals. A major challenge to the large-scale commercialization of thermochemical conversion technologies is securing an abundant feedstock supply that is economical and exhibits a low degree of variability. We propose blending different types of biomass to produce a uniform and high-quality feedstock as a solution. The US agricultural and forestry sectors have the potential to supply a vast amount of renewable cellulosic biomass such as energy grasses and forestry residues. However, a better understanding of how the chemical and physical properties of blended feedstocks influence the yield and quality of its thermochemical conversion products is required. Thus, this research investigates the pyrolytic conversion of binary blends of switchgrass and two different grades of pine residues. We utilized micro-scale pyrolysis instrumentation coupled with gas chromatography-mass spectrometry (Py-GC/MS) to measure the vapor-phase pyrolysis of a larger number of blended samples. Next, we used a smaller number of switchgrass/pine residue formulations as feedstocks for an intermediate-scale pyrolysis reactor to produce bio-oil. Discussion will be focused on the interactions between blended feedstock properties and the composition and yield of the resulting vapor-phase pyrolysis products and bio-oil. Results demonstrate that blending allows the use of lower-quality biomass sources while controlling the feedstock quality specifications.
BI02.08: Energy Storage and Production I
Session Chairs
Michael Molinari
Laurene Tetard
Wednesday PM, November 29, 2017
Sheraton, 3rd Floor, Gardner AB
10:30 AM - *BI02.08.01
Agricultural Waste Derived Activated Carbon for Electrochemical Energy Storage
Yunya Zhang 1 , Zan Gao 1 , Ningning Song 1 , Xiaodong Li 1
1 , University of Virginia, Charlottesville, Virginia, United States
Show AbstractWe converted recycled paper and banana peel into hierarchically porous activated carbon scaffolds. The activated carbon scaffolds were wrapped with graphene to improve sulfur loading and cathode conductivity in lithium sulfur batteries. The activated carbon graphene Li-S battery exhibited superior life span with an excellent capacity retention rate. An activated paper carbon interlayer was sandwiched between the Li anode and the separator to suppress the degradation of Li anode by protecting the Li anode from unfavorable reactions, further stretching the battery lifespan. The porous anode interlayer configuration should find more applications in other porous bio-mass materials for energy storage devices. The agricultural waste derived carbon presents a new promise for the design and fabrication of high performance energy storage devices while reducing material waste.
11:00 AM - BI02.08.02
Application of Low-Cost Cu–Sn Bimetal Alloy as Oxygen Reduction Reaction Catalyst for Improving the Performance of Microbial Fuel Cell
Md Noori 1 , Gaurav Dhar Bhowmick 1 , Bikash Tiwari 2 , M.M. Ghangrekar 2 , C K Mukherjee 1
1 Agricultural and Food Engineering, Indian Institute of Technology, Kharagpur, Kharagpur India, 2 Civil Engineering, Indian Institute of Technology, Kharagpur, Kharagpur India
Show AbstractRecently, microbial fuel cell (MFC) has been devised as low – cost solution for energy tapping from numerous solid and liquid wastes with a view to minimize waste hazard and to solve upcoming energy problems. The oxygen reduction reaction (ORR) in various studies was found as bottle neck in the performance of MFCs, which however was solved by catalyzing ORR using suitable catalysts. Platinum or other novel elements and alloys possess extravaganza characteristics to reduce overpotential losses in this chemical reduction process, but high cost associated with these elements or alloys demonstrated poor applicability in MFCs. Therefore, in this experiment a new bimetal low – cost Cu – Sn alloy was tested as catalyst for ORR in MFC and the results were compared with the commercially available 10% w/w Pt-C catalyst. The cyclic voltammetry (CV) for evaluating ORR of test cathode containing Cu-Sn catalysts at a loading of 2 mg/cm2 under oxygen saturated environment displayed sharp and large ORR current peak at applied potential of 0.01 mV, showing less overpotential demand for ORR. In addition, as compared to the Pt-based cathode, the Cu – Sn catalytic cathode had higher CV enclosed area, which demonstrated comparatively large capacitive redox current. Maximum power density of 457 mW/m2 obtained from MFC using Cu – Sn catalyst was found to be slightly higher than the power density of 446 mW/m2 recovered from the MFC using Pt treated cathode. The biochemical conversion of direct electric current in Cu – Sn based MFC at coulombic efficiency of 55.8% from 92% of total supplied organic matter (i.e. chemical oxygen demand) was also found to be higher with respect to Pt-based MFC (50% and 90%, respectively). These results also indicate the Cu – Sn based MFC as a good performer in terms of wastewater treatment. Furthermore, the sustainable power production per unit cathode fabrication cost of 14 W/$ was 33-times lower than the power production cost of 0.42 mW/$ associated to MFC with Pt-based cathode. This study demonstrated application of extremely low – cost Cu – Sn bimetal alloy as excellent ORR catalyst in MFC and would be very helpful to commission larger MFCs for real – time application for harvesting energy from wastewater and other potential wastes.
11:15 AM - BI02.08.03
Chemical Activation of Fast Pyrolysis Biochar for the Supercapacitor Electrode Application
Seunghyun Yoo 1 , Nanfei He 2 , Steve Kelley 1 , Wei Gao 2 , Sunkyu Park 1
1 Forest Biomaterials, North Carolina State University, Raleigh, North Carolina, United States, 2 Textile Engineering, North Carolina State University, Raleigh, North Carolina, United States
Show AbstractBiochar is a major byproduct of fast pyrolysis process and it is considered as an inexpensive solid carbon source. However, the fast-growing electric vehicle market is now function as a game changer of carbon material trading market. Biochar can be used as supercapacitor electrode material after activation process. The economic value of supercapcitor-grade carbon electrode is 2 to 5 times higher than that of conventional adsorbent-grade carbon. Our objective in this work is to understand the complex reactions associated with development of activated carbon and evaluate its electrochemical performances. The physical and the electronic structures of loblolly pine (Pinus Taeda) derived biochar and activated carbon were systematically analyzed by interpreting electron energy loss spectra, BET surface areas, x-ray diffraction patterns, and electrical conductivities. SEM and STEM images were also collected to better understand the formation of biomass derived carbon structures. Specifically, loblolly pine was carbonized at four different temperatures (300°C, 350°C, 500°C, and 700°C) using quartz tube furnace. Then, four biochar samples were impregnated with NaOH and heated to 800°C to produce an ‘activated’ carbon. Carbon sp2 content was quantitatively determined by electron energy loss spectroscopy. The sp2 content of biochar produced at 300°C is 58% and the sp2 content gradually increases to 73% as the carbonization temperature is elevated to 700°C. The sp2 contents of activated carbon are 74%, 78%, 79%, and 85%, where precursor biochar carbonization temperatures are 300°C, 350°C, 500°C, and 700°C. Polyaromatic cluster size and graphitic stacking thickness were determined by analyzing the x-ray diffraction patterns. The average size of the polyaromatic clusters and the graphitic stacking thickness both increased as the carbonization temperature increased. BET surface areas of activated carbon are 959.9cm2/g, 872.8cm2/g, 435.4cm2/g, and 16.2cm2/g. Then produced activated carbon is fabricated into supercapcitor electrode and its electrochemical performances were tested. The resulting supercapacitor had a high capacitance of 74 F/g at 20 mV/s scan rate (activated carbon derived from 300°C-produced biochar). Its highest energy density was 2.54 Wh/kg and highest power density was 725.44 W/kg. The details of biomass derived carbon electrical property development during the fast pyrolysis and the activation will be further discussed.
11:30 AM - BI02.08.04
Potentiodynamic Studies of the CO2 Generation on Pt, Pt/SnO2 and Pt/Rh/SnO2 Nanoparticles During the Electro-Oxidation of Ethanol
Xiaowei Teng 1 , Guangxing Yang 1
1 , Univ of New Hampshire, Durham, New Hampshire, United States
Show AbstractDirect ethanol fuel cells (DEFCs) are a promising technology for the generation of electricity via the direct conversion of ethanol into CO2, showing higher thermodynamic efficiency and volumetric energy density than hydrogen fuel cells. However, implementation of DEFCs is hampered by the low CO2 selectivity during the ethanol oxidation reaction (EOR). Comprehensive understanding of the electro-kinetics and reaction pathways of CO2 generation via C-C bond-breaking is not only a fundamental question for electro-catalysis, but also a key technological challenge since practical implementation of DEFC technology is contingent on its ability to selectively oxidize ethanol into CO2 to achieve exceptional energy density through 12-electron transfer reaction. Here, we present comprehensive in situ potentiodynamics studies of CO2 generation during the EOR on Pt, Pt/SnO2 and Pt/Rh/SnO2 catalysts using a house-made electrochemical cell equipped with a CO2 microelectrode. Highly sensitive CO2 measurements enable the real time detection of the partial pressure of CO2 during linear sweep voltammetry measurements, through which electro-kinetics details of CO2 generation can be obtained. In situ CO2 measurements provide the mechanistic understanding of potentiodynamics of the EOR, particularly the influence of *OH adsorbates on CO2 generation rate and selectivity. Density functional theory (DFT) simulations of Pt, Pt/SnO2, and Pt/Rh/SnO2 surfaces clarify reaction details over these catalysts. Our results show that at lower potential, inadequate *OH adsorbates impair the removal of reaction intermediates, and thus Pt/Rh/SnO2 exhibited the best performance toward CO2 generation, while at higher potential, Rh sites were overwhelmingly occupied (poisoned) by *OH adsorbates, and thus Pt/SnO2 exhibited the best performance toward CO2 generation.
BI02.09: Energy Storage and Production II
Session Chairs
Charles Cai
Loukas Petridis
Wednesday PM, November 29, 2017
Sheraton, 3rd Floor, Gardner AB
1:45 PM - *BI02.09.01
Processing Structure Relationships for the Use of Lignin Based Carbons in Energy Storage Applications
David Harper 1
1 , University of Tennessee, Knoxville, Tennessee, United States
Show AbstractWe have demonstrated that lignin can be converted into carbon materials can be used to displace mineral and fossil derived sources. Lignin’s unique chemical structure offers some disadvantages, but also some unique properties that prove superior to other carbon sources. Lignin develops nano-structured crystalline domains that hold significant promise for energy storage. The morphology of these crystalline domains is highly dependent on the gas environment of carbonization and ultimate reducing temperatures. Nevertheless, little is known about the kinetics of graphitization in reactive solid-gas environments and the influence of lignin’s physiochemical structure on carbon morphology. Specifically, we investigate processing variables include the moisture content, temperature, and duration of thermal stabilization, pyrolysis, and reduction. The resulting materials are characterized at the atomic- and micro-scales using electron microscopy, elemental analysis, neutron scatter, and x-ray diffraction. Lithium ion anode materials made from these carbons exhibit specific capacities in the range of 300–450 mAh g-1 based on the mass of lignin material, which compares favorably to flake graphite. High temperature carbonization, 2000 °C, produces large cryastine domains but lower overall crystallinity compared to 1050 °C. This led to lower overall battery capacity. Coulombic efficiencies are over 98% for most cycles. Consequently, a properly designed carbonization process for lignin is well suited to generating low-cost, high-efficiency electrodes.
2:15 PM - BI02.09.02
Semi-Interpenetrating Network Based on Crosslinked Poly(vinyl alcohol) and Quaternized Poly(2,6-dimethyl-1,4-phenylene oxide) as OH - Conducting Membranes
Ketian Zhang 1 , Michael McDonald 1 , Paula Hammond 1
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Show AbstractAlkaline fuel cells enable the use of non-noble metal catalysts. However, its development faces challenges from either the low OH- conductivity or the poor mechanical strength of the anion exchange membranes. In this work, we synthesized quaternized poly(2,6-dimethyl-1,4-phenylene oxide) (qPPO) with a high degree of quaternization, which provided high OH- conductivity. However, the neat polymer was brittle. Therefore, poly(vinyl alcohol) (PVA) and its crosslinking agent, glutaraldehyde, were dissolved together with qPPO in dilute HBF4 aqueous solution. Upon drop casting and drying, PVA was crosslinked and it formed a semi-interpenetrating network with qPPO. As the crosslinked PVA reinforced qPPO, the membranes can be made as thin as 10 microns while still preserve decent mechanical strength. The qPPO-to-PVA ratio was optimized considering both the conductivity and the tensile strength of the membranes.
BI02.10: Energy and Water
Session Chairs
David Harper
Swadeshmukul Santra
Wednesday PM, November 29, 2017
Sheraton, 3rd Floor, Gardner AB
3:30 PM - BI02.10.01
p-n Based Photoelectrochemical Device for Water Splitting Application—Alpha-Hematite (α-Fe2O3)–Titanium Dioxide (TiO2) as N-Electrode & Polyhexylthiophene (RRPHTh) - Nanodiamond (ND) as P-Electrode
Hussein Alrobei 1 2 , Hye Young Lee 1 , Manoj Ram 1
1 , University of South Florida, Tampa, Florida, United States, 2 , Sattam Bin Abdullaziz University , Riyadh, Alkharj, Saudi Arabia
Show AbstractAlpha (α)-hematite (Fe2O3) has received considerable attention as photoanode for water splitting application in a photoelectrochemical (PEC) device. α-Fe2O3 is chemically stable, abundant in nature with a band gap of 2.0-2. 2eV allowing to absorb significant part of visible light. However, its has drawback of high recombination rate of electron –hole pair, and reveals low concentration causes degradation of PEC device performance [1]. In common with Fe2O3, titanium dioxide (TiO2) has been known as one of the most explored electrode material due to its physical and chemical stability in aqueous and non-toxicity. However, TiO2 has large bandgap (3.0-3.2 eV) that results in absorbing small fraction on visible light (4-5 %) [2]. Incorporation of TiO2 in α-Fe2O3 could achieve better efficiencies as photoanode by enhancing the electron concentration, low combination rate, and both materials can have wide range of wavelength which could absorb light in both UV and visible spectrum range [1]. However, the photoanode properties α-Fe2O3 with different concentrations of TiO2 are mostly unknown. Under this work, α-Fe2O3-TiO2 nanomaterial was synthesized using a hydrothermal method. The α-Fe2O3-TiO2 nanomaterials containing different weight percentage (2.5, 5, 16, 50) of TiO2 with α-Fe2O3 were characterized using SEM, XRD, UV-Vis, FTIR and Raman techniques, respectively. The photoelectrochemical water splitting properties of α-Fe2O3-TiO2 nanomaterials were investigated by chronoamperometry and cyclic voltammetry techniques. The α-Fe2O3-TiO2 nanomaterials has shown enhanced photoelectrochemical properties than metal doped α-Fe2O3 photoelectrochemical devices.
3:45 PM - BI02.10.02
Integrated Triboelectric Nanogenerator Array Based on Air-Driven Membrane Structures for Harvesting Water Wave Energy
Liang Xu 1 , Yaokun Pang 1 , Chi Zhang 1 , Tao Jiang 1 , Xiangyu Chen 1 , Jianjun Luo 1 , Wei Tang 1 , Xia Cao 1 , Zhong Lin Wang 1 2
1 , Chinese Academy of Sciences, Beijing China, 2 , Georgia Institute of Technology, Atlanta, Georgia, United States
Show AbstractWater wave energy is a promising clean and renewable energy source, yet little has been exploited due to the high cost and a number of engineering challenges with present technologies, which are mainly based on an electro-magnetic generator to transform the mechanical energy into electricity. The triboelectric nanogenerator (TENG), based on the conjunction of contact electrification and electrostatic induction, is an emerging energy harvesting technology, which has the merits of low cost, light weight, simple structure and abundant choice of materials. It shows particular advantages in transforming low frequency mechanical energy into electricity, and is likely to be a brand new solution for utilizing water wave energy in the ocean and other water bodies. Currently, two major challenges lie in how to resonate with the water wave to most effectively harvest water wave energy and how to integrate and drive large-scale TENG units to multiply the output. This work demonstrates a device corresponding to such two issues. By an elaborately designed spring-levitated oscillator structure, tunable resonate state at low frequencies with water waves could be achieved in the device. By using deformable air-driven membrane structures, which utilizes air as a medium to transfer and distribute harvested energy, high-density TENG units can be driven synchronously and effectively. As a demonstration, a device integrating 38 TENG units is fabricated. It shows high output of transferred charges per cycle of 15 μC, short-circuit current of 187 μA and optimized peak power density of 13.23 W m-3. It can easily light up 600 LEDs with harvested water wave energy. The scale of the integrated TENG array can be augmented easily, as would further enhance the output. Such air-driven TENG is first demonstrated. It shows excellent scalability, and extraordinary flexibility in spatial arrangement due to the fluidity of air medium, thus is promising to be further developed into ultra-large-scale and high-density TENG array apparatus with simple structure and low cost, showing exciting perspective for using TENG technology as a novel technical route to exploit ocean energy, for powering ocean instruments and supplying electricity to the grid.
4:00 PM - BI02.10.03
Bismuth Oxyhalide Particles as a Candidate Material for Water Purification
Fan Yang 1 , Miriam Rafailovich 1
1 , Stony Brook University, Stony Brook, New York, United States
Show AbstractNano or micro sized particles, such as Titanium Dioxide, have been used in water purification. Besides the ability to purify water, to find the best particle to use, toxicity of the material and the cost while using it would be two important aspects taken into consideration.
We investigated the cytotoxicity of Bismuth Oxyhalide micro particles, which is a material with a photocatalytic activity under visible light, to human dermal fibroblasts. We found a critical concentration under which particles did not have adverse effects on fibroblasts. Cells were then cultured with particles at this critical concentration under the exposure of visible light to test the cytotoxicity of the material while it was being activated.
Our results indicate that Bismuth Oxyhalide particles had no adverse effects on human dermal fibroblasts under a certain concentration regardless of the photocatalytic activity. We consider these particles as a promising candidate material for water purification, since they are safe at a controlled concentration, and would decrease energy consumption as they don’t need UV light to be activated but only visible light.
This work was supported by the NSF, Inspire #1344267.
4:15 PM - BI02.10.04
Flexible Anti-Clogging Graphite Film for Scalable Solar Desalination by Heat Localization
Varun Kashyap 1 , Abdullah Al-Bayati 1 , Seyed Mohammad Sajadi 1 , Peyman Irajizad 1 , Sing Hi Wang 1 , Hadi Ghasemi 1
1 , University of Houston, Houston, Texas, United States
Show Abstract
Solar-thermal energy conversion is an economically promising route for power generation, desalination, and distillation. With recent introduction of heat localization concept, highly efficient solar harvesting has garnered more attention with accelerated research efforts. In this concept, the material structure localizes solar energy at the desired interface minimizing the heat loss by the bulk phase occurring in conventional solar bulk heating approaches. However, development of materials for long-term solar desalination through heat localization remains an open challenge due to clogging of the structure after a short period of time. Herein, we report a new efficient and flexible material structure for solar-desalination with anti- clogging characteristics. The material structure has a porous polymer skeleton with embedded graphite flakes and carbon fibers. The geometry of pores in this structure and their surface characteristics prevent any salt accumulation in the material structure. We have demonstrated five orders of desalination of highly-salty brine (1.52×105 mg/L) in a long-time performance with no change in its efficiency. The performance of this structure in the laboratory and outside environment is assessed. This cost-effective and durable material along with its easy fabrication procedure provides a path towards large- scale efficient solar desalination.