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Nanoparticle Interactions in Environmental Systems:
08:00am - 09:55am USA / Canada - Eastern - August 22, 2021 | Room: B402
Adeyemi Adeleye, Organizer, University of California Irvine; Arturo Keller, Organizer, University of California, Santa Barbara; Dr. Yiming Su, Presider, University of California Los Angeles; Virender Sharma, Presider, Texas AM University
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Division/Committee: [ENVR] Division of Environmental Chemistry

This session seeks leading edge research on the interactions of nanoparticles (metallic, carbonaceous, organic, and nanoplastics) with biogenic, geogenic, and anthropogenic components in the natural environment. The interactions and processes of interest include nanoparticle transformations in different media, surface accumulation of inorganic and organic substances, transport through biological membranes, and nanoparticle-induced redox reactions. Of particular interest are studies on novel nanoparticles (e.g., nanohybrids, nanocomposites, and metal-organic frameworks) (1) used in environmentally-relevant applications (e.g., agriculture, remediation, and CO2 capture), (2) incidentally generated from manufacturing (e.g. nanoplastics produced during 3D printing), or that reach the environment due to their use in outdoor environments (e.g., coatings, and personal care products). We also seek studies that address risk of exposure to nanoparticles, by human and ecological receptors.

Sunday
Introductory Remarks
08:00am - 08:05am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid

Sunday
Opportunities of nanotechnology in sustainable agricultural practices
08:05am - 08:30am USA / Canada - Eastern - August 22, 2021 | Room: B402
Dr. Yiming Su, Presenter, University of California Los Angeles; Xuefei Zhou; Yalei Zhang; Huan Meng; Tian Xia; Arturo Keller, University of California, Santa Barbara; Greg Lowry, Carnegie Mellon University; David Jassby
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Nanotechnology has been increasingly recognized as an important approach to achieve sustainable development of agriculture, particularly in the field of fertilizers and pesticides innovation. However, to promote the practical application of nanotechnology, it is essential to evaluate the economic and environmental benefits of nanotechnology to different crops. In the present study, we carry out a cost-benefit analysis about the application of nano fertilizers and pesticides in comparison with conventional formulations, identify the potential areas for implementing nano fertilizers and pesticides, and propose future studies needed to pave the way for wide application of nanotechnology in agricultural practices.
Sunday
Withdrawn
08:30am - 08:50am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid

Sunday
Biomolecular corona formation on copper oxide nanoparticles in pumpkin xylem fluid
08:50am - 09:10am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Coatings of biomolecules—biomolecular corona—acquired when nanoparticles interact with biological media, have been shown to influence the distribution, fate, and toxicity of nanoparticles in animal and bacterial systems. Mechanistic insight into the influence of biomolecular coronas on nanoparticle transport within plants is needed to understand the nanoparticle–plant interactions important for both the development of nano-enabled agriculture and to assess the impacts of inadvertent exposure to nanoparticles. We examined the interactions between copper oxide nanoparticles and pumpkin xylem fluid as a first step toward understanding biomolecular corona formation in plant vasculature systems. We find the corona formed is composed primarily of proteins, despite a higher concentration of carbohydrates in xylem fluid, and the most abundant proteins in the corona are not the most abundant ones in the xylem fluid. Additionally, the nanoparticle corona evolves over time with protein–nanoparticle interactions exhibiting long-term stability, while carbohydrate–nanoparticle interactions are mostly transient.
Sunday
Withdrawn
09:10am - 09:30am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid

Sunday
Towards a general framework for quantitative assessment of the potential risks associated with soil release of reduced carbon species
09:30am - 09:50am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Some reduced carbon species enriched in aromatic functionalities can provide ecosystem services when used as soil amendments. Charcoal has been used for this purpose for millennia. Biochar (biomass intentionally pyrolyzed for soil amendment) has been recently designed to mimic charcoal’s environmental benefits. Here we consider a third family of reduced carbon species that could be used for soil amendment: engineered carbon materials produced from natural gas pyrolysis (i.e. full decomposition of methane into solid carbon and hydrogen). We term these materials generically C0. C0 can be designed to be chemically similar to charcoal or biochar, with the aim of providing similar ecosystem services (improved soil water retention, improved nutrient retention, reduced fertilizer runoff, reduced soil CH4 and N2O production, etc.). Environmental risk assessment is a crucial first step before discussion of use of these materials as soil amendment. Here we begin this process by developing a procedure to assess the release of dissolved materials from C0. We report on the amount and chemistry of dissolved organic carbon (DOC) released by C0 subjected to a range of environmental aging treatments. Specifically, we subjected C0 to 1) 10-day UVA irradiation with light intensity of 50 µW/cm2, mimicking UV-driven reactions likely to occur in natural waters, 2) H2O2 oxidation (30% and 5%), mimicking natural, long-term environmental microbial oxidation, and 3) 10 mg L-1 monochloramine (NH2Cl) oxidation, mimicking reactions that could occur were C0 materials to inadvertently enter drinking water treatment systems. DOC released from C0 was < 2 mg L-1 regardless of aging method. This is significantly lower than DOC released from wildfire-derived charcoal (up to 70 mg L-1), soft wood biochar pyrolyzed at 550 and 700 °C, and commercial biochar under the same oxidation conditions. UVA 10 days is the most oxidizing treatment for C0. UVA-aged C0 had a relatively higher O/C ratio of 0.019±0.006. However, all three aging methods were incapable of significantly oxidizing C0. Next steps involve determining the chemical nature of DOC species released.
Sunday
Concluding Remarks
09:50am - 09:55am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid

Nanoparticle Interactions in Environmental Systems:
10:30am - 12:25pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Adeyemi Adeleye, Organizer, University of California Irvine; Arturo Keller, Organizer, University of California, Santa Barbara; Dr. Yiming Su, Presider, University of California Los Angeles; Virender Sharma, Presider, Texas AM University
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Division/Committee: [ENVR] Division of Environmental Chemistry

This session seeks leading edge research on the interactions of nanoparticles (metallic, carbonaceous, organic, and nanoplastics) with biogenic, geogenic, and anthropogenic components in the natural environment. The interactions and processes of interest include nanoparticle transformations in different media, surface accumulation of inorganic and organic substances, transport through biological membranes, and nanoparticle-induced redox reactions. Of particular interest are studies on novel nanoparticles (e.g., nanohybrids, nanocomposites, and metal-organic frameworks) (1) used in environmentally-relevant applications (e.g., agriculture, remediation, and CO2 capture), (2) incidentally generated from manufacturing (e.g. nanoplastics produced during 3D printing), or that reach the environment due to their use in outdoor environments (e.g., coatings, and personal care products). We also seek studies that address risk of exposure to nanoparticles, by human and ecological receptors.

Sunday
Introductory Remarks
10:30am - 10:35am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid

Sunday
Role of foliar biointerface properties and nanomaterial chemistry in controlling Cu transfer into tomato and Arabidopsis thaliana leaf tissue
10:35am - 11:00am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Although the use of nanoscale materials in agriculture is increasing, an understanding of the mechanisms of foliar uptake across the leaf surface and the role of material properties in that process remains incomplete. Three copper nanomaterials (copper oxide NPs, copper oxide nanosheets [NS] and copper phosphate NS) and copper sulfate were applied to tomato and wild type/mutant Arabidopsis thaliana leaves. The Arabidopsis mutants had differences in cuticle thickness and stomatal density. After application, three separate fractions of Cu (surface attached, cuticle, interior leaf tissue) were isolated from the leaf at 15 min to 8 h. For tomato, the nanoscale Cu was used to foliar treat tomato on a weekly basis in greenhouse and field experiments in the presence of the pathogen Fusarium oxysporum. For both tomato and wild type A. thaliana treated with copper sulfate, Cu accumulation and retention in the cuticle was 7-28 fold greater than the nanomaterials. Also, 2.4 times more Cu was retained in the cuticle from the NPs than the nanosheets, demonstrating that nanoscale morphology and composition mediate Cu accumulation in leaf tissue. After 8 h, the amount of Cu present in the interior leaf tissue of A. thaliana increased-stomatal mutants was 8.5-44.9% greater than the decreased stomatal mutants across all Cu types. A direct comparison of Cu tissue concentrations for increased-cuticle and decreased-cuticle mutants showed non-significant differences in element content. Exogenous pre-application of abscisic acid to close the stomata eliminated the difference in Cu uptake between A. thaliana stomatal mutants. In the greenhouse study, foliar applications of the nanoscale Cu increased tomato seedling biomass by 90% as compared to diseased and ionic Cu controls. In the field, copper phosphate NS reduced disease progress by 26.0% and increased fruit yield by over 45.5% per plant relative to the other treatments in diseased soil. These findings increase our understanding of the mechanisms of Cu nanomaterial attachment to and transfer across the plant leaf biointerface and enable optimization of material properties for effective and sustainable strategies as part of nano-enabled agriculture.
Sunday
Uptake and translocation of mesoporous SiO2-coated ZnO nanoparticles in tomato plants following foliar application
11:00am - 11:20am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Nanocarriers can provide controlled and sustained micronutrient delivery to food crops via foliar application, which can potentially reduce energy and water consumption, and soil and groundwater pollution. However, the uptake and translocation of nanocarriers encapsulated micronutrient have not been demonstrated. The objectives of this study were to compare the efficiency of Zn uptake using core-shell ZnO nanoparticles encapsulated in a nano sized mesoporous SiO2 shell (ZnO@SiO2 NPs) to bare ZnO nanoparticles (ZnO NPs), and Zn salt (ZnCl2) to tomato plants (Solanum lycopersicum), and to assess the particulate translocation of ZnO@SiO2 NPs to different plant parts. In this study, ~70 nm ZnO@SiO2 NPs with ~23 nm ZnO NP core were synthesized for delivery of Zn to plants by foliar uptake. In a model plant media (pH = 5), compared to the rapid dissolution of bare ZnO NPs (90% Zn dissolution after 4 h), ZnO@SiO2 NPs released Zn at a slower rate (40% Zn dissolution after 3 weeks). The slow and controlled release of ZnO@SiO2 NPs enabled a sustained Zn delivery over a longer period. A dosing of 40 µg Zn micronutrient of either ZnO@SiO2 NPs suspension, ZnO NPs suspension or ZnCl2 solution was performed on a single leaf after 2 weeks of plant growth period for different Zn treatments. The amount of Zn translocated in different treatments were measured by acid digestion of the plant followed by Inductively Coupled Plasma Mass Spectroscopy and Inductively Coupled Plasma Optical Emission Spectroscopy analyses. For ZnO NPs treatment, no Zn uptake was observed after 2 days of dosing. For ZnCl2 treatment and ZnO@SiO2 treatment, similar amounts of Zn uptake and translocation to upper leaves, shoots were observed 2 days after dosing (15.5 ± 2.4 µg Zn and 11.4 ± 2.2 µg Zn for ZnCl2 treatment and ZnO@SiO2 treatment, respectively). Most ZnO@SiO2 NPs were translocated in plants in its particulate form as evident from single particle inductively coupled plasma mass spectrometry measurement on different plant parts and transmission electron microscopy analysis on the cross section of the dosed leaf. These results suggest that the SiO2 shell enhanced the uptake of ZnO NPs in tomato plants. ZnO@SiO2 NPs had a better delivery efficiency compare to bare ZnO NPs and is likely to be able to provide Zn over a significant period of the plant growth period, reducing the need for multiple applications.
Sunday
Transcriptome responses to environmental stresses in crops exposed carbon nanotubes and graphene
11:20am - 11:40am USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Carbon-based nanomaterials (CBN) such as carbon nanotubes (CNT) and graphene can protect plant cells against the harmful influence of abiotic stresses including drought and high salinity. To understand the biological mechanisms of such unique effects of CBNs we analyze the total gene expression in plants (rice, tomato) exposed to environmental stress in presence of CBNs (CNT, graphene) by NGS. The application of CNT or graphene resulted in full or partial restoration of expression of 458 and 1620 genes respectfully affected by water-deficit stress in rice. CBN treatment of NaCl-exposed tomato seedlings led to full or partial restoration of 1639 and 1391 salt-affected transcripts, respectively. The genes with fully or partially restored expression were described as stress-response genes and transcriptional factors (aquaporins, dehydrins, heat shock proteins/co-chaperons, NAC, WRKY) and were associated with key stress-signaling pathways (ABA-signaling, InsP3 signaling, MAPK signaling) in tested species.
Sunday
Impacts of porous silica-nanoencapsulated pesticide on plant growth and soil microbial community
11:40am - 12:00pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Conventional pesticide applications are highly inefficient and it is estimated that over 90% of all pesticides applied are wasted due to off-target delivery, binding to soil, runoff and premature degradation. The use of nanocarriers to promote targeted delivery of pesticides have the potential to revolutionize current agricultural practices. In this work, we encapsulated azoxystrobin, a broad-spectrum fungicide widely used in agriculture, within porous-hollow silica nanoparticles (PHSN) and provided the formulation to Solanum lycopersicum to assess the effects of nanoencapsulated azoxystrobin on the plant growth and soil microbial community. A total of 66% of the total azoxystrobin was successfully encapsulated within the PHSN over 8 days of loading. The loading rate increased exponentially in the first 2 days and then gradually declined from that point onwards until it plateaued at day 8. The release profiles showed that while pure azoxystrobin formulation would provide 100% release within hours, the encapsulated pesticide followed a slow, controlled release over days, reaching 43.5 ± 5.8% after 10 days. The treatments with pesticide demonstrated an inhibitory effect of azoxystrobin in the plant development, with the free pesticide treatment yielding less biomass compared to other treatments and controls. Encapsulated azoxystrobin also inhibited the plant growth when compared to control treatments, however, to a lesser extent than the free pesticide. Five phenotypic traits were measured to quantify the effects on the plant health, including dry biomass, length of roots, length of shoot, number of leaves and length of the longest leaf. The soil microbial community shifted to some extent in all treatments, with the pesticide-dosed treatments showing more significant changes. There is, however, no clear trend to determine whether these changes were responsible for the changes in plant growth previously observed, because none of the shifts negatively impacted key bacterial and fungi communities directly related to nutrient cycling of the soil. Overall, the use of encapsulated pesticide within porous nanocarriers did not negatively impact the plant growth and soil microbiota, and provided sustained release of pesticides.
Sunday
Nutritional and agronomical impact of soil and foliar application of zinc oxide nanoparticles in corn plants under NPK fertilization
12:00pm - 12:20pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Miss Elena Venegas Rodriguez, Presenter, WNMU; Dr. Illya Medina Velo, Presenter, Houston Baptist University
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Agricultural practices highly rely on the use of fertilizers, such as nitrogen, phosphorus, and potassium (NPK). New approaches, including the use of nanoparticles, have been explored to enhance fertilization efficiency. The present study evaluated the effects of zinc oxide nanoparticles (nano-Zn) and zinc sulfate (ionic-Zn) amendment on corn (Zea Mays) development and yield. Plants were grown in a Zn-deficient soil (loamy sand, pH 7.8) until corn production. Plants were soil- and foliar-treated with nano-Zn or ionic-Zn at 30 mg/kg, under low (90:60:60 mg/kg) and high (180:120:120 mg/kg) NPK fertilization. Agronomical parameters showed increased root and stem biomass (89% and 135% higher than control, respectively) by soil-added nano-Zn under low-NPK fertilization. While both ionic- and nano-Zn enhanced biomass production by 54% disregarding the NPK level. Foliar application of ionic-Zn increased chlorophyll by 44%, disregarding the NPK level. Results on Zn uptake and nutrient accumulation will be shared at the meeting.
Sunday
Concluding Remarks
12:20pm - 12:25pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid

New Frontiers and Opportunities for Chemistry: Materials
02:00pm - 04:00pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Dr. H.N. Cheng, Organizer, Presider, USDA Agricultural Res. Service; Young-Shin Jun, Organizer, Presider, Washington University in St. Louis; Martin Kociolek, Organizer, Presider, Penn State Erie, The Behrend College; Michael Morello, Organizer, Presider, Retired: PepsiCo R&D
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual
Division/Committee: [COMSCI] Committee on Science

Chemistry is becoming increasingly multidisciplinary, and the future chemists and chemical engineers may find increasing opportunities to apply their chemical knowledge in new or expanded areas. Certainly, the skills and the tools of chemistry are positively needed to solve the grand challenges of today, such as diseases, climate change, energy, clean air and water, food, population, and sustainability. This colloquium will highlight some of the important growth areas, showing the prospects and opportunities for chemistry in the future. This symposium will also show how being adaptable, collaborative, and entrepreneurial will help chemists and chemical engineers succeed in the future.

Sunday
Getting in front of the additive manufacturing revolution: Sustainability needs and opportunities
02:00pm - 02:30pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Joseph DeSimone, Presenter, Stanford University
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual
In 21 Lessons for the 21st Century, Yuval Noah Harari makes the point that the unintended consequences of too many breakthrough technologies threaten our future: Facebook set out to bring people together but grew to foster divisiveness; Juul intended to end smoking but triggered addiction to vaping; encrypted messaging designed to protect privacy enabled an underworld to thrive. He argues that liberalism has no answers to the biggest problems we face: ecological collapse and technological disruption. The proliferation of plastics and the lack of chemical circularity is the posterchild for this perspective. Recent advances in additive manufacturing technologies demonstrate how the industry is poised to make the jump from a “prototyping only” $8 billion industry to replace injection molding techniques—a $330 billion industry. As the initial stages of this major technology transition come into focus, we are at a unique moment in time to put polymer additive manufacturing on a sustainable trajectory. This talk will describe needs and opportunities for recyclable and upcyclable polymers in the context of this major transition, ultimately toward achieving a circular economy.
Sunday
Placing 3D bioprinting in the context of tissue fabrication
02:30pm - 03:00pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Prof. Y Shrike Zhang, Presenter, Harvard Medical School
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual
Three-dimensional (3D) printing refers to the fabrication of constructs from a digital 3D model in a layer-wise or volumetric programmed manner. The flexibility, versatility, and functionality of 3D printing enable the fabrication of exquisite and intricate structures with maneuverable resolutions across multiple length scales. One major sub-category of 3D printing is 3D bioprinting, in which a combination of cells, growth factors, and biomaterials (i.e., bioink) may be used as the printing material for additive manufacturing of biological constructs. As an evolving field of biofabrication, 3D bioprinting is being explored for myriad applications including tissue engineering, regenerative medicine, patient-specific grafts, as well as tissue model engineering and personalizable drug screening, among others. Depending on the applications and the bioinks’ physicochemical properties, various technologies including nozzle-based and light-based are being developed for 3D bioprinting. This talk will provide an overview of the various bioprinting strategies developed or optimized within our laboratory over the past few years, with a number of examples that specifically relate chemistry to the improvement of bioprinting capacities also given.
Sunday
It’s about I: Invention, innovation, inspiration, and inclusivity
03:00pm - 03:30pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Kathryn Uhrich, Presenter
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual
My research focuses on the design, synthesis and characterization of biocompatible, biodegradable polymers that serve a critical need in therapeutics/drug delivery. My most well-known invention is “PolyAspirin”; it was the first example of a polymer that degrades into a bioactive such as salicylic acid (SA) that can locally reduce inflammation and pain. These polymers were evaluated for various wound healing applications, such as promoting bone regeneration in diabetic animals. Another invention is the amphiphilic macromolecules (AMs), which are also bioactive. The bioactive AMs were unique therapeutic coatings for metal cardiac stents to reduce smooth muscle cell (SMC) proliferation and platelet adhesion in humans. To date, this research has produced more than 190 peer-reviewed papers and generated nearly $30 million in federal and corporate research funding. In entrepreneurship and technology transfer, I’m an inventor on more than 70 U.S. and international issued patents based upon research performed in my research labs. I’ve also been involved in multiple start-up companies centered on biomedical polymers and worked in close partnership with companies, such as BASF, Chanel, Colgate-Palmolive, DuPont, ExxonMobil, and L’Oréal. The partnerships are typically to develop new materials and/or products that are nontoxic and biodegradable that meet an unmet consumer need in pharmaceutics, medical devices, personal care, and environmental applications. Encouraging curiosity, brainstorming, preparing for failure, and promoting teamwork are keys to the success of my research labs.
Sunday
Materials opportunities in a post Moore era
03:30pm - 04:00pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Rudy Wojtecki, Ph.D., Presenter, IBM Research
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual

As computational tasks and the complexity of addressable problems become more difficult computing will dramatically change. The future of computing may then shift from traditional architectures to an increased dependence on alternatives – deep neural networks for artificial intelligence and superconducting circuits for quantum computing, to name a few. It is, however, also important to acknowledge that scaling continues leading to the further densification of computational components. There are materials opportunities in both arenas. Our research efforts have focused on developing specialized stimuli-responsive material sets around two broad topic areas: (i) materials for area selective depositions and (ii) responsive materials for electronic packaging.
(i) Current approaches to nanoscale fabrication largely rely on subtractive processes, which often alters the chemical composition of a surface (such as oxidation) or damage materials by amorphizing an otherwise crystalline thin film, from reactive ion etching, for insance. As miniaturization reaches single nanometer regimes, surfaces and interfaces become dominant. The ability to add a film to a surface in a selected area allows one to grow components of a device without damage to surfaces or interfaces. With the use of specialized inhibiting chemistries area selective depositions can be achieved, with reduced defectivity as well as offering multiple capabilities such as self-aligning patternable monolayers that can be employed in an example of additive lithography.
(ii) As the packaging space is challenged to join an increasing number of separately manufactured components into integrated device the packaging materials requirements become more demanding. These materials sets make use of irreversible chemistries in curing and crosslinking that tend to reduce throughput and yield as errors or defects in processing cannot be addressed after processing. The ability to redesign these materials to introduce moieties that can be controllably broken and reformed offers the potential to access highly desirable materials characteristics in the packaging space such as reworkability and rehealability.

Nanoparticle Interactions in Environmental Systems:
02:00pm - 03:30pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Adeyemi Adeleye, Organizer, University of California Irvine; Arturo Keller, Organizer, University of California, Santa Barbara; Dr. Yiming Su, Presider, University of California Los Angeles; Virender Sharma, Presider, Texas AM University
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Division/Committee: [ENVR] Division of Environmental Chemistry

This session seeks leading edge research on the interactions of nanoparticles (metallic, carbonaceous, organic, and nanoplastics) with biogenic, geogenic, and anthropogenic components in the natural environment. The interactions and processes of interest include nanoparticle transformations in different media, surface accumulation of inorganic and organic substances, transport through biological membranes, and nanoparticle-induced redox reactions. Of particular interest are studies on novel nanoparticles (e.g., nanohybrids, nanocomposites, and metal-organic frameworks) (1) used in environmentally-relevant applications (e.g., agriculture, remediation, and CO2 capture), (2) incidentally generated from manufacturing (e.g. nanoplastics produced during 3D printing), or that reach the environment due to their use in outdoor environments (e.g., coatings, and personal care products). We also seek studies that address risk of exposure to nanoparticles, by human and ecological receptors.

Sunday
Introductory Remarks
02:00pm - 02:05pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid

Sunday
Cerium-based metal-organic framework for environmental remediation
02:05pm - 02:30pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Mohamed H. Hassan, Presenter, Clarkson University; Emanuela Andreescu, Clarkson University
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Phosphate-based fertilizers are in widespread use around the world to increase agricultural yields and sustain food production. While phosphorus is an essential resource for agricultural production its excessive accumulation can cause overgrowth of harmful algal blooms that can affect water quality, leading to eutrophication. Most of the traditional materials that can absorb phosphates and neutralize organophosphates suffer from limited specificity and low removal efficiency. Effective technologies are needed to eliminate the presence of these compounds and address toxicity issues. This presentation describes the use of cerium-based microporous materials that have exceptional stability, high surface area, highly porous structure and the ability to bind to phosphates and organophosphate pesticides in water. We have used cerium-based metal organic framework (Ce 1,4-benzenedicarboxylate) as a high capacity sorbent for phosphate removal from eutrophic waters due to the high binding affinity of phosphate at the MOF's defect sites. Experimental results show a fast phosphate removal, within 4 min with a maximum adsorption capacity of 179 mg.g-1, outperforming other porous materials. This MOF can also be used to neutralize the nerve agent paraoxon and it showed significantly enhanced degradation ability when cerium nanoparticles are encapsulated inside the MOF. These results are expected to help establish new design principles for developing the next generation sorbents and neutralizing platforms to reduce phosphate levels and mitigate the negative effects of these toxicants in the environment.
Phosphate removal with Ce-MOF from eutrophic water

Phosphate removal with Ce-MOF from eutrophic water


Sunday
Magnetic chitosan as nano-softener to improve groundwater quality
02:30pm - 02:50pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
The pressure exerted on water supplies continues to increase as population density in urban areas. Additionally, in the state of Baja California, México, from the 48 groundwater aquifers five have salinization problems and seven have some degree of saltwater intrusion. This situation along with the dryness of the Cali-Baja (bi-national) region makes it necessary to take action on finding efficient ways to treat this type of water and make it accessible for the population. The most popular technologies to improve water quality and aesthetics (such as alkalinity and hardness) are reverse osmosis, chemical precipitation, ion exchange, and electrochemical removal, but these processes often require a post-treatment adjustment, or they tend to be onerous. In this paper we show iron-oxide magnetic nanoparticles and its chemical modification with chitosan by co-precipitation method with high potential to be used on ground water quality improvement. Five different types of magnetic chitosan were synthetized varying the amount of chitosan added to the nanoparticles, previous the nucleation of the magnetite. All the magnetic chitosan were studied and compared by DLS and Zeta potential to choose the most promising material for water treatment application. The magnetic chitosan and raw magnetite were characterized previous their use by FT-IR, SEM/STEM, Zeta Potential, DLS, and TGA studies, proving the binding between magnetite and the biopolymer. Studies of the magnetic materials on groundwater, from the ranch “Cacho” (Tijuana, B.C., México), were carried out to prove their effectiveness to remove alkalinity and hardness, and the results indicate that magnetic chitosan and raw magnetite proved to be effective for trap and remove carbonates salts from groundwater, and at the same time, we have the possibility of recovering them to further uses and reduce the operation cost. With these characteristics, we can classify magnetite and magnetic chitosan as sustainable nano softeners.
a) DLS and b) Zeta potential of MNP (black line), MCH-100 (orange line), MCH-100S (purple line), MCH-200 (olive line), MCH-200S (Blue line) and MCH1000 (pink line).

a) DLS and b) Zeta potential of MNP (black line), MCH-100 (orange line), MCH-100S (purple line), MCH-200 (olive line), MCH-200S (Blue line) and MCH1000 (pink line).


Sunday
Influence of sulfolipid density on the extent of carbon dot interaction with chloroplast membranes
02:50pm - 03:10pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid
Nanoparticle delivery to plant chloroplasts has been explored for improving genetic traits and promoting growth. Nonetheless, little information is available regarding the influence of nanomaterial and chloroplast membranes properties on their interaction. In this study, we constructed model chloroplast membranes and interrogated the influence of carbon dot charge, membrane composition, and solution conditions on the interactions of carbon dots using quartz crystal microbalance with dissipation monitoring. We further examined the interaction of carbon dots with chloroplasts isolated from Arabidopsis thaliana using confocal laser-scanning microscopy. We find that the abundance of sulfoquinovosyl diacylglycerol in model membranes critically influences the affinity of the membrane for positively charged carbon dots. Rates of carbon dot attachment to model chloroplast membranes varied with ionic strength in a manner consistent with a dominant role for electrostatic interactions. We expect our findings to contribute to the development of structure–property–interaction relationships for nanoparticle interaction with chloroplasts.
Sunday
Withdrawn
03:10pm - 03:30pm USA / Canada - Eastern - August 22, 2021 | Room: B402
Division: [ENVR] Division of Environmental Chemistry
Session Type: Oral - Hybrid

New Frontiers and Opportunities for Chemistry: Nanotechnology
04:30pm - 06:30pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Dr. H.N. Cheng, Organizer, Presider, USDA Agricultural Res. Service; Young-Shin Jun, Organizer, Presider, Washington University in St. Louis; Martin Kociolek, Organizer, Presider, Penn State Erie, The Behrend College; Michael Morello, Organizer, Presider, Retired: PepsiCo R&D
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual
Division/Committee: [COMSCI] Committee on Science

Chemistry is becoming increasingly multidisciplinary, and the future chemists and chemical engineers may find increasing opportunities to apply their chemical knowledge in new or expanded areas. Certainly, the skills and the tools of chemistry are positively needed to solve the grand challenges of today, such as diseases, climate change, energy, clean air and water, food, population, and sustainability. This colloquium will highlight some of the important growth areas, showing the prospects and opportunities for chemistry in the future. This symposium will also show how being adaptable, collaborative, and entrepreneurial will help chemists and chemical engineers succeed in the future.

Sunday
Megalibraries: Tools for exploring and expanding the materials genome with big data and AI
04:30pm - 05:00pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Professor Chad A. Mirkin, Presenter, Northwestern University
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual
The discovery of new materials has driven societal development throughout human history. Existing materials discovery strategies largely consist of serial or low-throughput experiments driven by chemical intuition or iterations on previous results and are too slow to match the materials complexity and diversity available through ever-developing synthesis techniques. Methods for high-throughput synthesis and screening, coupled with data-driven optimization processes are a route towards rapid materials discovery. We have developed a cantilever-free scanning probe lithography-based approach that, through the deposition of polymeric nanoreactors and thermal annealing, enables the synthesis of “megalibraries”, consisting of as many as 5 billion positionally encoded nanoparticles designed to systematically vary in composition and/or size. The megalibraries can be tailored to encompass a wide variety of alloy and phase-separated nanoparticles that are comprised of as many as 8 different elements with up to four phases and six interfaces. From these libraries, we have discovered new catalysts for energy relevant transformations, designed complex structural motifs into polyelemental nanoparticles both through computational and machine learning methods, and paved the way for rapid materials discovery and data generation.
Sunday
Discovery and commercialization of nanostructured zeolites: An example of chemistry entrepreneurship that creates value and reduces CO2 emissions
05:00pm - 05:30pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Prof. Javier Garcia Martinez, Presenter, University of Alicante
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual
The development of intracrystalline mesoporosity within zeolites has been a long-standing goal in catalysis as it greatly contributes to alleviating the diffusion limitations of these widely used microporous materials. During my presentation, I will discuss the main techniques that have been developed during the last years to produce zeolites with controlled mesoarchitectures comparing the different methods, their advantages, and limitations. Among the different techniques used to characterize the composition, porosity, and structure of these materials, I will present unprecedented insights on the formation of intracrystalline mesoporosity in zeolites obtained by in situ synchrotron X-ray diffraction and Liquid Cell Transmission Electron Microscopy (Liq-TEM). By combining experimental results and theoretical calculations, the presence of intracrystalline mesoporosity was recently confirmed. Moreover, through the observation of individual zeolite crystals by Liq-TEM, we are able to provide the first time-resolved visualization of the formation of mesoporosity in zeolites.

The presence of this mesoporosity was further evidenced through ex situ gas adsorption, which also confirmed the preservation of most of the microporosity of the zeolites. All these new insights, obtained by combining a number of time-resolved techniques, are an example of the enormous potential of current in situ characterization methods for the rational design of hierarchical zeolites with superior properties and optimal catalytic performance as it has been proved at lab, pilot plant, and industrial scale.

These nanostructured catalysts, which are being produced at multi-ton scale by G.W. Grace, allow refiners to increase refining margins by as much as $0.90 per barrel and refinery profitability by $50 million per year. It is estimated that in a medium-size refinery the use of our technology allows for an annual reduction of 100,000 tons of CO2.

The commercialization of hierarchical zeolites through the MIT spin-off Rive Technology as superior refining catalysts is an example of academic entrepreneurship, which is expected to foster the development of new hierarchical zeolites and their use in both existing processes and new opportunities. Finally, I cover other applications of hierarchical zeolites in catalysis, including biomass valorization and fine chemistry, ending with a personal view of the new directions, and opportunities in this field.

Sunday
Multivariate reticular chemistry
05:30pm - 06:00pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Omar Yaghi, Presenter
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual
Chemists consider compounds having the same chemical composition, formula, and structure (the pattern of connectivity and geometry) to be the same except in the case of isomers where the atoms in molecules differ only by their spatial arrangement. This presentation will introduce multivariate reticular structures (such as MOFs) in which the spatial arrangement of multiple functionalities or metals varies across the crystal. Two such multivariate MOFs having the same composition, formula, and structure are likely not to be identical since their sequences (the spatial arrangement of variants) across the two MOF crystal structures are different. It is worth noting that recent evidence show that sequences in MOFs can adopt random arrangements of variants; however, conditions can be created for biasing of variants in order to achieve MOFs having sequences containing non-random short and long repeats. There is also evidence that some of these multivariate systems being endowed by sequences give rise to properties where the whole performs better than the sum of the parts. We, therefore, propose that sequences in synthetic crystals be added to the criteria of sameness for its impact on the properties of compounds.
Sunday
Withdrawn
06:00pm - 06:30pm USA / Canada - Eastern - August 22, 2021 | Room: Zoom Room 45
Division: [COMSCI] Committee on Science
Session Type: Oral - Virtual