Donghai Wang - US grants

Biofuels and biobased products can improve environmental quality, rural economies, and national security only through the cross-disciplinary efforts of scientists and engineers with an appreciation for the complexity of the societal, technological, and scientific issues involved. This Integrative Graduate Education and Research Traineeship (IGERT) project will prepare a diverse group of new Ph.D.s to have a comprehensive perspective on the biorefining industry. IGERT graduate student trainees will form interdisciplinary core teams encompassing the technological, agricultural, and socioeconomic issues of an aspect of biorefining. Dissertation projects will be conducted with overlapping faculty supervisory committee membership, regular joint meetings, and dissertation chapter(s) and publications addressing the collaborative, integrated research issues and results. New learning opportunities are provided in the classroom, seminars, workshops, certificate programs, and field experiences. This learning will be mutually deepened for trainees and undergraduates through research mentorship opportunities. International education opportunities will be available with partners in Europe and Brazil. This project will result in new technologies and practices that will improve the sustainability of the conversion of biomass to fuels and chemicals. As a result of this program, decisions regarding biorefining will be guided not only by technological and/or agricultural feasibility but also by the holistic impact on society. Graduates of this IGERT program will be uniquely prepared to have high-impact careers and to contribute to the biorefining industry through their personal appreciation of the diverse aspects of biorefining. IGERT trainees will have harvested biomass in the field hands-on, discussed and advanced technical and engineering issues, and pondered the impact of their actions on humanity and the environment. IGERT is an NSF-wide program intended to meet the challenges of educating U.S. Ph.D. scientists and engineers with the interdisciplinary background, deep knowledge in a chosen discipline, and the technical, professional, and personal skills needed for the career demands of the future. The program is intended to catalyze a cultural change in graduate education by establishing innovative new models for graduate education and training in a fertile environment for collaborative research that transcends traditional disciplinary boundaries.

1033538
Hohn

With concerns about the long-term supply of petroleum and the desire to decrease U.S. dependence on foreign oil, renewable fuels are increasingly being considered as replacements for petroleum-based fuels. Cellulosic ethanol from perennial energy crops, crop residue, and forestry biomass could replace a significant percentage of the current United States petroleum consumption. The challenge in producing ethanol from cellulose is the difficulty in breaking down cellulosic matter to sugars. Two primary methods are used for cellulose hydrolysis: mineral acids and enzymes. Mineral acids give fast hydrolysis rates, but their use requires expensive materials due to their corrosivity and they must be separated and reused or neutralized and discharged. Enzymes are more selective than acids towards glucose, but are expensive and cannot be reused.

Principal Investigators Hohn and Wang of the Department of Chemical Engineering at Kansas State University propose a new type of catalyst for pretreatment and hydrolysis of lignocellulosic materials: acid-functionalized magnetic nanoparticles. Their hypothesis is that active, separable lignocellulose hydrolysis catalysts can be synthesized by combining a magnetic core with ligands that provide strong acidity and enhanced interaction with lignocellulosic biomass. The approach is to synthesize magnetite nanoparticles and utilize the strong interaction between magnetite and acid functionalities to bind ligands to the nanoparticle. These ligands will contain multiple acid groups: some that bind to the nanoparticle, but others that are available to act as Brønsted acid sites. In addition, the ligand will contain functional groups (like aromatic rings) that will enhance the interaction between crystalline cellulose and the acid-functionalized nanoparticles. The experimental plan covers many aspects, including characterization of the catalysts and the reaction products after hydrolysis treatments, and the separability and reusability of the catalyst particles.

Hohn and Wang will be able to probe what catalyst properties such as acid site strength or the presence of hydroxyl groups are important for production of glucose from biomass. The intellectual merit of the proposed research is that it will be the first to investigate acid-functionalized nanoparticles for hydrolysis. It will generate new knowledge in lignocellulose hydrolysis, and will pave the way for future research in using nanotechnology in biomass conversion. In addition, glucose is a representative of sugars that can be derived from biomass. These sugar molecules then may be used as platform molecules for chemicals or fuels, thus serving to advance the replacement of petroleum. The broader impact of the proposed research is the benefit to society associated with developing technology to convert biomass to fuel that can decrease U.S. dependence on foreign oil. In addition, this research will be incorporated into a hands-on workshop that will be used in an established program designed to enhance recruitment of women in science and engineering.

This award supports fundamental research on ultrasonic vibration-assisted (UV-A) pelleting of cellulosic biomass in order to enable cost-effective manufacturing of cellulosic biofuels. Specific research tasks include (1) investigating effects of ultrasonic vibration on pelleting mechanisms, (2) testing a hypothesis of the underlying mechanism of how UV-A pelleting can increase pellets? strength and durability, (3) investigating mechanisms through which UV-A pelleting enhances sugar and ethanol yields, and (4) testing the hypothesis that UV-A pelleting can result in improved pretreatment procedures. These tasks will be conducted over a wide range of biomass types including sorghum stalks, switchgrass, wheat straw, corn stover, Miscanthus, and grass clippings.

Research results will provide the knowledge needed to overcome some technical barriers that have hindered large-scale manufacturing of cellulosic biofuels. Large-scale manufacturing of cellulosic biofuels will greatly benefit the U.S. economy, energy security, the environment, and society in general. This research features a unique collaboration across manufacturing engineering, biological engineering, and industry. This collaboration provides excellent synergy for project resources, ensures the relevance of the research to industry, and expedites technology commercialization. The interdisciplinary nature of the research will have a positive impact on engineering education at Kansas State University, an EPSCoR institution.

DESCRIPTION (provided by applicant): Pyrogenic arthritis, pyoderma gangrenosum and acne (PAPA) syndrome, previously referred to as streaking leucocyte factor disease, is a rare autosomal dominant autoinflammatory disorder characterized by sterile inflammation of the joints and skin, arthritis and severe acne. The disease is strongly associated with two defined mutations in the PSTPIP1 gene. The associated arthritis often leads to joint destruction and debilitation. Neither PAPA syndrome related pyoderma gangrenosum nor acne respond well to conventional therapy, including steroids or high dose antibiotics, although there are now reports of successful therapy using human interleukin (IL)-1 receptor antagonist, suggesting a causal role for IL-1?. In vitro studies have shown that dysregulation of caspase-1 activating inflammasomes may contribute to the pathogenesis. It is thought that mutant PSTPIP1 multimerizes spontaneously, subsequently binds PYRIN, and activates caspase 1 via the adapter ASC. However, little is known about the normal physiological function of PSTPIP1 and nor how mutant PSTPIP1 proteins cause inflammasome activation. To elucidate the function of PSTPIP1, we have established a conditional allele of the Pstpip1 encoding gene in mice. Ablation of PSTPIP1 expression can be achieved in a conditional manner. Using this conditional knockout strain, we will test the importance of PSTPIP1 in the process of inflammasome activation both in vivo and in vitro. Biochemical studies as well as infectious challenges of cells derived from these mice, or the mice themselves, should shed light on the normal physiological role of PSTPIP1. In addition, we have also generated mouse strains in which ectopic expression of mutants of PSTPIP1 that correspond to the human mutations can be induced in a tissue or cell lineage specific manner using the Rosa 26 locus targeting technology. We hypothesize that ectopic expression of mutant PSTPIP1 will lead to PAPA-like disease conditions in these mice. By analyzing the resultant phenotypes in the transgenic mice, we expect to gain insights into how mutant PSTPIP1 causes PAPA syndrome. In addition, we believe the proposed research will provide insights into the pathophysiological processes of autoinflammatory diseases and lead to new clues in designing therapies for immune disorders.

Technical Abstract

Recently, a new class of high-energy-density, Li- and Mn-rich layered cathode materials has been discovered. The project aims to build the fundamental knowledge base needed to progress towards design and processing of the materials with desired properties through integrated first-principles calculations, CALPHAD modeling, materials processing, and battery assembling and testing. This fundamental knowledge base also builds the genome foundation to discover new cathode materials. The new cathode material resides in a multi-component space of xLi2MnO3ª(1-x)LiMO2 with M being alloying elements including Mn, Co, and Ni. In the project, first-principles calculations will be used to systematically investigate the effects of these common alloying elements and potential outliers on electronic structures and charge transfers and predict thermodynamic properties of individual phases as a function of temperature and compositions. CALPHAD modeling will be utilized to establish phase relations and optimize the composition space (x and M) for superior charging-discharging performance. To validate the predictions from first-principles calculations and CALPHAD modeling, cathode materials will be synthesized with tailored composition and assemble coin cells to test battery performance. The project objectives are:

1.Establish fundamental understanding of effects of alloying elements and search for potential outliers;
2.Develop a thermodynamic description of the Li-Mn-Co-Ni-O system plus potential outliers;
3.Synthesize and characterize cathode materials and test battery performance based on computational modeling and feedback to improve databases.


Nontechnical Summary

The development of new materials and the capability of tailoring existing materials to meet new and demanding applications are critical for continued improvements in the quality of human life. Materials are a determining factor in the global competitiveness of the U.S. manufacturing industry as materials account for up to half of the costs of most manufactured products. Li-ion rechargeable batteries are the key constituent for low cost and high-energy-density storages needed for numerous applications such as electronic devices and electric vehicles. The development of novel cathodes is critical because of the limitations of cost and energy density for cathodes used in current rechargeable Li-ion batteries. Recently, a new class of high-energy-density, Li- and Mn-rich layered cathode materials has been discovered. The project aims to build the fundamental knowledge base needed to progress towards design and processing of the materials with desired properties through integrated first-principles calculations, thermodynamic modeling, materials processing, and battery assembling and testing. This fundamental knowledge base also builds the genome foundation to discover new cathode materials.
The proposal's intellectual merit lies on its collaborative, synergistic approaches between theory, computation, and experiments to rapidly build a chemistry-processing-structure-property-performance knowledge base for the Li- and Mn-rich layered cathode materials. This integrated approach will be based on the combined expertise in simulations, syntheses, and evaluation of battery materials. The research project aims to move the low cost and high-energy-density cathode materials research in the US to a new level by further building the foundation to answer fundamental questions that can only be addressed efficiently via combined computational and experimental methodology. These include: what is the best combination of Li/Mn/M layers in terms of cost and performance? what are the composition/temperature variations for their robust processing? and what are the potential outliers of alloying elements for superior performances?
Broader impacts include following aspects, in addition to economic impact of low-cost and high-energy-density cathode materials on battery manufacturing, a) educate students to be professionals mastering both innovative computational and experimental approaches with cross-disciplinary knowledge of materials and batteries; b) encourage students to make presentations at professional meetings to improve communication skills; c) foster students' writing skills through peer reviewed journal publications; d) participate in activities to broaden the participation of underrepresented groups through the SEEMS (Summer Experience in Earth and Mineral Science) programs for high school students and WISER (Women in Science and Engineering Research) program for first year students, e) contribute to new materials research paradigm in shortening the time for developing new materials and improving existing materials to minimize the cost to the society and the negative impact to the environment, and increasing the competitiveness of US manufacturing.

DESCRIPTION (provided by applicant): Inflammation has to be constantly restrained to avoid tissue or organ damage. Imbalanced production of proinflammatory cytokine production and interferons underlies a variety of diseases such as autoimmunity and cancer. Protein geranylgeranylation is a post-translational lipid modification that regulates a variety of cellular functions. Loss of protein geranylgeranylation leads to imbalanced cytokine production and inflammatory disease conditions such as that in the autoinflammatory mevalonate kinase deficiency in humans or in mice deficient for key enzymes catalyzing protein geranylgeranylation. We propose to use a mouse model in combination with biochemical approaches and human genetics to elucidate the mechanisms by which protein geranylgeranylation regulates inflammatory processes through maintenance of balanced cytokine production. Knowledge gained from the proposed research will not only benefit MKD patients, but also patients suffering from common inflammatory diseases such as arthritis and atherosclerosis.

Non-Technical Abstract
Electrical energy storage is a key component of the renewables-friendly future power grid with high-energy efficiency, stability, and resilience. Sodium ion batteries have a significant advantage over widely used Lithium ion batteries, owing to the low cost and abundance of sodium precursor. Phosphorus-based materials are promising as anodes for sodium ion batteries due to their high capacity and low cost. However, similar to alloy anodes in lithium ion batteries, phosphorus undergoes ~300% volume change during charge/discharge, leading to pulverization of the active materials, unstable growth of the solid electrolyte interphase, and poor cyclability. With the support of the Solid State nad Materials Chemistry program, this research project strives to bring low-cost, high-performance, long-cycling sodium ion batteries closer to real-world applications by understaning the degradation mechanisms of phosphorus-based anode materials. Such batteries would enable greater integration of intermittent renewable power sources such as wind and solar, decrease dependence on fossil fuels, and improve the overall efficiency, stability, and resilience of the power grid. The research project also enhances involvement of women and minorities in science and engineering, and stimulates the interests of students at Penn State in the fast-evolving research field of nanostructured energy storage materials.

Technical Abstract
The research objective of this award is to uncover the underlying mechanisms of electro-chemically driven mechanical degradation in phosphorus-carbon hybrids as anode materials for sodium ion batteries through an integrated experimental-modeling approach. Experimentally, in situ TEM studies allow atomic-scale observation of phase transformation and failure mechanisms. Combined with the low-cost, scalable synthesis methods and advanced full-cell battery testing and characterization, the experimental studies enable the research team to build an atomic-scale picture of microstructure, morphology, and composition evolution of the hybrids during electrochemical cycling. The proposed multiscale models seamlessly integrate with the experimental characterizations to identify the leading degradation mechanisms and accordingly optimize the material designs. The integrated experimental-modeling approach helps foster transformative progress for developing high-performance energy storage materials.

Today's economy and society are highly dependent on liquid fuels for transportation. Currently, more than 90 percent of the liquid transportation fuels used in the U.S. are petroleum-based. It is imperative to develop alternative liquid fuels that are domestically produced and environmentally benign. Biofuels, derived from cellulosic biomass such as agricultural and forestry residues and dedicated energy crops, offer one of the best near- to mid-term alternatives. Size reduction of cellulosic biomass is the key step in the manufacturing of biofuels. Size reduction is an energy intensive process, and particle size dictates the energy consumption in this process. This award supports research to understand the relationship between cellulosic biomass particle size and biofuel yield. Successful completion of this research will build a foundation for future biofuel manufacturing technologies. This research will have a significant impact on the overall cost and energy balance of biofuel manufacturing, greatly benefiting the U.S. economy and energy security, as well as the environment and society, in general. This project will have a positive impact on engineering education. A new course accompanied by hands-on lab sessions will be created to strengthen the undergraduate engineering curricula and engage students in participating projects on renewable energy manufacturing.

The research objective is to test three hypotheses to explain inconsistency in the relationship between cellulosic biomass particle size and enzymatic hydrolysis sugar yield. In this research, it is hypothesized that the inconsistences are caused by the use of different sugar yield definitions, particle size ranges, and pretreatment methods. The prevailing biofuel manufacturing technology and the three most widely used cellulosic biomass currently in the industry, wheat straw, corn stover, and switchgrass, will be used in the research. Experimental investigations on both lab and pilot scale biofuel conversion facilities will be conducted to test the hypotheses. Additionally, structural features, morphological changes, and chemical compositions of cellulosic biomass will be characterized by using electron microscopy, x-ray diffraction analysis, UV spectrophotometry, high performance liquid chromatography, IR spectroscopy, Simon's stain, and nuclear magnetic resonance techniques. Based on the experimental results, a sugar yield model, incorporating all the significant structural, morphological, and chemical features, will be developed and validated. The outcome of this research will provide insights in the dynamic degradation of sugar compounds during hydrolysis. It will advance the knowledge base needed to make both strategic and operational decisions in biofuel manufacturing.

Zika virus infection during pregnancy causes brain abnormality in newborns, most remarkably small heads (microcephaly). Microcephaly is usually caused by defects in the development of the brain cortex. The brain cortex develops from the division, proliferation and differentiation of neuron precursors (neuroprogenitors). It is known that Zika virus can cause the depletion of neuroprogenitors and cell death, however, little is known about how this happens. Cholesterol is a fundamental lipid component that is essential for mammalian cell function and proliferation. Defects of cholesterol biosynthesis also causes microcephaly. Interestingly, host innate immune response to viral infection lead to production of interferons. While interferon can control viral infection, it also severely inhibits cholesterol biosynthesis. We propose that it was the innate anti-viral interferon response that causes a collateral damage to the developing brain during Zika virus infection. We plan to use animal models as well as stem cell technology to test our hypothesis. Our study may lead to new strategies to prevent microcephaly and other brain abnormalities associated with maternal Zika virus infection.

This project explores the potential of composite silicon anodes for multifunctional lithium ion (Li-ion) based devices. Li-ion batteries are widely used for high power and energy density applications, such as electric vehicles, cell phones, laptop computers, and unmanned aerial vehicles. Silicon anodes promise even higher electrochemical energy densities, but their use is complicated by the high volumetric expansion that silicon undergoes when fully lithiated. Furthermore, open-circuit voltage in Li-ion cells with silicon anodes is highly sensitive to mechanical stress. This project will harness these effects to create novel multifunctional structures capable of integrated energy storage, mechanical actuation, and inertial, vibration, and chemical sensing. The fundamental capabilities and trade-offs of this new and novel class of devices will be characterized through modeling, design optimization, and experimental testing. Project outcomes will have broad impacts on a variety of technologies, including medical microrobots, wearable electronic devices, and electric vehicles. A diverse research team of graduate and undergraduate students will work together on fundamental research tasks, as well as in translational engineering workshops to learn skills crucial to converting fundamental research into commercial products and systems.

This project seeks a fundamental understanding of the coupled electrochemical and mechanical dynamics of lithiated Si composite structures, through theoretical, experimental, and device design research. Fundamental equations of electrochemistry and mechanics will be combined to predict the displacement and force provided by these active structures. The governing partial differential equations will be simplified via supportable engineering assumptions, linearization, and model order reduction, to produce numerically efficient models providing an insightful understanding of the underlying physics and chemistry. These models will be used in turn to design the chemistry, morphology, and mesoscale structure of composite anodes, including the Si, binder, and conductive additives, to explore the Pareto frontier between electrical and mechanical power. For the first time, the large volume change associated with lithiation of Si composites will be harnessed to create actuated structures that move in a desired fashion when charged and discharged. Also for the first time, the Larché-Cahn potential will be used to make batteries that self-sense their stress state. Starting from novel, first principle models and a notional mesostructure, the full governing equations will be simplified to efficiently and accurately predict output voltage based on applied loads and electrical current input. Chemical composition, morphology, and structure will be varied to study the tradeoff between energy storage and sensitivity to applied loads. The new actuating and self-sensing energy storage structures will be paired with standard cathodes and electrolytes, and tested for electrical, mechanical, and sensor performance. The results of the project will be encapsulated in first-principles models, which will be experimentally validated against measurements of voltage, current, displacement, and applied load.