Division Of Chemistry Research Articles

General meeting of the Division of Chemistry and Materials Science, Russian Academy of Sciences

General meeting of the Division of Chemistry and Materials Science, Russian Academy of Sciences

Apply for an undergraduate research fellowship

The American Chemical Society Division of Organic Chemistry is accepting applications for the 2020 Summer Undergraduate Research Fellowships. The $5,000 awards provide funding for summer research opportunities for outstanding undergraduate organic chemistry students attending colleges and universities in the US. Nominations are due Feb. 14. For more information, visit bit.ly/2NmZsUq.

Organic Material Chemistry Laboratory （Saimoto & Ifuku lab.）, Division of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University

Organic Material Chemistry Laboratory （Saimoto & Ifuku lab.）, Division of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University

バイオ医薬品の品質評価技術の進歩と国際調和：国立医薬品食品衛生研究所生物薬品部 30 年の歩みに焦点を絞って

バイオ医薬品の品質評価技術の進歩と国際調和：国立医薬品食品衛生研究所生物薬品部 30 年の歩みに焦点を絞って

Robert Donald Bruce Fraser 1924–2019

Robert Donald Bruce (Bruce) Fraser was a biophysicist who gained world-wide distinction for his extensive structural studies of fibrous proteins. Bruce began a part-time BSc degree at Birkbeck College, London, while working as a laboratory assistant. In 1942, aged 18, he interrupted his studies and volunteered for training as a pilot in the Royal Air Force (RAF). He was sent to the Union of South Africa and was selected for instructor training, specialising in teaching pilot navigation. At the end of the war he completed his BSc at King’s College, London, and followed this with a PhD. Bruce studied the structure of biological molecules, including DNA, using infra-red micro-spectroscopy in the Biophysics Unit at King’s led by physicist J. T. Randall FRS. During that time Bruce built a structure for DNA that was close to the Watson-Crick structure that gained them and Maurice Wilkins at Kings College, the Nobel Prize in 1962. In 1952, he immigrated to Australia with his family to a position in the newly formed Wool Textile Research Laboratories at the Commonwealth Scientific and Industrial Research Organisation (CSIRO). Here, Bruce established a biophysics group for research on the structure of wool and other fibrous proteins that flourished until his retirement. Over that period he was internationally recognized as the pre-eminent fibrous protein structuralist world-wide. Having been acting chief, Bruce was subsequently appointed chief of the Division of Protein Chemistry and he remained in that role until he took retirement in 1987.

27th Annual GP2A Medicinal Chemistry Conference.

The 27th annual GP2A (Groupement des Pharmacochimistes de l′Arc Atlantique/Group of Medicinal Chemists in the Atlantic Arc) conference took place from 21 to 23 August 2019, at the East Midlands Conference Centre (University Park, Nottingham, United Kingdom) and was hosted by the Division of Biomolecular Science and Medicinal Chemistry (BSMC), within the School of Pharmacy at the University of Nottingham. The event brought together an international delegation of researchers with interests in medicinal chemistry and interfacing disciplines. In addition, a pre-conference workshop provided an opportunity for younger researchers to develop their theoretical knowledge in quantitative pharmacology. s of presentations by the 14 invited speakers and 6 young researchers, in addition to 41 posters, are included in this report.

Undergraduates awarded research fellowships

The 2019 recipients of the American Chemical Society Division of Organic Chemistry’s Summer Undergraduate Research Fellowships (SURF) have been announced. They are Yotam Ashkenazi of the University...

Desarrollo de un sistema de información para la eficiente gestión de sustancias químicas con base en la Norma Oficial Mexicana NOM-018-STPS-2015

The technologies of the information nowadays are essential in the development of our daily life. They have been reflected in various activities and serve the purpose of integrating various branches of science. Having this in mind, the development team achieved to identify that in the division of chemistry at the technological university of San Juan del Rio, there was the necessity to have a web platform to consult the substances that are in storage. And also provide a tool for the implementation of the official Mexican norm NOM-018-STPS-2015 which has the purpose of identifying the dangers and risks of dangerous chemical substances through the use of pictograms. The software development stages were implemented using XP (Xtreme Programming) being that it’s an agile methodology and it allows to prioritize tasks according to the client’s requirements, using the programming languages PHP 7, MySQL and HTML 5. The acquired result was a web system with the modules of queries, substances information, which was used by students of chemistry engineering who evaluated the platform via a survey, and accomplished a 75% of satisfaction.

Analytical Division presents 2019 awards

The American Chemical Society Division of Analytical Chemistry has announced the 2019 recipients of its awards, which recognize important contributions to the major scientific aspects of the discipline. The awards will be presented during a symposium at the fall ACS national meeting in San Diego. Patrick Unwin, a professor of chemistry at the University of Warwick, is the winner of the ACS Division of Analytical Chemistry Award in Electrochemistry. His research group has pioneered techniques for innovative nanoscale electrochemical imaging. Joel Harris, a professor of chemistry at the University of Utah, is the recipient of the ACS Division of Analytical Chemistry Award in Spectrochemical Analysis. His research focuses on analytical spectroscopy studies of low concentrations of molecules in liquids and at liquid-solid interfaces. Charles Lucy, a professor emeritus at the University of Alberta, is the winner of the ACS Division of Analytical Chemistry J. Calvin Giddings Award for Excellence in

Purity assessment using the mass balance approach for inorganic in-house certified reference material production at Inmetro

The production of Certified Reference Materials (CRMs) is one of the essential activities of the National Institute of Metrology, Quality and Technology (Inmetro) to ensure metrological traceability of inorganic elemental measurements in Brazil. This work presents a set of procedures for purity assessment and in-house certification of high-purity salts, implemented at the Laboratory of Inorganic Analysis, from the Chemical and Thermal Metrology Division at Inmetro. We developed and validated methodologies based on inductively coupled plasma mass spectrometry, energy-dispersive X-ray fluorescence spectrometry and inductively coupled plasma optical emission spectrometry measurements with standard addition calibration in order to determine the mass fraction of up to 71 elements considered as possible impurities. The purity of inorganic salts was determined using the mass balance approach with expanded measurement uncertainties smaller than a mass fraction of 0.007 %. All procedures were performed according to the ISO 17034:2016 standard. The CRMs will be used for the production and certification of single-element calibration solutions at Inmetro.

On Certain Counting Polynomial of Titanium Dioxide Nanotubes

Background: In 1936, Polya introduced the concept of a counting polynomial in chemistry. However, the subject established little attention from chemists for some decades even though the spectra of the characteristic polynomial of graphs were considered extensively by numerical means in order to obtain the molecular orbitals of unsaturated hydrocarbons. Counting polynomial is a sequence representation of a topological stuff so that the exponents precise the magnitude of its partitions while the coefficients are correlated to the occurrence of these partitions. Counting polynomials play a vital role in topological description of bipartite structures as well as counts of equidistant and non-equidistant edges in graphs. Omega, Sadhana, PI polynomials are wide examples of counting polynomials. Methods: Mathematical chemistry is a division of abstract chemistry in which we debate and forecast the chemical structure by using mathematical models. Chemical graph theory is a subdivision of mathematical chemistry in which the structure of a chemical compound can be embodied by a labelled graph whose vertices are atoms and edges are covalent bonds between the atoms. We use graph theoretic technique in finding the counting polynomials of TiO2 nanotubes. : Let ! be the molecular graph of TiO2. Then (!, !) = !!10!!+8!−2!−2 + (2! +1) !10!!+8!−2! + 2(! + 1)10!!+8!−2 Results: In this paper, the omega, Sadhana and PI counting polynomials are studied. These polynomials are useful in determining the omega, Sadhana and PI topological indices which play an important role in studies of Quantitative structure-activity relationship (QSAR) and Quantitative structure-property relationship (QSPR) which are used to predict the biological activities and properties of chemical compounds. Conclusion: These counting polynomials play an important role in topological description of bipartite structures as well as counts equidistance and non-equidistance edges in graphs. Computing distancecounting polynomial is under investigation.

Editorial page, special issue honoring Professor Mark Cushman.

This issue of Medicinal Research Reviews is dedicated to an accomplished scientist and excellent mentor, Dr. Mark Cushman, Distinguished Professor of Medicinal Chemistry in the Department of Medicinal Chemistry and Molecular Pharmacology, College of Pharmacy, Purdue University. Professor Cushman completed 2 years of pre-pharmacy studies in 1965 at Fresno State College (now California State University, Fresno). Thereafter, he received a Doctor of Pharmacy degree (1969) and a Ph.D. in Medicinal Chemistry (1973) both from the University of California San Francisco. As a graduate student, he worked under the direction of Dr. Neal Castagnoli, Jr. During his graduate studies, he focused on the development of organic methodology and the synthesis of tetrahydrocannabinol. A highlight of his graduate work is the condensation of Schiff bases with succinic anhydrides—now known as the Castagnoli-Cushman reaction. Upon graduation, he moved to Massachusetts Institute of Technology (MIT) to perform research in the laboratory of George Büchi, Ph.D. In 1975 he joined the College of Pharmacy of Purdue University as an assistant professor and he rose through the ranks to his current position as a Distinguished Professor of Medicinal Chemistry. Dr. Cushman and his research group have made seminal contributions to the broad field of medicinal chemistry. He is primarily known for his work on developing small-molecule therapeutics against cancer, especially indenoisoquinolines and other noncamptothecin inhibitors of topoisomerase 1. He has over 340 published papers and 39 patents, some of which have been licensed to private companies for further development. Currently, three drug candidates from his lab are undergoing clinical trials. Dr. Cushman has also made important contributions to the discovery of inhibitors of tyrosyl-DNA phosphodiesterase 1 and retinoid X receptor activators. In addition, his group has published pivotal papers on the synthesis and evaluation of nonnucleoside reverse transcriptase and riboflavin synthase inhibitors. His group has also been very active in the synthesis of natural products including nitidine chloride, coryladine, (±)-rhalictricavine, berlambine, (±)-canadine, chelidonine, and Abyssinian. His work is characterized by both a high level of detail and careful attention to mechanistic insights to understand chemical and biological functions. Professor Cushman has received various awards including the Philip S. Portoghese Joint Lectureship sponsored by the Journal of Medicinal Chemistry and the ACS Division of Medicinal Chemistry (2018), the Ole Gisvold Lectureship in Medicinal Chemistry from the Department of Medicinal Chemistry at the University of Minnesota (2018), the University of California San Francisco 150th Anniversary Alumni Excellence Award (2015), and the Webster-Sibilsky Lecturer, University of Illinois (2012). He is a Fellow of the American Association for the Advancement of Science (2012), a senior Fulbright Scholar (1983-1984), and currently serves as an Associate Editor for the Journal of Medicinal Chemistry. He is also a member of the Board of Directors of Gibson Oncology. He was recently selected as a Fellow of the National Academy of Inventors (2018) and as a Highly Prolific Author by the Journal of Medicinal Chemistry (2017). This issue hopes to honor his broad contributions to the fields of organic and medicinal chemistry. The reviews presented herein try to highlight (although not in an extensive way), some of the most important scientific accomplishments made by Dr. Cushman and his group. Even though his papers and patents clearly indicate his impact in the field, publications do not do justice to his scientific contributions. Dr. Cushman is an example of hard work, enthusiasm, and dedication. He set the bar very high for all of his 39 graduate students and 64 postdocs and visiting scholars by being in the laboratory early and leaving late. He demanded excellence from others but always did the same of himself. He is detail-oriented, a perfectionist who always made sure research was done at a high level and with integrity, ethics, and honesty above everything else. He loves organic and medicinal chemistry and would make sure that each of his students and trainees understood the mechanism of a reaction and the mode of action of their compounds. The best thing, and I can speak for each one my labmates, is that Dr. Cushman allowed us to fail. He usually knew what reaction was going to work and which one would not. However, he would give us the freedom to try and to experiment. He would review the problem, analyze the data, and guide us in the right direction but would make sure we were the ones finding the answer to the problem (which of course, he sometimes knew before the process even started). This mentoring style helped us to grow as scientists and to become the best we could be. It has been my pleasure to coordinate this issue and see a glimpse of just how far his research—and his positive influence—has extended.

Abstracts Presented at the American Chemical Society National Meetings: Analysis of Their Characteristics

ABSTRACTThis paper analyzes the abstracts from the 244th – 248th American Chemical Society national meetings, 2012–2014 for the Divisions of Biological Chemistry and Organic Chemistry. The main objective of the study was to identify the percentage of abstracts that were published as related papers and the time it took to do so. It also investigated likely factors that determined whether the abstracts will be published as papers. These factors included the number of author(s) per abstract, the number of institutions involved in the research, and the country of origin of the research. The paper also highlights the percentage of papers that were published before and after the conferences and the quality of the journals in which they were published. The citation characteristics of the articles published before and after the conference are also covered.

Correction to: Bis-chelates of nickel(II) and copper(II) with an O,S-donor piperazine ligand

After the publication of this article ‘Bis-chelates of nickel(II) and copper(II) with an O,S-donor piperazine ligand,’ it came to our attention that Debashis Ray was omitted from the list of authorship. Debashis Ray supervised this work at IIT Kharagpur and has been added as an author to this publication. The authors would also like to clarify that this work was carried out at the Department of Chemistry, Indian Institute of Technology (IIT) Kharagpur and this is the affiliation for both authors for this article. During this work, Haridas Mandal was a Ph.D. student at IIT Kharagpur, working under the supervision of Prof. Ray. He has since moved to the Chemical Division, Southern Region, Geological Survey of India, and this is his current affiliation. Dr. Mandal is thankful to the Department of Science and Technology, Govt. of India, New Delhi, for providing the single-crystal X-ray diffractometer in the Department of Chemistry, IIT Kharagpur, under its FIST program.

On the Conversion Efficiency of CO2 Electroreduction on Gold

Benjamin A. Zhang is a PhD student at Harvard University. His research focus is on the control of mass transport and concentration gradients in electrochemical reactions, in particular CO2 reduction, through nano- and mesostructuring of electrodes. Cyrille Costentin is Professor at Universite Paris Diderot. He received his undergraduate education at Ecole Normale Superieure de Cachan and his PhD at Universite Paris Diderot. He is currently a Visiting Scientist in the group of D.G. Nocera at Harvard University. His interests include mechanisms and reactivity in electron transfer chemistry with particular emphasis on proton-coupled electron transfer and catalysis of electrochemical reactions. Daniel G. Nocera is the Patterson Rockwood Professor of Energy at Harvard University. His group studies mechanisms of biological and chemical energy conversion.

Effect of Phytase and Farm Yard Manure on Growth, Nutrient Uptake and Yield of Soybean in Non-Calcareous Soil

A pot culture experiment was conducted during Kharif -2014 at Division of Soil Science and Agricultural Chemistry, College of Agriculture, Pune to assess the effect of phytase and FYM levels on growth, nutrient uptake and yield of soybean in non-calcareous soil. The treatment consisted of four levels of each phytase (0, 1200, 2400 and 3600 IU) and FYM (0, 2.5, 5, 7.5 t ha-1) replicated thrice in factorial randomized block design. Growth attributes (viz., plant height, root length, root shoot ratio, fresh and dry weight of roots, number and weight of root nodules), plant dry matter accumulation were studied at 50% flowering of soybean. Further, grain and straw yield along with nutrient uptake were also studied at harvest of soybean. Application of phytase @ 3600 IU or FYM @ 7.5 t ha-1 or their combine application reported significantly higher plant height, root length, root shoot ratio, fresh and dry weight of roots, number and weight of root nodules than rest of the treatment at 50 % flowering of soybean. Significantly higher mean straw yield was recorded with the application of phytase @ 3600 IU (12.86 and 14.31 g pot-1) at 50 % flowering and at harvest. Significantly higher grain and straw yield was recorded with the application of phytase @ 3600 IU (17.34 and 14.31 g pot-1) which was statistically at par with phytase @ 2400 IU (17.28 and 13.74 g pot-1). Combine application of phytase @ 3600 IU along with FYM @ 7.5 t ha-1 recorded significantly higher nitrogen (643.93 and 801.95 mg pot-1), phosphorus (82.89 and 128.08 mg pot-1) and potassium (354.75 and 114.72 mg pot-1) uptake was recorded with the application of phytase @ 3600 IU at 50 % flowering and at harvest of soybean respectively.

Effect of Green Manuring Crops on Carbon Mineralization, Dehydrogenase and β-Glucosidase Activities in Inceptisols

Pot culture and incubation studies were conducted to assess the carbon mineralization and soil enzyme activities with green manure crop residue in Inceptisols. The studies were undertaken with six green manure crop residues viz., sunhemp (Crotolaria juncea), cluster bean (Cymopsis tetragonaloba), cow pea (Vigna unguiculata), mutant dhaincha (Sesbania rostrata), green gram (Vigna mungo) and soybean (Glycine max L. Merrill) which were grown up to 50 per cent flowering in the pot along with control at Division of Soil Science and Agricultural Chemistry, College of Agriculture, Pune during 2020-21 in completely randomized design with three replications. Carbon mineralization and soil enzyme activities i.e. dehydrogenase and β- glucosidase were studied by incorporating green manure crop residues in soil. In the incubation study, the mutant dhaincha recorded significantly higher release of CO2-C throughout the incubation period than othertreatments. The rate of release of CO2-C was slow at 0 and 15 days after incubation but increased at 45 days after incubation and thereafter, gradual decline in all green manures incorporated treatments was observed. Higher dehydrogenase and β- glucosidase activity were recorded in sun hemp treated pots.

A Study of Role Stressors and Job Satisfaction: The Case of MNCs in Collectivist Context.

Job stressors in organizational studies are commonly known as role stressors. These include role overload (RO), role conflict (RC), role ambiguity (RA) and job insecurity (JI). We explored the predicting role of these stressors on the overall level of job stress (JS) and job satisfaction (JSF). Moreover, we tested the role of JS as a mediator between the relationship of role stressors and JSF in a multinational corporation (MNC) in a non-western collectivist context (Pakistan). We obtained data through field surveys from 173 engineering employees from the electrical, mechanical, safety and chemical divisions. Role stressors significantly predicted overall level of JS and JSF. JS was also found to partially mediate the relationship between role stressors and JSF. The study findings suggest that foreign ownership needs to focus not only on the economic value, but also the organizational and job design to mitigate the detrimental role of selected stressors. The results of this study have important implications for MNCs in general, and in developing countries in particular. Theoretical and managerial implications are discussed with recommendations.

(Invited) Challenges and Opportunities in Developing Anode Catalysts for Direct Ethanol and Ammonia Fuel Cells

Direct liquid fuel cells (DLFC) are attractive alternatives of batteries and hydrogen fuel cells for applications where high energy density and easy to refill are critical. For example, in powering a 200W-1kWh drone, a DLFC system can weigh only 1/10 of a battery and refill is simpler than hydrogen and faster than battery recharging. Among liquid fuels, ethanol stands out for its high energy density and ammonia is carbon free. A drawback is the lack of anode catalysts for complete oxidation of ethanol and ammonia at low potentials with sufficient activity per mass of platinum group metals (PGM). Dr. Shimshon Gottesfeld is currently leading an ARPA-E project on “Direct ammonia hydroxide exchange membrane fuel cells”, and I am in the team to develop high performance catalysts for ammonia oxidation reaction (AOR) with low PGM contents. While I learned from reading his papers on a wide range of topics and talking with him at conferences in many years, working under his leadership made me further appreciate his contribution in advancing fuel cell technologies. Inspired by his sharp and open mind in choosing and solving technical issues and in pursuing deep fundamental understandings, I’d like to discuss the challenges in developing anode catalysts for ethanol and ammonia oxidation and to illustrate promising directions and opportunities based on new insights in reaction mechanisms and material/structure/performance correlations. The performances of ethanol oxidation reaction (EOR) and AOR in alkaline media on the best catalysts that we recently developed will be presented and compared. The results show that facile EOR is possible at ambient temperature when a direct 12-electron EOR pathway is activated. Analyses of in situ infrared reflection absorption spectra indicate that the C-C bond splits via ethanol dissociation and full oxidation completes without CO as poisoning intermediate. However, carbonate formation in alkaline media lowers pH and reduces EOR activity. Carbon-free ammonia circumvents this issue, but AOR activity needs enhancement from elevated temperature due to the high activation barrier for N-N bond formation. Most studies so far focused on Pt-based catalysts and the polarization curves were measured at ambient temperature. Our study of temperature-dependent AOR kinetics found that activity enhancement from 25 to 60 oC is in the order of Ir (5.5) > IrPt (4.2) > Pt (2.0).1 For both EOR and AOR, Ir is effective in promoting dehydrogenation, and thus, in lowering the onset potentials. Thus, Ir-based catalysts are more promising than Pt-based catalysts for AOR. I’ll also show that the C-C bond cleavage in EOR and the N-N bond formation in AOR prefer distinctly different atomic structures. The new insights point out opportunities and directions for future studies. Acknowledgements The author thanks Zhixiu Liang, Liang Song, Jingyi Chen, Shiqing Deng, and Eli Stavitski for their collaborations. The work was funded by the Advanced Research Projects Agency-Energy (ARPA-E), U.S. Department of Energy, under Award Number DE-AR0000805 and by the Division of Chemical Sciences, Geosciences and Biosciences Division, US Department of Energy under contract DE-SC0012704. References Song, L. et al. Temperature-Dependent Kinetics and Reaction Mechanism of Ammonia Oxidation on Pt, Ir, and PtIr Alloy Catalysts. J. Electrochem. Soc. 165, J3095–J3100 (2018).

Iridium-Based Catalysts for Electro-Oxidation of Ammonia in Alkaline Media

Ammonia is an attractive carbon-free liquid fuel for alkaline membrane fuel cells. While ethanol has higher energy density than ammonia, its product, CO2, reacts with OH- to form carbonate in alkaline media, which can cause kinetic loss and cell failure. Thus, carbon-free is an advantage of ammonia.[1, 2] In the 6-electron ammonia oxidation reaction (AOR), 2NH­3 +6OH- = N2 + 3H2O + 6e-, formation of the N-N bond is a rate-limiting step with rather high activation barrier. Most of research focused on Pt-based catalysts because Pt is essential for high current peak at ambient temperature. Ir is known for its low onset potential for AOR. As our recent temperature-dependent kinetic study showed, alloy PtIr/C is currently the best commercial catalyst for AOR at 60 oC and the temperature enhancement factor between 60 and 25 oC is in the order of Ir (5.5) > IrPt (4.2) > Pt (2.0).[3] Thus, developing Ir-based catalysts holds the promise for improving anode performance in fuel cells operating at elevated temperatures. In this talk, we show that Fe nitride can promote the AOR activity on Ir, Pt, and IrPt catalysts. Three carbon-supported catalysts, Ir4Fe2Nx/C, Ir3Pt1Fe2Nx/C, and Pt3Fe2Nx/C, were prepared by reducing and nitriding metal chloride precursors on Vulcan XC-72 carbon in a tube furnace with mixed hydrogen and ammonia gases. We dispersed the catalysts on gas diffusion electrodes with a loading of platinum group metals (PGM) of 100 μg/cm2 and plot the AOR polarization curves with the currents normalized to PGM loadings in Figure 1. Even though Pt3Fe2Nx/C achieved the highest peak current density, its activity at low overpotential range (0.35- 0.5 V) is much lower than those containing Ir. The compression of the Ir lattice induced by the small alloyed Fe atoms results in slightly higher AOR peak current density of Ir4Fe2Nx/C than Ir/C, while the peak potentials remain unchanged. As the Pt: platinum-group-metal ratio increases from 0 in Ir/C and Ir4Fe2N/C to 100% in Pt3Fe2Nx/C, the peak potential increase gradually, which correspond well with the peak position for Ir3Pt1Fe2Nx/C catalysts which located between Ir/C and IrPt/C. When comparing AOR activity of Ir3Pt1Fe2Nx/C with Ir4Fe2Nx/C, substitution of 1/4 Ir atoms in Ir4Fe2Nx/C with Pt atoms leads to an optimal activity for AOR among the tested samples as a consequence of combining the low onset potentials of Ir4Fe2Nx/C and high peak current density of Pt3Fe2Nx/C. More detailed results of this work will be discussed in the presentation. Figure 2 shows the X-ray diffraction patterns of these three catalysts in comparison with two commercial catalysts of Ir/C and IrPt/C. There is no peak corresponding to any Fe or Fe nitride structures, indicating that Fe is well alloyed with Ir and/or Pt. It appears that AOR activity on Ir-based catalysts prefers neither expansion or contraction of Ir lattice. The diffraction peak for Ir3Pt1Fe2Nx/C locates at the same angle as the Ir/C which may be as an integrated effect from Pt (bigger than Ir) and Fe (smaller than Ir) atoms. Acknowledgements This research was funded by the Advanced Research Projects Agency-Energy (ARPA-E), U.S. Department of Energy, under Award Number DE-AR0000805 and by the Division of Chemical Sciences, Geosciences and Biosciences Division, US Department of Energy under contract DE-SC0012704.