Catalytic amino acid production from biomass-derived intermediates

Deng, Weiping; Wang, Yunzhu; Zhang, Sui; Gupta, Krishna M.; Hulsey, Max J.; Asakura, Hiroyuki; Liu, Lingmei; Han, Yu; Karp, Eric M.; Beckham, Gregg T.; Dyson, Paul J.; Jiang, Jianwen; Tanaka, Tsunehiro; Wang, Ye; Yan, Ning

doi:10.1073/pnas.1800272115

Title: Catalytic amino acid production from biomass-derived intermediates

Journal Article · Mon Apr 30 00:00:00 EDT 2018 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1800272115· OSTI ID:1437219

Deng, Weiping ^[1];

^[2]; Zhang, Sui ^[2]; Gupta, Krishna M. ^[2]; Hulsey, Max J. ^[2]; Asakura, Hiroyuki ^[3]; Liu, Lingmei ^[4]; Han, Yu ^[4]; Karp, Eric M. ^[5];

^[5];

^[6]; Jiang, Jianwen ^[2]; Tanaka, Tsunehiro ^[3]; Wang, Ye ^[7];

^[2]

National Univ. of Singapore (Singapore). Dept. of Chemical and Biomolecular Engineering; Xiamen Univ., Xiamen (China). State Key Lab. for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering
National Univ. of Singapore (Singapore). Dept. of Chemical and Biomolecular Engineering
Kyoto Univ. (Japan). Graduate School of Engineering, Dept. of Molecular Engineering; Kyoto Univ. (Japan). Elements Strategy Initiative for Catalysts & Batteries
King Abdullah Univ. of Science Technology, Thuwal (Saudi Arabia). Advanced Membranes and Porous Materials Center, Physical Sciences and Engineering Division
National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
Ecole Polytechnique Federale Lausanne (Switzlerland). Inst. des Sciences et Ingenierie Chimiques
Xiamen Univ., Xiamen (China). State Key Lab. for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering

Amino acids are the building blocks for protein biosynthesis and find use in myriad industrial applications including in food for humans, in animal feed, and as precursors for bio-based plastics, among others. However, the development of efficient chemical methods to convert abundant and renewable feedstocks into amino acids has been largely unsuccessful to date. To that end, here we report a heterogeneous catalyst that directly transforms lignocellulosic biomass-derived a-hydroxyl acids into a-amino acids, including alanine, leucine, valine, aspartic acid, and phenylalanine in high yields. The reaction follows a dehydrogenation-reductive amination pathway, with dehydrogenation as the rate-determining step. Ruthenium nanoparticles supported on carbon nanotubes (Ru/CNT) exhibit exceptional efficiency compared with catalysts based on other metals, due to the unique, reversible enhancement effect of NH₃ on Ru in dehydrogenation. Based on the catalytic system, a two-step chemical process was designed to convert glucose into alanine in 43% yield, comparable with the well-established microbial cultivation process, and therefore, the present strategy enables a route for the production of amino acids from renewable feedstocks. Moreover, a conceptual process design employing membrane distillation to facilitate product purification is proposed and validated. Overall, this study offers a rapid and potentially more efficient chemical method to produce amino acids from woody biomass components.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1437219

Report Number(s):: NREL/JA-5100-71523

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 115, Issue 20; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 127 works

Citation information provided by
Web of Science

References (46)

Comparison of Fast Pyrolysis Behavior of Cornstover Lignins Isolated by Different Methods Zhang, Jing; Kim, Kwang Ho; Choi, Yong S. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 7 https://doi.org/10.1021/acssuschemeng.7b01393	journal	June 2017
Highly efficient production of lactic acid from cellulose using lanthanide triflate catalysts Wang, Fen-Fen; Liu, Chun-Ling; Dong, Wen-Sheng Green Chemistry, Vol. 15, Issue 8 https://doi.org/10.1039/c3gc40836a	journal	January 2013
Direct Amination of Secondary Alcohols Using Ammonia Pingen, Dennis; Müller, Christian; Vogt, Dieter Angewandte Chemie International Edition, Vol. 49, Issue 44 https://doi.org/10.1002/anie.201002583	journal	July 2010
Production of Primary Amines by Reductive Amination of Biomass-Derived Aldehydes/Ketones Liang, Guanfeng; Wang, Aiqin; Li, Lin Angewandte Chemie International Edition, Vol. 56, Issue 11 https://doi.org/10.1002/anie.201610964	journal	February 2017
Reductive Catalytic Fractionation of Corn Stover Lignin Anderson, Eric M.; Katahira, Rui; Reed, Michelle ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 12 https://doi.org/10.1021/acssuschemeng.6b01858	journal	October 2016
MOF-derived cobalt nanoparticles catalyze a general synthesis of amines Jagadeesh, Rajenahally V.; Murugesan, Kathiravan; Alshammari, Ahmad S. Science, Vol. 358, Issue 6361 https://doi.org/10.1126/science.aan6245	journal	September 2017
Progress toward Lignin Valorization via Selective Catalytic Technologies and the Tailoring of Biosynthetic Pathways Key, Rebecca E.; Bozell, Joseph J. ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 10 https://doi.org/10.1021/acssuschemeng.6b01319	journal	August 2016
Heterogeneous Ni Catalysts for N-Alkylation of Amines with Alcohols Shimizu, Ken-ichi; Imaiida, Naomichi; Kon, Kenichi ACS Catalysis, Vol. 3, Issue 5 https://doi.org/10.1021/cs4001267	journal	April 2013
Quantification of acidic compounds in complex biomass-derived streams Karp, Eric M.; Nimlos, Claire T.; Deutch, Steve Green Chemistry, Vol. 18, Issue 17 https://doi.org/10.1039/C6GC00868B	journal	January 2016
Facile preparation of Ni/Al2O3 catalytic formulations with the aid of cyclodextrin complexes: Towards highly active and robust catalysts for the direct amination of alcohols Tomer, Ajay; Wyrwalski, Frédéric; Przybylski, Cédric Journal of Catalysis, Vol. 356 https://doi.org/10.1016/j.jcat.2017.10.006	journal	December 2017
Synthesis of α-Amino Acid Amides: Ruthenium-Catalyzed Amination of α-Hydroxy Amides Zhang, Min; Imm, Sebastian; Bähn, Sebastian Angewandte Chemie International Edition, Vol. 50, Issue 47 https://doi.org/10.1002/anie.201104309	journal	October 2011
Scaleable catalytic asymmetric Strecker syntheses of unnatural α-amino acids Zuend, Stephan J.; Coughlin, Matthew P.; Lalonde, Mathieu P. Nature, Vol. 461, Issue 7266 https://doi.org/10.1038/nature08484	journal	October 2009
Quantitative chemocatalytic production of lactic acid from glucose under anaerobic conditions at room temperature Li, Luyang; Shen, Feng; Smith, Richard L. Green Chemistry, Vol. 19, Issue 1 https://doi.org/10.1039/C6GC02443B	journal	January 2017
The Give and Take of Alcohol Activation Watson, A. J. A.; Williams, J. M. J. Science, Vol. 329, Issue 5992 https://doi.org/10.1126/science.1191843	journal	August 2010
Catalytic Transformation of Lignin for the Production of Chemicals and Fuels Li, Changzhi; Zhao, Xiaochen; Wang, Aiqin Chemical Reviews, Vol. 115, Issue 21, p. 11559-11624 https://doi.org/10.1021/acs.chemrev.5b00155	journal	October 2015
General Synthesis of Amino Acid Salts from Amino Alcohols and Basic Water Liberating H ₂ Hu, Peng; Ben-David, Yehoshoa; Milstein, David Journal of the American Chemical Society, Vol. 138, Issue 19 https://doi.org/10.1021/jacs.6b03488	journal	May 2016
Simultaneous saccharification and fermentation of kraft pulp by recombinant Escherichia coli for phenyllactic acid production Kawaguchi, Hideo; Uematsu, Kouji; Ogino, Chiaki Biochemical Engineering Journal, Vol. 88 https://doi.org/10.1016/j.bej.2014.04.014	journal	July 2014
Conversion of Sugars to Lactic Acid Derivatives Using Heterogeneous Zeotype Catalysts Holm, Martin Spangsberg; Saravanamurugan, Shunmugavel; Taarning, Esben Science, Vol. 328, Issue 5978, p. 602-605 https://doi.org/10.1126/science.1183990	journal	April 2010
Selective Synthesis of Primary Amines Directly from Alcohols and Ammonia Gunanathan, Chidambaram; Milstein, David Angewandte Chemie International Edition, Vol. 47, Issue 45 https://doi.org/10.1002/anie.200803229	journal	October 2008
pH-Dependent Chemoselective Synthesis of α-Amino Acids. Reductive Amination of α-Keto Acids with Ammonia Catalyzed by Acid-Stable Iridium Hydride Complexes in Water Ogo, Seiji; Uehara, Keiji; Abura, Tsutomu Journal of the American Chemical Society, Vol. 126, Issue 10 https://doi.org/10.1021/ja031633r	journal	March 2004
The Catalytic Amination of Alcohols Bähn, Sebastian; Imm, Sebastian; Neubert, Lorenz ChemCatChem, Vol. 3, Issue 12 https://doi.org/10.1002/cctc.201100255	journal	October 2011
Direct amination of dodecanol with NH3 over heterogeneous catalysts. Catalyst screening and kinetic modelling Ruiz, Doris; Aho, Atte; Saloranta, Tiina Chemical Engineering Journal, Vol. 307 https://doi.org/10.1016/j.cej.2016.08.083	journal	January 2017
Conversion of glucose into levulinic acid with solid metal(IV) phosphate catalysts Weingarten, Ronen; Kim, Yong Tae; Tompsett, Geoffrey A. Journal of Catalysis, Vol. 304 https://doi.org/10.1016/j.jcat.2013.03.023	journal	August 2013
Pyrolysis reaction networks for lignin model compounds: unraveling thermal deconstruction of β-O-4 and α-O-4 compounds Choi, Yong S.; Singh, Rahul; Zhang, Jing Green Chemistry, Vol. 18, Issue 6 https://doi.org/10.1039/C5GC02268A	journal	January 2016
Production of furfural and carboxylic acids from waste aqueous hemicellulose solutions from the pulp and paper and cellulosic ethanol industries Xing, Rong; Qi, Wei; Huber, George W. Energy & Environmental Science, Vol. 4, Issue 6 https://doi.org/10.1039/c1ee01022k	journal	January 2011
Amino acids production focusing on fermentation technologies – A review D'Este, Martina; Alvarado-Morales, Merlin; Angelidaki, Irini Biotechnology Advances, Vol. 36, Issue 1 https://doi.org/10.1016/j.biotechadv.2017.09.001	journal	January 2018
Valorization of Lignocellulosic Biomass Luque, Rafael; Triantafyllidis, Kostas ChemCatChem, Vol. 8, Issue 8 https://doi.org/10.1002/cctc.201600226	journal	April 2016
Rational, combinatorial, and genomic approaches for engineering L-tyrosine production in Escherichia coli Santos, C. N. S.; Xiao, W.; Stephanopoulos, G. Proceedings of the National Academy of Sciences, Vol. 109, Issue 34 https://doi.org/10.1073/pnas.1206346109	journal	August 2012
Direct Conversion of Cellulose to Glycolic Acid with a Phosphomolybdic Acid Catalyst in a Water Medium Zhang, Jizhe; Liu, Xin; Sun, Miao ACS Catalysis, Vol. 2, Issue 8 https://doi.org/10.1021/cs300342k	journal	July 2012
Scalable organocatalytic asymmetric Strecker reactions catalysed by a chiral cyanide generator Yan, Hailong; Suk Oh, Joong; Lee, Ji-Woong Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms2216	journal	January 2012
Transformation of Cellulose and its Derived Carbohydrates into Formic and Lactic Acids Catalyzed by Vanadyl Cations Tang, Zhenchen; Deng, Weiping; Wang, Yanliang ChemSusChem, Vol. 7, Issue 6 https://doi.org/10.1002/cssc.201400150	journal	May 2014
Mechanistic Insight into the Conversion of Tetrose Sugars to Novel α-Hydroxy Acid Platform Molecules Dusselier, Michiel; Van Wouwe, Pieter; de Clippel, Filip ChemCatChem, Vol. 5, Issue 2, p. 569-575 https://doi.org/10.1002/cctc.201200476	journal	November 2012
Shape-selective zeolite catalysis for bioplastics production Dusselier, Michiel; Van Wouwe, Pieter; Dewaele, Annelies Science, Vol. 349, Issue 6243 https://doi.org/10.1126/science.aaa7169	journal	July 2015
Chemistry goes green Clark, James H. Nature Chemistry, Vol. 1, Issue 1 https://doi.org/10.1038/nchem.146	journal	April 2009
Fast and Selective Sugar Conversion to Alkyl Lactate and Lactic Acid with Bifunctional Carbon–Silica Catalysts de Clippel, Filip; Dusselier, Michiel; Van Rompaey, Ruben Journal of the American Chemical Society, Vol. 134, Issue 24 https://doi.org/10.1021/ja301678w	journal	June 2012
Hydroxycinnamates in lignification Ralph, John Phytochemistry Reviews, Vol. 9, Issue 1, p. 65-83 https://doi.org/10.1007/s11101-009-9141-9	journal	August 2009
Synthesis of Itaconic Acid Ester Analogues via Self-Aldol Condensation of Ethyl Pyruvate Catalyzed by Hafnium BEA Zeolites Wang, Yuran; Lewis, Jennifer D.; Román-Leshkov, Yuriy ACS Catalysis, Vol. 6, Issue 5 https://doi.org/10.1021/acscatal.6b00561	journal	April 2016
Chemical synthesis of lactic acid from cellulose catalysed by lead(II) ions in water Wang, Yanliang; Deng, Weiping; Wang, Binju Nature Communications, Vol. 4, Article No. 2141 https://doi.org/10.1038/ncomms3141	journal	July 2013
Conversion of Biomass into Chemicals over Metal Catalysts Besson, Michèle; Gallezot, Pierre; Pinel, Catherine Chemical Reviews, Vol. 114, Issue 3 https://doi.org/10.1021/cr4002269	journal	October 2013
Alanine production in an H+-ATPase- and lactate dehydrogenase-defective mutant of Escherichia coli expressing alanine dehydrogenase Wada, Masaru; Narita, Kotomi; Yokota, Atsushi Applied Microbiology and Biotechnology, Vol. 76, Issue 4 https://doi.org/10.1007/s00253-007-1065-y	journal	June 2007
Selective Synthesis of Primary Amines Directly from Alcohols and Ammonia Gunanathan, Chidambaram; Milstein, David Angewandte Chemie, Vol. 120, Issue 45 https://doi.org/10.1002/ange.200803229	journal	October 2008
Synthesis of α-Amino Acid Amides: Ruthenium-Catalyzed Amination of α-Hydroxy Amides Zhang, Min; Imm, Sebastian; Bähn, Sebastian Angewandte Chemie, Vol. 123, Issue 47 https://doi.org/10.1002/ange.201104309	journal	October 2011
Production of Primary Amines by Reductive Amination of Biomass-Derived Aldehydes/Ketones Liang, Guanfeng; Wang, Aiqin; Li, Lin Angewandte Chemie, Vol. 129, Issue 11 https://doi.org/10.1002/ange.201610964	journal	February 2017
Asymmetric Catalysis: Science and Opportunities (Nobel Lecture) Copyright© The Nobel Foundation 2002. We thank the Nobel Foundation, Stockholm, for permission to print this lecture. Noyori, Ryoji Angewandte Chemie International Edition, Vol. 41, Issue 12 https://doi.org/10.1002/1521-3773(20020617)41:12<2008::aid-anie2008>3.0.co;2-4	journal	June 2002
Expanding the biomass derived chemical space Brun, Nicolas; Hesemann, Peter; Esposito, Davide Chemical Science, Vol. 8, Issue 7 https://doi.org/10.1039/c7sc00936d	journal	January 2017
Converting MOFs into amination catalysts Chen, Li-Feng; Xu, Qiang Science, Vol. 358, Issue 6361 https://doi.org/10.1126/science.aap8004	journal	October 2017

Cited By (23)

Catalytic Synthesis of N -(5-Methylfurfuryl)aniline from Bio-Derived Carbohydrates Xiao, Jianjun; Jin, Qi; Yang, Jiaqi Asian Journal of Organic Chemistry, Vol. 8, Issue 3 https://doi.org/10.1002/ajoc.201800690	journal	January 2019
Catalytic Production of Alanine from Waste Glycerol Wang, Yunzhu; Furukawa, Shinya; Song, Song Angewandte Chemie, Vol. 132, Issue 6 https://doi.org/10.1002/ange.201912580	journal	December 2019
Catalytic Production of Alanine from Waste Glycerol Wang, Yunzhu; Furukawa, Shinya; Song, Song Angewandte Chemie International Edition, Vol. 59, Issue 6 https://doi.org/10.1002/anie.201912580	journal	February 2020
Catalytic Synthesis of 2,5‐Furandicarboxylic Acid from Concentrated 2,5‐Diformylfuran Mediated by N ‐hydroxyimides under Mild Conditions Xia, Fei; Ma, Jiping; Jia, Xiuquan Chemistry – An Asian Journal, Vol. 14, Issue 19 https://doi.org/10.1002/asia.201901001	journal	August 2019
Single‐Site Molybdenum Catalyst for the Synthesis of Fumarate Jiang, Huifang; Lu, Rui; Si, Xiaoqin ChemCatChem, Vol. 11, Issue 17 https://doi.org/10.1002/cctc.201900332	journal	July 2019
Protein‐Rich Biomass Waste as a Resource for Future Biorefineries: State of the Art, Challenges, and Opportunities De Schouwer, Free; Claes, Laurens; Vandekerkhove, Annelies ChemSusChem, Vol. 12, Issue 7 https://doi.org/10.1002/cssc.201802418	journal	April 2019
Efficient and Selective Oxidation of 5-Hydroxymethylfurfural into 2, 5-Diformylfuran Catalyzed by Magnetic Vanadium-Based Catalysts with Air as Oxidant Lai, Jinhua; Zhou, Shuolin; Cheng, Feng Catalysis Letters, Vol. 150, Issue 5 https://doi.org/10.1007/s10562-019-03041-w	journal	November 2019
Biochemical coupling strategy promotes saccharification of bamboo leaves biomass via xylanase and heteropolyacids Xiao, Zhuqian; Zhang, Qiang; Wang, Xiaolei Biomass Conversion and Biorefinery https://doi.org/10.1007/s13399-019-00518-x	journal	October 2019
N-formyl-stabilizing quasi-catalytic species afford rapid and selective solvent-free amination of biomass-derived feedstocks Li, Hu; Guo, Haixin; Su, Yaqiong Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08577-4	journal	February 2019
Amination of β-hydroxyl acid esters via cooperative catalysis enables access to bio-based β-amino acid esters Afanasenko, Anastasiia; Yan, Tao; Barta, Katalin Communications Chemistry, Vol. 2, Issue 1 https://doi.org/10.1038/s42004-019-0229-x	journal	November 2019
Oxidant free conversion of alcohols to nitriles over Ni-based catalysts Wang, Yunzhu; Furukawa, Shinya; Zhang, Zhang Catalysis Science & Technology, Vol. 9, Issue 1 https://doi.org/10.1039/c8cy01799a	journal	January 2019
Conversion of levulinic acid to γ-valerolactone over Ru/Al ₂ O ₃ –TiO ₂ catalyst under mild conditions Wang, Ruifeng; Chen, Lungang; Zhang, Xinghua RSC Advances, Vol. 8, Issue 71 https://doi.org/10.1039/c8ra07938b	journal	January 2018
One-pot conversion of lysine to caprolactam over Ir/H-Beta catalysts Sebastian, Joby; Zheng, Mingyuan; Jiang, Yu Green Chemistry, Vol. 21, Issue 9 https://doi.org/10.1039/c9gc00415g	journal	January 2019
Synthesis of gasoline and jet fuel range cycloalkanes and aromatics from poly(ethylene terephthalate) waste Tang, Hao; Li, Ning; Li, Guangyi Green Chemistry, Vol. 21, Issue 10 https://doi.org/10.1039/c9gc00571d	journal	January 2019
Synthesis of jet fuel range high-density polycycloalkanes with polycarbonate waste Tang, Hao; Hu, Yancheng; Li, Guangyi Green Chemistry, Vol. 21, Issue 14 https://doi.org/10.1039/c9gc01627a	journal	January 2019
Catalytic oxidative dehydrogenation of malic acid to oxaloacetic acid Drif, Asmaa; Pineda, Antonio; Morvan, Didier Green Chemistry, Vol. 21, Issue 17 https://doi.org/10.1039/c9gc01768b	journal	January 2019
Upgrading of levulinic acid into diverse N-containing functional chemicals Xue, Zhimin; Yu, Dongkun; Zhao, Xinhui Green Chemistry, Vol. 21, Issue 20 https://doi.org/10.1039/c9gc02415h	journal	January 2019
Cellulose conversion into lactic acid over supported HPA catalysts Marianou, Asimina A.; Michailof, Chrysoula C.; Ipsakis, Dimitrios Green Chemistry, Vol. 21, Issue 22 https://doi.org/10.1039/c9gc02622c	journal	January 2019
Surface amino-functionalization of Sn-Beta zeolite catalyst for lactic acid production from glucose Shen, Zheng; Kong, Ling; Zhang, Wei RSC Advances, Vol. 9, Issue 33 https://doi.org/10.1039/c9ra01264h	journal	January 2019
Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium Qiu, Zihang; Lv, Leiyang; Li, Jianbin Chemical Science, Vol. 10, Issue 18 https://doi.org/10.1039/c9sc00595a	journal	January 2019
Self-supported hydrogenolysis of aromatic ethers to arenes Meng, Qinglei; Yan, Jiang; Liu, Huizhen Science Advances, Vol. 5, Issue 11 https://doi.org/10.1126/sciadv.aax6839	journal	November 2019
Oxidant free conversion of alcohols to nitriles over Ni-based catalysts Wang, Y.; Furukawa, S.; Zhang, Z. Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.37700	text	January 2019
Catalyst: Is the Amino Acid a New Frontier for Biorefineries? Yan, Ning; Wang, Yunzhu Chem, Vol. 5, Issue 4 https://doi.org/10.1016/j.chempr.2019.03.016	journal	April 2019

Similar Records

Analysis of the cyanobacterial amino acid metabolism with a precise genome-scale metabolic reconstruction of Anabaena sp. UTEX 2576

Journal Article · Wed Apr 07 00:00:00 EDT 2021 · Biochemical Engineering Journal · OSTI ID:1437219

Norena-Caro, Daniel A.; Zuniga, Cristal; Pete, Amber J.; +6 more

Leaf ontogeny as a factor in susceptibility to ozone: amino acid and carbohydrate changes during expansion

Journal Article · Thu Jul 01 00:00:00 EDT 1971 · Am. J. Bot.; (United States) · OSTI ID:1437219

Ting, I P; Mukerji, S K

AUTOMATIC AMINO ACID ANALYZER AS A NEW TOOL IN RADIATION RESEARCH

Journal Article · Tue Jan 01 00:00:00 EST 1963 · Proc. Japan Conf. Radioisotopes · OSTI ID:1437219

Hatano, H; Ganno, S; Amma, T

Related Subjects

09 BIOMASS FUELS
amino acids
a-hydroxyl acids
amination
catalysis
ruthenium

Title: Catalytic amino acid production from biomass-derived intermediates

Citation Formats

References (46)

Cited By (23)

Similar Records

Related Subjects