Citation: LI Maosheng, CHEN Jinlong, TAO Youhua. Regio- and Stereoselective Ring-Opening Metathesis Polymerization of Amino Acid Functionalized Cyclooctenes[J]. Chinese Journal of Applied Chemistry, ;2020, 37(3): 280-292. doi: 10.11944/j.issn.1000-0518.2020.03.190253 shu

Regio- and Stereoselective Ring-Opening Metathesis Polymerization of Amino Acid Functionalized Cyclooctenes

a.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of the Chinese Academy of Sciences, Beijing 100039, China

Corresponding author: TAO Youhua, youhua.tao@ciac.ac.cn
Received Date: 25 September 2019
Revised Date: 11 October 2019
Accepted Date: 7 November 2019

Fund Project: the National Natural Science Foundation of China 21805272the Jilin Science and Technology Bureau 20180201070GXSupported by the National Natural Science Foundation of China(No.21805272), and the Jilin Science and Technology Bureau(No.20180201070GX)

Figures(9)

Synthesis of side-chain amino acid-bearing polymers with controllable primary structures is still a long-term challenge in polymer chemistry compared to biomacromolecules (such as proteins and DNA) with completely precise microstructures. Here, we describe the synthesis of high trans-stereoregular (>99%) and high head-to-tail regioregularity (>99%) leucine-based homopolymers and block copolymers with relatively low polydispersities ranging from 1.3 to 1.6, using two designed monomers, namely (cyclooct-2-ene-1-carbonyl)-L-leucine methyl ester (1) and (cyclooct-2-ene-1-carbonyl)-L-leucine (2), via Grubbs 2nd catalyst at mild conditions. Importantly, the block copolymer of monomers1 and2 with molar ratio n(1):n(2)=50:50 is soluble in acetone to form reverse micelles with radius around 30 nm, which is composed of a hydrophilic core of poly(2) and a hydrophobic shell of poly(1). However, the random copolymers with the same proportion was partially insoluble in the solvent. These amino acid-bearing polymers with well-defined regio-/stereoregular structures provide the basis for relevant applications in biomimetic materials.
- amino acid-bearing polymers,
- ring-opening metathesis polymerization,
- regio- and stereoselectivity,
- block copolymers,
- reverse micelles
1. [1]
  Laursen J S, Harris P, Fristrup P. Triangular Prism-Shaped β-Peptoid Helices as Unique Biomimetic Scaffolds[J]. Nat Commun, 2015,6:7013-7022. doi: 10.1038/ncomms8013
2. [2]
  Lai H, Chen X, Lu Q. A New Strategy to Synthesize Bottlebrushes with a Helical Polyglutamate Backbone via N-Carboxyanhydride Polymerization and RAFT[J]. Chem Commun, 2014,50:14183-14186. doi: 10.1039/C4CC06575A
3. [3]
  TAO Youhua. New Polymerization Methodology of Amino Acid Based on Lactam Polymerization[J]. Acta Polym Sin, 2016(9):1151-1159.
4. [4]
  Li M, Tao Y, Tang J. Synergetic Organocatalysis for Eliminating Epimerization in Ring-Opening Polymerizations Enables Synthesis of Stereoregular Isotactic Polyester[J]. J Am Chem Soc, 2019,141(1):281-289. doi: 10.1021/jacs.8b09739
5. [5]
  Wang S X, Tao Y, Wang J. A Versatile Strategy for the Synthesis of Sequence-Defined Peptoids with Side-Chain and Backbone Diversity via Amino Acid Building Blocks[J]. Chem Sci, 2019,10:1531-1538. doi: 10.1039/C8SC03415J
6. [6]
  Wang S, He W, Xiao C. Synthesis of Y-Shaped OEGylated Poly(amino acid)s:The Impact of OEG Architecture[J]. Biomacromolecules, 2019,20(4):1655-1666. doi: 10.1021/acs.biomac.9b00026
7. [7]
  Tao Y, Wang S, Zhang X. Synthesis and Properties of Alternating Polypeptoids and Polyampholytes as Protein-Resistant Polymers[J]. Biomacromolecules, 2018,19(3):936-942. doi: 10.1021/acs.biomac.7b01719
8. [8]
  He W, Tao Y, Wang X. Functional Polyamides:A Sustainable Access via Lysine Cyclization and Organocatalytic Ring-Opening Polymerization[J]. Macromolecules, 2018,51(20):8248-8257. doi: 10.1021/acs.macromol.8b01790
9. [9]
  Chen J, Li M, He W. Facile Organocatalyzed Synthesis of Poly(ε-lysine) under Mild Conditions[J]. Macromolecules, 2017,50(23):9128-9134. doi: 10.1021/acs.macromol.7b02331
10. [10]
  Zhang X, Wang S, Liu J. Ugi Reaction of Natural Amino Acids:A General Route Toward Facile Synthesis of Polypeptoids for Bioapplications[J]. ACS Macro Lett, 2016,5(9):1049-1054. doi: 10.1021/acsmacrolett.6b00530
11. [11]
  Tao Y, Wang Z, Tao Y H. Polypeptoids Synthesis Based on Ugi Reaction:Advances and Perspectives[J]. Biopolymers, 2019,110(3).
12. [12]
  Zhang H, Chen J, Zhang X. Multidentate Comb-Shape Polypeptides Bearing Trithiocarbonate Functionality:Synthesis and Application for Water-Soluble Quantum Dots[J]. Biomacromolecules, 2017,18(3):924-910. doi: 10.1021/acs.biomac.6b01760
13. [13]
  Tao Y, Chen X, Jia F. New Chemosynthetic Route to Linear ε-Poly-lysine[J]. Chem Sci, 2015,6:6385-6391. doi: 10.1039/C5SC02479J
14. [14]
  Bellomo E G, Wyrsta M D, Pakstis L. Stimuli-Responsive Polypeptide Vesicles by Conformation-Specific Assembly[J]. Nat Mater, 2004,3:244-248. doi: 10.1038/nmat1093
15. [15]
  Deming T J. Synthetic Polypeptides for Biomedical Applications[J]. Prog Polym Sci, 2007,32:858-875. doi: 10.1016/j.progpolymsci.2007.05.010
16. [16]
  Kiessling L L, Fishman J M. Biologically Active Polymers[B]. Handbook of Metathesis; Wiley-VCH Verlag GmbH & Co.KGaA: 2015: 169-206.
17. [17]
  Chen X, Lai H, Xiao C. New Bio-renewable Polyester with Rich Side Amino Groups from L-Lysine via Controlled Ring-Opening Polymerization[J]. Polym Chem, 2014,5:6495-6502. doi: 10.1039/C4PY00930D
18. [18]
  Mori H, Endo T. Amino-Acid-Based Block Copolymers by RAFT Polymerization[J]. Macromol Rapid Commun, 2012,33:1090-1107. doi: 10.1002/marc.201100887
19. [19]
  Ayres L, Hans P, Adams J. Peptide Polymer Vesicles Prepared by Atom Transfer Radical Polymerization[J]. J Polym Sci Polym Chem, 2005,43:6355-6366. doi: 10.1002/pola.21107
20. [20]
  O'Reilly R K. Using Controlled Radical Polymerisation Techniques for the Synthesis of Functional Polymers Containing Amino Acid Moieties[J]. Polym Int, 2010,59:568-573.
21. [21]
  Lee Y, Sampson N S. Polymeric ADAM Protein Mimics Interrogate Mammalian Sperm Egg Binding[J]. ChemBioChem, 2009,10:929-937. doi: 10.1002/cbic.200800791
22. [22]
  Bauri K, De P, Shah P N. Polyisobutylene-Based Helical Block Copolymers with pH-Responsive Cationic Side-Chain Amino Acid Moieties by Tandem Living Polymerizations[J]. Macromolecules, 2013,46(15):5861-5870. doi: 10.1021/ma401395f
23. [23]
  Mori H, Takahashi E, Ishizuki A. Tryptophan-Containing Block Copolymers Prepared by RAFT Polymerization:Synthesis, Self-Assembly, and Chiroptical and Sensing Properties[J]. Macromolecules, 2013,46(16):6451-6465. doi: 10.1021/ma400596r
24. [24]
  Bielawski C W, Hillmyer M A. Telechelic Polymers from Olefin Metathesis Methodologies[B]. Handbook of Metathesis; Grubbs, R. H., ED.; Wiley-VCH: Weinheim, Germany, 2003: 255-282.
25. [25]
  Penczek S, Cypryk M, Duda A. Living Ring-opening Polymerizations of Heterocyclic Monomers[J]. Prog Polym Sci, 2007,32:247-282. doi: 10.1016/j.progpolymsci.2007.01.002
26. [26]
  Wu J, Yu T L, Chen C T. Recent Developments in Main Group Metal Complexes Catalyzed/Initiated Polymerization of Lactides and Related Cyclic Esters[J]. Coord Chem Rev, 2006,250:602-626. doi: 10.1016/j.ccr.2005.07.010
27. [27]
  Maynard H D, Okada S Y, Grubbs R H. Inhibition of Cell Adhesion to Fibronectin by Oligopeptide-Substituted Polynorbornenes[J]. J Am Chem Soc, 2001,123(7):1275-1279. doi: 10.1021/ja003305m
28. [28]
  Biagini SC G, Gareth Davies R, Gibson V C. Ruthenium Initiated Ring Opening Metathesis Polymerisation of Amino-acid and -Ester Functionalised Norbornenes and a Highly Selective Chain-End Functionalisation Reaction Using Molecular Oxygen[J]. Polymer, 2001,42:6669-6671. doi: 10.1016/S0032-3861(01)00146-X
29. [29]
  Sutthasupa S, Shiotsuki M, Masuda T. Alternating Ring-Opening Metathesis Copolymerization of Amino Acid Derived Norbornene Monomers Carrying Nonprotected Carboxy and Amino Groups Based on Acid? Base Interaction[J]. J Am Chem Soc, 2009,131(30):10546-10551. doi: 10.1021/ja903248c
30. [30]
  Osawa K, Kobayashi S, Tanaka M. Synthesis of Sequence-Specific Polymers with Amide Side Chains via Regio-/Stereoselective Ring-Opening Metathesis Polymerization of 3-Substituted cis-Cyclooctene[J]. Macromolecules, 2016,49(21):8154-8161. doi: 10.1021/acs.macromol.6b01829
31. [31]
  Kobayashi S, Fukuda K, Kataoka M. Regioselective Ring-Opening Metathesis Polymerization of 3-Substituted Cyclooctenes with Ether Side Chains[J]. Macromolecules, 2016,49(7):2493-2501. doi: 10.1021/acs.macromol.6b00273
32. [32]
  Zhang J, Matta M E, Martinez H. Precision Vinyl Acetate/Ethylene(VAE) Copolymers by ROMP of Acetoxy-Substituted Cyclic Alkenes[J]. Macromolecules, 2013,46(7):2535-2543. doi: 10.1021/ma400092z
33. [33]
  Zhang J, Matta M E, Hillmyer M A. Synthesis of Sequence-Specific Vinyl Copolymers by Regioselective ROMP of Multiply Substituted Cyclooctenes[J]. ACS Macro Lett, 2012,1(12):1383-1387. doi: 10.1021/mz300535r
34. [34]
  Martinez H, Mir P, Charbonneau P. Selectivity in Ring-Opening Metathesis Polymerization of Z-Cyclooctenes Catalyzed by a Second-generation Grubbs Catalyst[J]. ACS Catal, 2012,2(12):2547-2556. doi: 10.1021/cs300549u
35. [35]
  Kobayashi S, Pitet L M, Hillmyer M A. Regio- and Stereoselective Ring-Opening Metathesis Polymerization of 3-Substituted Cyclooctenes[J]. J Am Chem Soc, 2011,133(15):5794-5797. doi: 10.1021/ja201644v
36. [36]
  Martinez H, Ren N, Matta M E. Ring-Opening Metathesis Polymerization of 8-Membered Cyclic Olefins[J]. Polym Chem, 2014,5:3507-3532. doi: 10.1039/c3py01787g
37. [37]
  Li M, Cui F, Li Y. Crystalline Regio-/Stereoregular Glycine-Bearing Polymers from ROMP:Effect of Microstructures on Materials Performances[J]. Macromolecules, 2016,49(24):9415-9424. doi: 10.1021/acs.macromol.6b02244
38. [38]
  Bates C M, Bates F S. 50th Anniversary Perspective:Block Polymers-Pure Potential[J]. Macromolecules, 2017,50(1):3-22.
39. [39]
  Ahmed S R, Bullock S E, Cresce A V. Polydispersity Control in Ring Opening Metathesis Polymerization of Amphiphilic Norbornene Diblock Copolymers[J]. Polymer, 2003,44:4943-4948. doi: 10.1016/S0032-3861(03)00487-7
40. [40]
  Gill G B, Idris M S, Kirollos K S. Ene Reactions of Indane-1, 2, 3-trione(A Super-Enophile) and Related Vicinal Tricarbonyl Systems[J]. J Chem Soc, Perkin Transactions 1, 1992,18:2355-2365.
41. [41]
  Gill G B, Idris M S, Kirollos K S. Oxidative Cleavage of Indane-1, 2, 3-Trione-Ene Adducts; A Convenient Synthesis of Allyl and Allenyl Carboxylic Acids[J]. J Chem Soc, Perkin Trans 1, 1992,18:2367-2369.
42. [42]
  Te Velde G, Bickelhaupt F M, Baerends E J. Chemistry with ADF[J]. J Comput Chem, 2001,22:931-967. doi: 10.1002/jcc.1056
43. [43]
  Baerends E J, Ellis D E, Ros P. Self-consistent Molecular Hartree-Fock-Slater Calculations Ⅰ.The Computational Procedure[J]. Chem Phys, 1973,2:41-51. doi: 10.1016/0301-0104(73)80059-X
44. [44]
  Baerends E J and Ros P. Self-Consistent Molecular Hartree-Fock-Slater Calculations Ⅱ.The Effect of Exchange Scaling in Some Small Molecules[J]. Chem Phys, 1973,2:52-59. doi: 10.1016/0301-0104(73)80060-6
45. [45]
  Becke A D. Density-Functional Exchange-Energy Approximation with Correct Asymptotic Behavior[J]. Phys Rev A, 1988,38:3098-3100. doi: 10.1103/PhysRevA.38.3098
46. [46]
  Perdew J P. Accurate and Simple Density Functional for the Electronic Exchange Energy:Generalized Gradient Approximation[J]. Phys Rev B, 1986,33:8822-8824. doi: 10.1103/PhysRevB.33.8822
47. [47]
  Perdew J P. Erratum:Density-Functional Approximation for the Correlation Energy of the Inhomogeneous Electron Gas[J]. Phys Rev B, 1986,34:7406-7406.
48. [48]
  Yamamoto Y, Yatagai H, Maruyama K. Reaction of Allylic Boron and Aluminum "ate" Complexes with Organic Halides and Carbonyl Compounds. Trialkylboranes as Regio-, Stereo-, and Chemoselective Control Elements[J]. J Am Chem Soc, 1981,103(8):1969-1975. doi: 10.1021/ja00398a016
49. [49]
  Rabotyagova O S, Cebe P, Kaplan D L. Protein-Based Block Copolymers[J]. Biomacromolecules, 2011,12(2):269-289. doi: 10.1021/bm100928x
50. [50]
  Broyer R M, Grover G N, Maynard H D. Emerging Synthetic Approaches for Protein-Polymer Conjugations[J]. Chem Commun, 2011,47:2212-2226. doi: 10.1039/c0cc04062b
51. [51]
  Sutthasupa S, Shiotsuki M, Matsuoka H. ing-Opening Metathesis Block Copolymerization of Amino Acid Functionalized Norbornene Monomers. Effects of Solvent and pH on Micelle Formation[J]. Macromolecules, 2010,43(4):1815-1822. doi: 10.1021/ma902405g
52. [52]
  Förster S, Antonietti M. Amphiphilic Block Copolymers in Structure-Controlled Nanomaterial Hybrids[J]. Adv Mater, 1998,10:195-217. doi: 10.1002/(SICI)1521-4095(199802)10:3<195::AID-ADMA195>3.0.CO;2-V
53. [53]
  Rodríguez-Hernández J, Chécot F, Gnanou Y. Toward Smart' Nano-objects by Self-assembly of Block Copolymers in Solution[J]. Prog Polym Sci, 2005,30:691-724. doi: 10.1016/j.progpolymsci.2005.04.002
1. [1]
  Yue Sun , Liming Yang , Yaohang Cheng , Guanghui An , Guangming Li . Pd(I)-catalyzed ring-opening arylation of cyclopropyl-α-aminoamides: Access to α-ketoamide peptidomimetics. Chinese Chemical Letters, 2024, 35(6): 109250-. doi: 10.1016/j.cclet.2023.109250
2. [2]
  Qinghong Zhang , Qiao Zhao , Xiaodi Wu , Li Wang , Kairui Shen , Yuchen Hua , Cheng Gao , Yu Zhang , Mei Peng , Kai Zhao . Visible-light-induced ring-opening cross-coupling of cycloalcohols with vinylazaarenes and enones via β-C-C scission enabled by proton-coupled electron transfer. Chinese Chemical Letters, 2025, 36(2): 110167-. doi: 10.1016/j.cclet.2024.110167
3. [3]
  Shan Jiang , Lingchen Meng , Wenyue Ma , Qingkai Qi , Wei Zhang , Bin Xu , Leijing Liu , Wenjing Tian . Corrigendum to 'Morphology controllable conjugated network polymers based on AIE-active building block for TNP detection' [Chin. Chem. Lett. 32 (2021) 1037-1040]. Chinese Chemical Letters, 2024, 35(12): 108998-. doi: 10.1016/j.cclet.2023.108998
4. [4]
  Kexin Yuan , Yulei Liu , Haoran Feng , Yi Liu , Jun Cheng , Beiyang Luo , Qinglian Wu , Xinyu Zhang , Ying Wang , Xian Bao , Wanqian Guo , Jun Ma . Unlocking the potential of thin-film composite reverse osmosis membrane performance: Insights from mass transfer modeling. Chinese Chemical Letters, 2024, 35(5): 109022-. doi: 10.1016/j.cclet.2023.109022
5. [5]
  Tong Zhang , Chao Sun , Shubin Yang , Zimin Cai , Sifeng Zhu , Wendian Liu , Yun Luan , Cheng Wang . Inhalation of taraxasterol loaded mixed micelles for the treatment of idiopathic pulmonary fibrosis. Chinese Chemical Letters, 2024, 35(8): 109248-. doi: 10.1016/j.cclet.2023.109248
6. [6]
  Mengjuan Sun , Muye Zhou , Yifang Xiao , Hailei Tang , Jinhua Chen , Ruitao Zhang , Chunjiayu Li , Qi Ya , Qian Chen , Jiasheng Tu , Qiyue Wang , Chunmeng Sun . Reversibly size-switchable polyion complex micelles for antiangiogenic cancer therapy. Chinese Chemical Letters, 2024, 35(7): 109110-. doi: 10.1016/j.cclet.2023.109110
7. [7]
  Xue Zhao , Rui Zhao , Qian Liu , Henghui Chen , Jing Wang , Yongfeng Hu , Yan Li , Qiuming Peng , John S Tse . A p-d block synergistic effect enables robust electrocatalytic oxygen evolution. Chinese Chemical Letters, 2024, 35(11): 109496-. doi: 10.1016/j.cclet.2024.109496
8. [8]
  Yiwen Lin , Yijie Chen , Chunhui Deng , Nianrong Sun . Integration of resol/block-copolymer carbonization and machine learning: A convenient approach for precise monitoring of glycan-associated disorders. Chinese Chemical Letters, 2024, 35(12): 109813-. doi: 10.1016/j.cclet.2024.109813
9. [9]
  Yihan Zhou , Duo Gao , Yaying Wang , Li Liang , Qingyu Zhang , Wenwen Han , Jie Wang , Chunliu Zhu , Xinxin Zhang , Yong Gan . Worm-like micelles facilitate the intestinal mucus diffusion and drug accumulation for enhancing colorectal cancer therapy. Chinese Chemical Letters, 2024, 35(6): 108967-. doi: 10.1016/j.cclet.2023.108967
10. [10]
  Yu Qin , Mingyang Huang , Chenlu Huang , Hannah L. Perry , Linhua Zhang , Dunwan Zhu . O₂-generating multifunctional polymeric micelles for highly efficient and selective photodynamic-photothermal therapy in melanoma. Chinese Chemical Letters, 2024, 35(7): 109171-. doi: 10.1016/j.cclet.2023.109171
11. [11]
  Peiyan Zhu , Yanyan Yang , Hui Li , Jinhua Wang , Shiqing Li . Rh(Ⅲ)‐Catalyzed sequential ring‐retentive/‐opening [4 + 2] annulations of 2H‐imidazoles towards full‐color emissive imidazo[5,1‐a]isoquinolinium salts and AIE‐active non‐symmetric 1,1′‐biisoquinolines. Chinese Chemical Letters, 2024, 35(10): 109533-. doi: 10.1016/j.cclet.2024.109533
12. [12]
  Yiyue Ding , Qiuxiang Zhang , Lei Zhang , Qilu Yao , Gang Feng , Zhang-Hui Lu . Exceptional activity of amino-modified rGO-immobilized PdAu nanoclusters for visible light-promoted dehydrogenation of formic acid. Chinese Chemical Letters, 2024, 35(7): 109593-. doi: 10.1016/j.cclet.2024.109593
13. [13]
  Dongdong YANG , Jianhua XUE , Yuanyu YANG , Meixia WU , Yujia BAI , Zongxuan WANG , Qi MA . Design and synthesis of two coordination polymers for the rapid detection of ciprofloxacin based on triphenylpolycarboxylic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2466-2474. doi: 10.11862/CJIC.20240266
14. [14]
  Yuanyuan Zeng , Fang Liu , Jun Wang , Bianfei Shao , Tao He , Zhongzheng Xiang , Yan Wang , Shunyao Zhu , Tian Yang , Siting Yu , Changyang Gong , Lei Liu . Fisetin micelles precisely exhibit a radiosensitization effect by inhibiting PDGFRβ/STAT1/STAT3/Bcl-2 signaling pathway in tumor. Chinese Chemical Letters, 2025, 36(2): 109734-. doi: 10.1016/j.cclet.2024.109734
15. [15]
  Zhenghua ZHAO , Qin ZHANG , Yufeng LIU , Zifa SHI , Jinzhong GU . Syntheses, crystal structures, catalytic and anti-wear properties of nickel(Ⅱ) and zinc(Ⅱ) coordination polymers based on 5-(2-carboxyphenyl)nicotinic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 621-628. doi: 10.11862/CJIC.20230342
16. [16]
  Weizhong LING , Xiangyun CHEN , Wenjing LIU , Yingkai HUANG , Yu LI . Syntheses, crystal structures, and catalytic properties of three zinc(Ⅱ), cobalt(Ⅱ) and nickel(Ⅱ) coordination polymers constructed from 5-(4-carboxyphenoxy)nicotinic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1803-1810. doi: 10.11862/CJIC.20240068
17. [17]
  Long TANG , Yaxin BIAN , Luyuan CHEN , Xiangyang HOU , Xiao WANG , Jijiang WANG . Syntheses, structures, and properties of three coordination polymers based on 5-ethylpyridine-2,3-dicarboxylic acid and N-containing ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1975-1985. doi: 10.11862/CJIC.20240180
18. [18]
  Hailong He , Wenbing Wang , Wenmin Pang , Chen Zou , Dan Peng . Double stimulus-responsive palladium catalysts for ethylene polymerization and copolymerization. Chinese Chemical Letters, 2024, 35(7): 109534-. doi: 10.1016/j.cclet.2024.109534
19. [19]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
20. [20]
  Yao HUANG , Yingshu WU , Zhichun BAO , Yue HUANG , Shangfeng TANG , Ruixue LIU , Yancheng LIU , Hong LIANG . Copper complexes of anthrahydrazone bearing pyridyl side chain: Synthesis, crystal structure, anticancer activity, and DNA binding. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 213-224. doi: 10.11862/CJIC.20240359

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(1660)
HTML views(213)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142