Precise Pentamers with Diverse Monomer Sequences and Their Thermal Properties

Rui-Zhe Liu; Lei Zhang; Kun-Kun Guo; Jiang-Tao Xu

doi:10.1007/s10118-022-2689-1

Your Location：

Home >

Browse articles >

Precise Pentamers with Diverse Monomer Sequences and Their Thermal Properties

RESEARCH ARTICLE | Updated：2022-04-26

- Precise Pentamers with Diverse Monomer Sequences and Their Thermal Properties
- Chinese Journal of Polymer Science Vol. 40, Issue 5, Pages: 447-455(2022)
- Affiliations：
  
  a.School of Chemical Engineering, UNSW Sydney, NSW 2052, Australia
  b.College of Materials Science and Engineering, Hunan University, Changsha 410082, China
- Author bio：
  
  j.xu@unsw.edu.au
- Funds：
- DOI：10.1007/s10118-022-2689-1
  CLC：
- Received：08 December 2021，
  
  Revised：2021-12-27，
  
  Accepted：30 December 2021，
  
  Online First：09 March 2022，
  
  Published：01 May 2022
- Accepted：
Scan QR Code
Liu, R. Z.; Zhang, L.; Guo, K. K.; Xu, J. T. Precise pentamers with diverse monomer sequences and their thermal properties. Chinese J. Polym. Sci. 2022, 40, 447–455

Rui-Zhe Liu, Lei Zhang, Kun-Kun Guo, et al. Precise Pentamers with Diverse Monomer Sequences and Their Thermal Properties[J]. Chinese Journal of Polymer Science, 2022, 40(5): 447-455.
Liu, R. Z.; Zhang, L.; Guo, K. K.; Xu, J. T. Precise pentamers with diverse monomer sequences and their thermal properties. Chinese J. Polym. Sci. 2022, 40, 447–455 DOI： 10.1007/s10118-022-2689-1.

Rui-Zhe Liu, Lei Zhang, Kun-Kun Guo, et al. Precise Pentamers with Diverse Monomer Sequences and Their Thermal Properties[J]. Chinese Journal of Polymer Science, 2022, 40(5): 447-455. DOI： 10.1007/s10118-022-2689-1.

摘要

Abstract

Sequenced-defined oligomer has been emerged as one of the hot topics in polymer chemistry due to its capability of precisely controlling both chain length and monomer sequence. Recent efforts have focused on development of synthetic methodologies using state-of-the-art chemistry tools. However

investigating the impact of minor changes in monomer sequence on physical properties of these materials is still underdeveloped. Herein

four sequenced pentamers are synthesized by a reversible addition-fragmentation chain transfer (RAFT) single unit monomer insertion technique

in which a base pentamer possesses a relatively rigid backbone comprising of five cyclic monomer units. One of the cyclic units in this base pentamer is replaced by an acyclic monomer at different locations (the 1

and 5

unit) to produce three modified pentamers

which leads to a significant decrease of glass transition temperature (

) compared to the base pentamer. Meanwhile

the modified pentamers with identical primary structures but distinct monomer sequences also present different

values depending on the position of the acyclic monomer unit. The middle (3

) position of the acyclic unit causes profound decrease of

due to its increased molecular flexibility. These synthetic pentamers have been demonstrated to be excellent oligomeric plasticizers to modulate thermal transitions of bulk polymer materials.

关键词

Keywords

references

Lutz, J. F.; Ouchi, M.; Liu, D. R.; Sawamoto, M . Sequence-controlled polymers . Science , 2013 . 341 1238149 DOI: 10.1126/science.1238149 http://doi.org/10.1126/science.1238149 .

Lutz, J. F . Defining the field of sequence-controlled polymers . Macromol. Rapid Commun. , 2017 . 38 1700582 DOI: 10.1002/marc.201700582 http://doi.org/10.1002/marc.201700582 .

van Genabeek, B.; Lamers, B. A. G.; Hawker, C. J.; Meijer, E. W.; Gutekunst, W. R.; Schmidt, B. V. K. J . Properties and applications of precision oligomer materials; where organic and polymer chemistry join forces . J. Polym. Sci. , 2021 . 59 373 - 403 . DOI: 10.1002/pol.20200862 http://doi.org/10.1002/pol.20200862 .

De Neve, J.; Haven, J . J.; Maes, L.; Junkers, T. Sequence-definition from controlled polymerization: the next generation of materials . Polym. Chem. , 2018 . 9 4692 - 4705 . DOI: 10.1039/C8PY01190G http://doi.org/10.1039/C8PY01190G .

Xu, J . Single unit monomer insertion: a versatile platform for molecular engineering through radical addition reactions and polymerization . Macromolecules , 2019 . 52 9068 - 9093 . DOI: 10.1021/acs.macromol.9b01365 http://doi.org/10.1021/acs.macromol.9b01365 .

Solleder, S. C.; Schneider, R. V.; Wetzel, K. S.; Boukis, A. C.; Meier, M. A. R . Recent progress in the design of monodisperse, sequence-defined macromolecules . Macromol. Rapid Commun. , 2017 . 38 1600711 DOI: 10.1002/marc.201600711 http://doi.org/10.1002/marc.201600711 .

Meier, M. A. R.; Barner-Kowollik, C . A new class of materials: sequence-defined macromolecules and their emerging applications . Adv. Mater. , 2019 . 31 1806027 DOI: 10.1002/adma.201806027 http://doi.org/10.1002/adma.201806027 .

Huang, Z.; Shi, Q.; Guo, J.; Meng, F.; Zhang, Y.; Lu, Y.; Qian, Z.; Li, X.; Zhou, N.; Zhang, Z.; Zhu, X . Binary tree-inspired digital dendrimer . Nat. Commun. , 2019 . 10 1918 DOI: 10.1038/s41467-019-09957-6 http://doi.org/10.1038/s41467-019-09957-6 .

Solleder, S. C.; Zengel, D.; Wetzel, K. S.; Meier, M. A. R . A scalable and high-yield strategy for the synthesis of sequence-defined macromolecules . Angew. Chem. Int. Ed. , 2016 . 55 1204 - 1207 . DOI: 10.1002/anie.201509398 http://doi.org/10.1002/anie.201509398 .

Wu, Y.-H.; Zhang, J.; Du, F. S.; Li, Z. C . Dual sequence control of uniform macromolecules through consecutive single addition by selective passerini reaction . ACS Macro Lett. , 2017 . 6 1398 - 1403 . DOI: 10.1021/acsmacrolett.7b00863 http://doi.org/10.1021/acsmacrolett.7b00863 .

Takizawa, K.; Tang, C.; Hawker, C. J . Molecularly defined caprolactone oligomers and polymers: synthesis and characterization . J. Am. Chem. Soc. , 2008 . 130 1718 - 1726 . DOI: 10.1021/ja077149w http://doi.org/10.1021/ja077149w .

Takizawa, K.; Nulwala, H.; Hu, J.; Yoshinaga, K.; Hawker, C. J . Molecularly defined (L)-lactic acid oligomers and polymers: synthesis and characterization . J. Polym. Sci., Part A: Polym. Chem. , 2008 . 46 5977 - 5990 . DOI: 10.1002/pola.22944 http://doi.org/10.1002/pola.22944 .

Ren, J. M.; Lawrence, J.; Knight, A. S.; Abdilla, A.; Zerdan, R. B.; Levi, A. E.; Oschmann, B.; Gutekunst, W. R.; Lee, S. H.; Li, Y.; McGrath, A. J.; Bates, C. M.; Qiao, G. G.; Hawker, C. J . Controlled formation and binding selectivity of discrete oligo(methyl methacrylate) stereocomplexes . J. Am. Chem. Soc. , 2018 . 140 1945 - 1951 . DOI: 10.1021/jacs.7b13095 http://doi.org/10.1021/jacs.7b13095 .

Ji, Y.; Zhang, L.; Gu, X.; Zhang, W.; Zhou, N.; Zhang, Z.; Zhu, X . Sequence-controlled polymers with furan-protected maleimide as a latent monomer . Angew. Chem. Int. Ed. , 2017 . 56 2328 - 2333 . DOI: 10.1002/anie.201610305 http://doi.org/10.1002/anie.201610305 .

Huang, Z.; Zhao, J.; Wang, Z.; Meng, F.; Ding, K.; Pan, X.; Zhou, N.; Li, X.; Zhang, Z.; Zhu, X . Combining orthogonal chain-end deprotections and thiol-maleimide Michael coupling: engineering discrete oligomers by an iterative growth strategy . Angew. Chem. Int. Ed. , 2017 . 56 13612 - 13617 . DOI: 10.1002/anie.201706522 http://doi.org/10.1002/anie.201706522 .

Wang, S.; Tao, Y.; Wang, J.; Tao, Y.; Wang, X . A versatile strategy for the synthesis of sequence-defined peptoids with side-chain and backbone diversity via amino acid building blocks . Chem. Sci. , 2019 . 10 1531 - 1538 . DOI: 10.1039/C8SC03415J http://doi.org/10.1039/C8SC03415J .

Tao, Y.; Wang, S.; Zhang, X.; Wang, Z.; Tao, Y.; Wang, X . Synthesis and properties of alternating polypeptoids and polyampholytes as protein-resistant polymers . Biomacromolecules , 2018 . 19 936 - 942 . DOI: 10.1021/acs.biomac.7b01719 http://doi.org/10.1021/acs.biomac.7b01719 .

Tao, Y.; Tao, Y . Ugi reaction of amino acids: from facile synthesis of polypeptoids to sequence-defined macromolecules . Macromol. Rapid Commun. , 2021 . 42 2000515 DOI: 10.1002/marc.202000515 http://doi.org/10.1002/marc.202000515 .

Zhu, Y.; Tao, Y . Sequence-controlled and sequence-defined polypeptoids via the Ugi reaction: synthesis and sequence-driven properties . Polym. Chem. , 2021 . 12 4895 - 4902 . DOI: 10.1039/D1PY00658D http://doi.org/10.1039/D1PY00658D .

Zydziak, N.; Konrad, W.; Feist, F.; Afonin, S.; Weidner, S.; Barner-Kowollik, C . Coding and decoding libraries of sequence-defined functional copolymers synthesized via photoligation . Nat. Commun. , 2016 . 7 13672 DOI: 10.1038/ncomms13672 http://doi.org/10.1038/ncomms13672 .

Kametani, Y.; Ouchi, M . One-pot preparation of methacrylate/styrene alternating copolymers via radical copolymerization and alcoholysis modification: sequence impacts on glass transition temperature . ACS Polym. Au , 2021 . 1 10 - 15 . DOI: 10.1021/acspolymersau.1c00012 http://doi.org/10.1021/acspolymersau.1c00012 .

Kametani, Y.; Tournilhac, F.; Sawamoto, M.; Ouchi, M . Unprecedented sequence control and sequence-driven properties in a series of AB-alternating copolymers consisting solely of acrylamide units . Angew. Chem. Int. Ed. , 2020 . 59 5193 - 5201 . DOI: 10.1002/anie.201915075 http://doi.org/10.1002/anie.201915075 .

Nishimori, K.; Ouchi, M . AB-alternating copolymers via chain-growth polymerization: synthesis, characterization, self-assembly, and functions . Chem. Commun. , 2020 . 56 3473 - 3483 . DOI: 10.1039/D0CC00275E http://doi.org/10.1039/D0CC00275E .

Zhang, S.; Bauer, N. E.; Kanal, I. Y.; You, W.; Hutchison, G. R.; Meyer, T. Y . Sequence effects in donor-acceptor oligomeric semiconductors comprising benzothiadiazole and phenylenevinylene monomers . Macromolecules , 2017 . 50 151 - 161 . DOI: 10.1021/acs.macromol.6b02215 http://doi.org/10.1021/acs.macromol.6b02215 .

Zhang, S.; Hutchison, G. R.; Meyer, T. Y . Sequence effects in conjugated donor-acceptor trimers and polymers . Macromol. Rapid Commun. , 2016 . 37 882 - 887 . DOI: 10.1002/marc.201600086 http://doi.org/10.1002/marc.201600086 .

Li, J.; Stayshich, R. M.; Meyer, T. Y . Exploiting sequence to control the hydrolysis behavior of biodegradable PLGA copolymers . J. Am. Chem. Soc. , 2011 . 133 6910 - 6913 . DOI: 10.1021/ja200895s http://doi.org/10.1021/ja200895s .

Maron, E.; Swisher, J. H.; Haven, J. J.; Meyer, T. Y.; Junkers, T.; Börner, H. G . Learning from peptides to access functional precision polymer sequences . Angew. Chem. Int. Ed. , 2019 . 58 10747 - 10751 . DOI: 10.1002/anie.201902217 http://doi.org/10.1002/anie.201902217 .

Li, J.; Rothstein, S. N.; Little, S. R.; Edenborn, H. M.; Meyer, T. Y . The effect of monomer order on the hydrolysis of biodegradable poly(lactic- co -glycolic acid) repeating sequence copolymers . J. Am. Chem. Soc. , 2012 . 134 16352 - 16359 . DOI: 10.1021/ja306866w http://doi.org/10.1021/ja306866w .

Norris, B. N.; Zhang, S.; Campbell, C. M.; Auletta, J. T.; Calvo-Marzal, P.; Hutchison, G. R.; Meyer, T. Y . Sequence matters: modulating electronic and optical properties of conjugated oligomers via tailored sequence . Macromolecules , 2013 . 46 1384 - 1392 . DOI: 10.1021/ma400123r http://doi.org/10.1021/ma400123r .

Washington, M. A.; Swiner, D. J.; Bell, K. R.; Fedorchak, M. V.; Little, S. R.; Meyer, T. Y . The impact of monomer sequence and stereochemistry on the swelling and erosion of biodegradable poly(lactic- co -glycolic acid) matrices . Biomaterials , 2017 . 117 66 - 76 . DOI: 10.1016/j.biomaterials.2016.11.037 http://doi.org/10.1016/j.biomaterials.2016.11.037 .

Schneider, R. V.; Waibel, K. A.; Arndt, A. P.; Lang, M.; Seim, R.; Busko, D.; Bräse, S.; Lemmer, U.; Meier, M. A. R . Sequence-definition in stiff conjugated oligomers . Sci. Rep. , 2018 . 8 17483 DOI: 10.1038/s41598-018-35933-z http://doi.org/10.1038/s41598-018-35933-z .

Liu, R.; Zhang, L.; Huang, Z.; Xu, J . Sequential and alternating RAFT single unit monomer insertion: model trimers as the guide for discrete oligomer synthesis . Polym. Chem. , 2020 . 11 4557 - 4567 . DOI: 10.1039/D0PY00390E http://doi.org/10.1039/D0PY00390E .

Lin, S.; Zhang, L.; Huang, Z.; Kumar, P. V.; Xu, J . Discriminatory photoactivation of diastereomeric RAFT agents . Macromolecules , 2019 . 52 7157 - 7166 . DOI: 10.1021/acs.macromol.9b01534 http://doi.org/10.1021/acs.macromol.9b01534 .

Barnes, J. C.; Ehrlich, D. J. C.; Gao, A. X.; Leibfarth, F. A.; Jiang, Y.; Zhou, E.; Jamison, T. F.; Johnson, J. A . Iterative exponential growth of stereo- and sequence-controlled polymers . Nat. Chem. , 2015 . 7 810 - 815 . DOI: 10.1038/nchem.2346 http://doi.org/10.1038/nchem.2346 .

Leibfarth, F. A.; Johnson, J. A.; Jamison, T. F . Scalable synthesis of sequence-defined, unimolecular macromolecules by flow-IEG . Proc. Natl. Acad. Sci. U.S.A. , 2015 . 112 10617 - 10622 . DOI: 10.1073/pnas.1508599112 http://doi.org/10.1073/pnas.1508599112 .

Golder, M. R.; Jiang, Y.; Teichen, P. E.; Nguyen, H. V. T.; Wang, W.; Milos, N.; Freedman, S. A.; Willard, A. P.; Johnson, J. A . Stereochemical sequence dictates unimolecular diblock copolymer assembly . J. Am. Chem. Soc. , 2018 . 140 1596 - 1599 . DOI: 10.1021/jacs.7b12696 http://doi.org/10.1021/jacs.7b12696 .

Nguyen, H. V. T.; Jiang, Y.; Mohapatra, S.; Wang, W.; Barnes, J. C.; Oldenhuis, N. J.; Chen, K. K.; Axelrod, S.; Huang, Z.; Chen, Q.; Golder, M. R.; Young, K.; Suvlu, D.; Shen, Y.; Willard, A. P.; Hore, M. J. A.; Gómez-Bombarelli, R.; Johnson, J. A. Bottlebrush polymers with flexible enantiomeric side chains display differential biological properties. Nat. Chem. 2021 , doi:10.1038/s41557-021-00826-8.

Hartweg, M.; Jiang, Y.; Yilmaz, G.; Jarvis, C. M.; Nguyen, H. V. T.; Primo, G. A.; Monaco, A.; Beyer, V. P.; Chen, K. K.; Mohapatra, S.; Axelrod, S.; Gómez-Bombarelli, R.; Kiessling, L. L.; Becer, C. R.; Johnson, J. A . Synthetic glycomacromolecules of defined valency, absolute configuration, and topology distinguish between human lectins . JACS Au , 2021 . 1 1621 - 1630 . DOI: 10.1021/jacsau.1c00255 http://doi.org/10.1021/jacsau.1c00255 .

Martens, S.; Van den Begin, J.; Madder, A.; Du Prez, F. E.; Espeel, P . Automated synthesis of monodisperse oligomers, featuring sequence control and tailored functionalization . J. Am. Chem. Soc. , 2016 . 138 14182 - 14185 . DOI: 10.1021/jacs.6b07120 http://doi.org/10.1021/jacs.6b07120 .

Huang, Z.; Noble, B. B.; Corrigan, N.; Chu, Y.; Satoh, K.; Thomas, D. S.; Hawker, C. J.; Moad, G.; Kamigaito, M.; Coote, M. L.; Boyer, C.; Xu, J . Discrete and stereospecific oligomers prepared by sequential and alternating single unit monomer insertion . J. Am. Chem. Soc. , 2018 . 140 13392 - 13406 . DOI: 10.1021/jacs.8b08386 http://doi.org/10.1021/jacs.8b08386 .

Huang, Z.; Corrigan, N.; Lin, S.; Boyer, C.; Xu, J . Upscaling single unit monomer insertion to synthesize discrete oligomers . J. Polym. Sci., Part A: Polym. Chem. , 2019 . 57 1947 - 1955 . DOI: 10.1002/pola.29330 http://doi.org/10.1002/pola.29330 .

Liu, R.; Yang, C.; Huang, Z.; French, R.; Gu, Z.; Cheng, J.; Guo, K.; Xu, J . Unravelling sequence effect on glass transition temperatures of discrete unconjugated oligomers . Macromol. Rapid Commun. , 2021 . 42 2100666 .

Zhang, L.; Liu, R.; Huang, Z.; Xu, J . How does the single unit monomer insertion technique promote kinetic analysis of activation and initiation in photo-RAFT processes . Polym. Chem. , 2021 . 12 581 - 593 . DOI: 10.1039/D0PY01413C http://doi.org/10.1039/D0PY01413C .

Mokhtar, S. M.; Mikhael, M. G.; Aly, R. O.; Elsabee, M. Z . Copolymerization of indene with N -phenylmaleimide . Polym. J. , 1988 . 20 979 - 985 . DOI: 10.1295/polymj.20.979 http://doi.org/10.1295/polymj.20.979 .

Xu, X.; Douglas, J. F.; Xu, W. S . Influence of side-chain length and relative rigidities of backbone and side chains on glass formation of branched polymers . Macromolecules , 2021 . 54 6327 - 6341 . DOI: 10.1021/acs.macromol.1c00834 http://doi.org/10.1021/acs.macromol.1c00834 .

Dudowicz, J.; Freed, K. F.; Douglas, J. F . The glass transition temperature of polymer melts . J. Phys. Chem. B , 2005 . 109 21285 - 21292 . DOI: 10.1021/jp0523266 http://doi.org/10.1021/jp0523266 .

Rahman, M.; Brazel, C. S . The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges . Prog. Polym. Sci. , 2004 . 29 1223 - 1248 . DOI: 10.1016/j.progpolymsci.2004.10.001 http://doi.org/10.1016/j.progpolymsci.2004.10.001 .

Yao, F.; Liu, Q.; Zhang, Z.; Zhu, X . RAFT polymerization of styrene and maleimide in the presence of fluoroalcohol: hydrogen bonding effects with classical alternating copolymerization as reference . Polymers , 2017 . 9 89 DOI: 10.3390/polym9030089 http://doi.org/10.3390/polym9030089 .

Fox, T. G . Influence of diluent and of copolymer composition on the glass temperature of a polymer system . Bull. Am. Phys. Soc. , 1956 . 1 123 .

Hiemenz, P. C.; Lodge, T. P. Polymer chemistry. Chapter 12. CRC Press, 2007 .

Views

113

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Alternating Poly(ether-alt-ester)s with High Glass Transition Temperature Enabled by Rotationally Constrained Biaryl Units

Machine Learning-assisted Prediction of Polymer Glass Transition Temperature: A Structural Feature Approach

Physical Properties of Polymers under Soft and Hard Nanoconfinement: A Review

Nanoparticle Dispersion and Glass Transition Behavior of Polyimide-grafted Silica Nanocomposites

Silk Sericin-inspired Poly-β-homoserine for Protein Protection

Related Author

Xiao-Bing Lu

Ye Liu

Zheng-Fei Liu

Yu-Tao Wang

Hadi Shirali

Bardia Afsordeh

Ming-Chao Ma

Yun-Long Guo

Related Institution

State Key Laboratory of Fine Chemicals, Dalian University of Technology

Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, PO Box 15875-441, Tehran

Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran

University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University

School of Materials Science and Engineering, Shanghai Jiao Tong University

⁰