Abstract
Rational design of “giant” building blocks promotes the modular construction of polymeric counterparts at a large length scale. In this study, a series of biscylooctyne- and bisazide-functionalized polyhedral oligomeric silsesquioxane (POSS) monomers with different regio-configurations were synthesized. Homo and alternating giant polymeric chains were then efficiently prepared by strain-promoted azide-alkyne cycloaddition (SPAAC) polymerization. The obtained monomers and polymers were characterized by proton nuclear magnetic resonance (1H NMR), size exclusion chromatography (SEC), and matrix-assisted laser desorption ionization time-of-flight (MALDI-ToF) mass spectrometry. The influence of the feeding ratio, monomer concentration, and regio-configuration on the step-growth polymerization was investigated. Due to the large monomer size, the giant chains can be purified and fractionated by preparative SEC. This work provides a facile and efficient approach for the modular construction of main-chain polymers with nanosized building blocks.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Flory PJ, Volkenstein M. Statistical mechanics of chain molecules. Biopolymers. 1969;8:699–700.
Reches M, Snyder PW, Whitesides GM. Folding of electrostatically charged beads-on-a-string as an experimental realization of a theoretical model in polymer science. Proc Natl Acad Sci USA. 2009;106:17644 https://doi.org/10.1073/pnas.0905533106.
Kitagishi H, Oohora K, Yamaguchi H, Sato H, Matsuo T, Harada A, et al. Supramolecular hemoprotein linear assembly by successive interprotein heme−heme pocket interactions. J Am Chem Soc. 2007;129:10326–7. https://doi.org/10.1021/ja073295q.
Zou L-N, Cheng X, Rivers ML, Jaeger HM, Nagel SR. The packing of granular polymer chains. Science. 2009;326:408–10. https://doi.org/10.1126/science.1177114.
Liu K, Nie Z, Zhao N, Li W, Rubinstein M, Kumacheva E. Step-growth polymerization of inorganic nanoparticles. Science. 2010;329:197–200. https://doi.org/10.1126/science.1189457.
Macdonell A, Johnson NAB, Surman AJ, Cronin L. Configurable nanosized metal oxide oligomers via precise “Click” coupling control of hybrid polyoxometalates. J Am Chem Soc. 2015;137:5662–5. https://doi.org/10.1021/jacs.5b02466.
Wu D, Sinha N, Lee J, Sutherland BP, Halaszynski NI, Tian Y, et al. Polymers with controlled assembly and rigidity made with click-functional peptide bundles. Nature. 2019;574:658–62. https://doi.org/10.1038/s41586-019-1683-4.
Lin Z, Xiong Y, Xiang S, Gang O. Controllable covalent-bound nanoarchitectures from DNA frames. J Am Chem Soc. 2019;141:6797–801. https://doi.org/10.1021/jacs.9b01510.
Duan H, Yang Y, Zhang Y, Yi C, Nie Z, He J. What is next in polymer-grafted plasmonic nanoparticles? Giant. 2020;4:100033 https://doi.org/10.1016/j.giant.2020.100033.
Liu Y, Liu T, Yan X, Guo Q-Y, Wang J, Zhang R, et al. Mesoatom alloys via self-sorting approach of giant molecules blends. Giant. 2020;4:100031 https://doi.org/10.1016/j.giant.2020.100031.
Feng F, Guo D, Shao Y, Yan X, Yue K, Pan Z, et al. Thickness control of 2D nanosheets assembled from precise side-chain giant molecules. Chem Sci. 2021;12:5216–23. https://doi.org/10.1039/d1sc00021g.
Feng F, Shao Y, Wu W, Li X, Hong C, Jin L, et al. Crystallization of precise side-chain giant molecules with tunable sequences and functionalities. Macromolecules. 2021;54:11093–11100. https://doi.org/10.1021/acs.macromol.1c01958.
Tricard S, Feinstein E, Shepherd RF, Reches M, Snyder PW, Bandarage DC, et al. Analog modeling of worm-like chain molecules using macroscopic beads-on-a-string. Phys. Chem. Chem. Phys. 2012;14:9041–6. https://doi.org/10.1039/c2cp40593h.
Zhang W-B, Cheng SZD. Giant is different: size effects and the nature of macromolecules. Giant. 2020;1:100011 https://doi.org/10.1016/j.giant.2020.100011.
Zhang W-B, Yu X, Wang C-L, Sun H-J, Hsieh I-F, Li Y, et al. Molecular nanoparticles are unique elements for macromolecular science: from “nanoatoms” to giant molecules. Macromolecules. 2014;47:1221–39. https://doi.org/10.1021/ma401724p.
Liu Y, Liu G, Zhang W, Du C, Wesdemiotis C, Cheng SZD. Cooperative soft-cluster glass in giant molecular clusters. Macromolecules. 2019;52:4341–8. https://doi.org/10.1021/acs.macromol.9b00549.
Zou Q, Zhu Y, Ruan Y, Zhang R, Liu G. Coarse-grained soft-clusters remain non-diffusing in the melt state. Giant. 2021;8:100070 https://doi.org/10.1016/j.giant.2021.100070.
Zhu Y, Luo J, Zou Q, Ouyang X, Ruan Y, Liu Y, et al. Glassy feature in melts of 3-dimensional architectured polymer blends. Polymer. 2022;238:124336 https://doi.org/10.1016/j.polymer.2021.124336.
Li Y, Dong X-H, Zou Y, Wang Z, Yue K, Huang M, et al. Polyhedral oligomeric silsesquioxane meets “click” chemistry: rational design and facile preparation of functional hybrid materials. Polymer. 2017;125:303–29. https://doi.org/10.1016/j.polymer.2017.08.008.
Maegawa T, Irie Y, Imoto H, Fueno H, Tanaka K, Naka K. Para-bisvinylhexaisobutyl-substituted t8 caged monomer: synthesis and hydrosilylation polymerization. Polym Chem. 2015;6:7500–4. https://doi.org/10.1039/c5py01262g.
Fujii S, Minami S, Urayama K, Suenaga Y, Naito H, Miyashita O, et al. Beads-on-string-shaped poly(azomethine) applicable for solution processing of bilayer devices using a same solvent. ACS Macro Lett. 2018;7:641–5. https://doi.org/10.1021/acsmacrolett.8b00271.
Liu Z, Yang Z, Chen X, Tan R, Li G, Gan Z, et al. Discrete giant polymeric chains based on nanosized monomers. JACS Au. 2021;1:79–86. https://doi.org/10.1021/jacsau.0c00014.
Li G, Gan Z, Liu Y, Wang S, Guo Q-Y, Liu Z, et al. Molecular patchy clusters with controllable symmetry breaking for structural engineering. ACS Nano. 2020;14:13816–23. https://doi.org/10.1021/acsnano.0c06189.
Liu Z, Chen X, Yang Z, Wang S, Gan Z, Li G, et al. Precise amphiphilic giant polymeric chain based on nanosized monomers with exact regio-configuration. ACS Nano. 2021;15:12367–74. https://doi.org/10.1021/acsnano.1c04486.
Liu Z, Wang S, Li G, Yang Z, Gan Z, Dong X-H. Discrete giant polymeric chain with precise sequence and regio-configuration: a concise multiblock model system. Macromolecules. 2022;55:5954–63. https://doi.org/10.1021/acs.macromol.2c00992.
Liu Z, Wang S, Yang Z, Dong X. Regioisomeric giant triblock molecules: role of the linker. Macromol. Rapid Commun. 2023;44:2200509 https://doi.org/10.1002/marc.202200509.
Kolb HC, Finn MG, Sharpless KB. Click chemistry: diverse chemical function from a few good reactions. Angew. Chem. Int. Ed. 2001;40:2004–21. 10.1002/1521-3773(20010601)40:11<;2004::aid-anie2004>3.0.co;2-5
Agard NJ, Prescher JA, Bertozzi CR. A strain-promoted [3 + 2] azide−alkyne cycloaddition for covalent modification of biomolecules in living systems. J Am Chem Soc. 2004;126:15046–7. https://doi.org/10.1021/ja044996f.
Lutz J. Copper‐free azide–alkyne cycloadditions: new insights and perspectives. Angew. Chem. Int. Ed. 2008;47:2182–4. https://doi.org/10.1002/anie.200705365.
Han S-Y, Wang X-M, Shao Y, Guo Q-Y, Li Y, Zhang W-B. Janus POSS based on mixed [2:6] octakis-adduct regioisomers. Chem Eur J. 2016;22:6397–403. https://doi.org/10.1002/chem.201600579.
Chadwick R, Gyzen SV, Liogier S, Adronov A. Scalable synthesis of strained cyclooctyne derivatives. Synthesis. 2014;46:669–77. https://doi.org/10.1055/s-0033-1340509.
Wu J-C, Wang D-X, Huang Z-T, Wang M-X. Synthesis of diverse N,O-bridged Calix[1]Arene[4]Pyridine-C60 dyads and triads and formation of intramolecular self-inclusion complexes. J Org Chem. 2010;75:8604–14. https://doi.org/10.1021/jo1019267.
Sun Y, Tan R, Ma Z, Gan Z, Li G, Zhou D, et al. Discrete block copolymers with diverse architectures: resolving complex spherical phases with one monomer resolution. ACS Cent. Sci. 2020;6:1386–93. https://doi.org/10.1021/acscentsci.0c00798.
Shao Y, Yang S, Zhang W. Macromolecular isomerism in giant molecules. Chem Eur J. 2020;26:2985–92. https://doi.org/10.1002/chem.201904419.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (22273026, 51773066, and 51890871), the Recruitment Program of Guangdong (2016ZT06C322), the Research Funds from State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Soochow University (SDGC2109), and the 111 Project (B18023).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Wang, S., Li, G., Liu, Z. et al. Facile construction of giant polymeric chains through strain-promoted azide-alkyne cycloaddition. Polym J 55, 1129–1139 (2023). https://doi.org/10.1038/s41428-023-00816-2
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41428-023-00816-2