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RAFT Dispersion Polymerization of Nitrobenzene-based Monomer and Photo-response of its Polymer Nanoparticles

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Abstract

The poly[N,N-(dimethylamino) ethyl methacrylate] (PDMAEMA) macro-RAFT agent mediated dispersion polymerization of photo-responsive nitrobenzene-based monomer of o-nitrobenzyl methacrylate (NBMA) was performed and the polymerization kinetics and evolution of the block copolymer nanoparticles morphology during the RAFT dispersion copolymerization were investigated in detail. This dispersion RAFT polymerization underwent initial homogeneous polymerization at initial stage and then a subsequent stage of slowed heterogeneous polymerization occurred until the monomer conversion of the polymerization reaction is basically unchanged at about 50% at 24 h. The reason of deceleration of the second stage that is different from the second stage of acceleration for common monomer is discussed. The PDMAEMA-b-PNBMA nanoparticles were prepared by PDMAMEA-mediated RAFT dispersion polymerization, and the photo-response of PDMAEMA-b-PNBMA nanoparticles was also studied.

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References

  1. W. Hou, R. Liu, S. Bi, Q. He, H. Wang, J. Gu, Photo-responsive polymersomes as drug delivery system for potential medical applications. Molecules 25, (21) (2020)

    Article  Google Scholar 

  2. X.T. Cao, Y.H. Kim, J.M. Park, K.T. Lim, One-pot syntheses of dual-responsive core cross-linked polymeric micelles and covalently entrapped drug by click chemistry. Eur. Polym. J. 78, 264–273 (2016)

    Article  CAS  Google Scholar 

  3. C.M.Q. Le, X.T. Cao, T.T.K. Tu, Y.S. Gal, K.T. Lim, Facile approach to prepare pH and redox-responsive nanogels via Diels-Alder click reaction. Express Polym. Lett. 12(8), 688–698 (2018)

    Article  CAS  Google Scholar 

  4. T.P. Huynh, P. Sonar, H. Haick, Advanced materials for Use in Soft Self-Healing Devices. Adv. Mater. 29, (19) (2017)

    Article  Google Scholar 

  5. L. Li, J.M. Scheiger, P.A. Levkin, Design and applications of Photoresponsive Hydrogels. Adv. Mater. 31(26), e1807333 (2019)

  6. W. Luo, G. Wang, Photo-responsive fluorescent materials with Aggregation‐Induced Emission characteristics. Adv. Opt. Mater. 8, (24) (2020)

    Article  Google Scholar 

  7. W. Du, X. Liu, L. Liu, J.W.Y. Lam, B.Z. Tang, Photoresponsive Polymers with Aggregation-Induced Emission. ACS Appl. Polym. Mater. 3(5), 2290–2309 (2021)

    Article  CAS  Google Scholar 

  8. Z.G. Zheng, Y. Li, H.K. Bisoyi, L. Wang, T.J. Bunning, Q. Li, Three-dimensional control of the helical axis of a chiral nematic liquid crystal by light. Nature 2016, 531 (7594), 352–356

  9. E. Pantuso, G. Filpo, F.P. Nicoletta, Light-Responsive Polym. Membr. Adv. Opt. Mater. 7, (16) (2019)

    Google Scholar 

  10. Y. Arisaka, N. Yui, Suspending polyrotaxane dissociation via photo-reversible capping of terminals. Macromol. Rapid Commun. 40(20), e1900323 (2019)

  11. W. Shen, J. Zheng, Z. Zhou, D. Zhang, Approaches for the synthesis of o-nitrobenzyl and coumarin linkers for use in photocleavable biomaterials and bioconjugates and their biomedical applications. Acta Biomater. 115, 75–91 (2020)

    Article  CAS  PubMed  Google Scholar 

  12. W. Zhao, Y. Li, X. Zhang, R. Zhang, Y. Hu, C. Boyer, F.J. Xu, Photo-responsive supramolecular hyaluronic acid hydrogels for accelerated wound healing. J. Control Release 323, 24–35 (2020)

    Article  CAS  PubMed  Google Scholar 

  13. C. Hu, W. Xu, C.M. Conrads, J. Wu, A. Pich, Visible light and temperature dual-responsive microgels by crosslinking of spiropyran modified prepolymers. J. Colloid Interface Sci. 2021, 582 (Pt B), 1075–1084

  14. A. Bagheri, C. Boyer, M. Lim, Synthesis of light-responsive pyrene-based polymer nanoparticles via Polymerization-Induced Self-Assembly. Macromol. Rapid Commun. 40(2), e1800510 (2019)

  15. C. Zhao, S. Shuai, S. Zhou, Y. Liu, W. Huo, H. Zhu, Z. Rao, Y. Li, K. Zhou, W. Ge, J. Hao, Synthesis and characterization of photo-responsive flower-like copolymer micelles with o-nitrobenzyl as the junction point. Mater. Lett. 2020, 261

  16. H. Huo, X. Ma, Y. Dong, F. Qu, Light/temperature dual-responsive ABC miktoarm star terpolymer micelles for controlled release. Eur. Polym. J. 87, 331–343 (2017)

    Article  CAS  Google Scholar 

  17. J. Liu, Y.Q. Sun, Y. Huo, H. Zhang, L. Wang, P. Zhang, D. Song, Y. Shi, W. Guo, Simultaneous fluorescence sensing of Cys and GSH from different emission channels. J. Am. Chem. Soc. 136(2), 574–577 (2014)

    Article  CAS  PubMed  Google Scholar 

  18. G.-Y. Liu, C.-J. Chen, D.-D. Li, S.-S. Wang, J. Ji, Near-infrared light-sensitive micelles for enhanced intracellular drug delivery. J. Mater. Chem. 22, (33) (2012)

    Google Scholar 

  19. J. Yang, J.I. Song, Q. Song, J.Y. Rho, E.D.H. Mansfield, S.C.L. Hall, M. Sambrook, F. Huang, S. Perrier, Hierarchical self-assembled photo-responsive tubisomes from a cyclic peptide-bridged amphiphilic Block Copolymer. Angew Chem. Int. Ed. Engl. 59(23), 8860–8863 (2020)

    Article  CAS  PubMed  Google Scholar 

  20. Y. Kitayama, A. Harada, pH-Responsive Capsule polymer particles prepared by Interfacial Photo-Cross-Linking: Effect of the Alkyl Chain length of the pH-Responsive Monomer. ACS Appl. Mater. Interfaces 13(29), 34973–34983 (2021)

    Article  CAS  PubMed  Google Scholar 

  21. J. Yeow, C. Boyer, Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA): New Insights and Opportunities. Adv Sci (Weinh) 2017, 4 (7), 1700137

  22. P. Gurnani, S. Perrier, Controlled radical polymerization in dispersed systems for biological applications. Prog. Polym. Sci. 2020, 102

  23. Y. Zhang, L. Yu, X. Dai, L. Zhang, J. Tan, Structural difference in Macro-RAFT Agents redirects Polymerization-Induced Self-Assembly. ACS Macro Lett 8(9), 1102–1109 (2019)

    Article  CAS  PubMed  Google Scholar 

  24. M.C. Spiridon, N. Demazy, C. Brochon, E. Cloutet, G. Hadziioannou, K. Aissou, G. Fleury, Optical alignment of Si-Containing Nanodomains formed by Photoresponsive Amorphous Block Copolymer Thin Films. Macromolecules 2020, 53 (1), 68–77

  25. P. Wang, N. Li, S. Li, Y. Zhang, Strategies for preparing hybrid nanomaterials via Polymerization-Induced Self-Assembly. Eur. Polym. J. 2022, 172

  26. N.J. Warren, S.P. Armes, Polymerization-induced self-assembly of block copolymer nano-objects via RAFT aqueous dispersion polymerization. J. Am. Chem. Soc. 136(29), 10174–10185 (2014)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  27. J. Wang, X. Hu, N. Zhu, K. Guo, Continuous flow photo-RAFT and light-PISA. Chem. Eng. J. 2021, 420

  28. X. Wang, Z. An, New Insights into RAFT Dispersion Polymerization-Induced Self-Assembly: from Monomer Library, Morphological Control, and Stability to driving forces. Macromol. Rapid Commun. 40(2), e1800325 (2019)

  29. L. Qiu, H. Zhang, T. Bick, J. Martin, P. Wendler, A. Boker, U. Glebe, C. Xing, Construction of highly ordered Glyco-Inside Nano-Assemblies through RAFT Dispersion polymerization of galactose-decorated Monomer. Angew Chem. Int. Ed. Engl. 60(20), 11098–11103 (2021)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  30. F. D’Agosto, J. Rieger, M. Lansalot, RAFT-Mediated Polymerization-Induced Self-Assembly. Angew Chem. Int. Ed. Engl. 59(22), 8368–8392 (2020)

    Article  PubMed  Google Scholar 

  31. H. Phan, V. Taresco, J. Penelle, B. Couturaud, Polymerisation-induced self-assembly (PISA) as a straightforward formulation strategy for stimuli-responsive drug delivery systems and biomaterials: recent advances. Biomater Sci 2021, 9 (1), 38–50

  32. C. Liu, C.-Y. Hong, C.-Y. Pan, Polymerization techniques in polymerization-induced self-assembly (PISA). Polym. Chem 11(22), 3673–3689 (2020)

    Article  CAS  Google Scholar 

  33. J. Rieger, Guidelines for the synthesis of Block Copolymer particles of various morphologies by RAFT dispersion polymerization. Macromol. Rapid Commun. 36(16), 1458–1471 (2015)

    Article  CAS  PubMed  Google Scholar 

  34. X. Luo, A morphological transition of poly(ethylene glycol)-block-polystyrene with polymerization-induced self-assembly guided by using cosolvents. Eur. Polym. J. 2021, 158

  35. M. Huo, Z. Xu, M. Zeng, P. Chen, L. Liu, L.-T. Yan, Y. Wei, J. Yuan, Controlling vesicular size via Topological Engineering of Amphiphilic Polymer in Polymerization-Induced Self-Assembly. Macromolecules 50(24), 9750–9759 (2017)

    Article  CAS  Google Scholar 

  36. J. Lesage, X. de la Haye, I. Zhang, F. Chaduc, M. Brunel, F. Lansalot, D’Agosto, The Effect of Hydrophile Topology in RAFT-Mediated Polymerization-Induced Self-Assembly. Angew Chem. Int. Ed. Engl. 55(11), 3739–3743 (2016)

    Article  Google Scholar 

  37. Y. Zhang, M. Cao, G. Han, T. Guo, T. Ying, W. Zhang, Topology affecting Block Copolymer Nanoassemblies: Linear Block Copolymers versus Star Block Copolymers under PISA Conditions. Macromolecules 2018, 51 (14), 5440–5449

  38. F. Lv, Z. An, P. Wu, What Determines the Formation of Block Copolymer Nanotubes? Macromolecules 2019, 53 (1), 367–373

  39. P. Gao, H. Cao, Y. Ding, M. Cai, Z. Cui, X. Lu, Y. Cai, Synthesis of Hydrogen-Bonded pore-switchable cylindrical vesicles via visible-light-mediated RAFT room-temperature aqueous dispersion polymerization. ACS Macro Lett 5(12), 1327–1331 (2016)

    Article  CAS  PubMed  Google Scholar 

  40. Q. Yu, Y. Ding, H. Cao, X. Lu, Y. Cai, Use of Polyion Complexation for Polymerization-Induced Self-Assembly in Water under visible light irradiation at 25 degrees C. ACS Macro Lett 2015, 4 (11), 1293–1296

  41. L. Shen, Y. Li, Q. Lu, X. Qi, X. Wu, J. Shen, Facile preparation of one-dimensional nanostructures through polymerization-induced self-assembly mediated by host–guest interaction. Polym. Chem 11(26), 4208–4212 (2020)

    Article  CAS  Google Scholar 

  42. X.G. Qiao, P.Y. Dugas, B. Charleux, M. Lansalot, E. Bourgeat-Lami, Synthesis of Multipod-like Silica/Polymer latex particles via nitroxide-mediated Polymerization-Induced Self-Assembly of Amphiphilic Block Copolymers. Macromolecules 2015, 48 (3), 545–556

  43. X. Liu, W. Gao, In situ growth of self-assembled protein-polymer nanovesicles for enhanced intracellular protein delivery. ACS Appl. Mater. Interfaces 2017, 9 (3), 2023–2028

  44. M. Chen, J.-W. Li, W.-J. Zhang, C.-Y. Hong, C.-Y. Pan, pH- and reductant-responsive polymeric vesicles with robust membrane-cross-linked structures: in situ cross-linking in Polymerization-Induced Self-Assembly. Macromolecules 2019, 52 (3), 1140–1149

  45. P. Saha, M. Kather, S.L. Banerjee, N.K. Singha, A. Pich, Aqueous solution behavior of thermoresponsive polyzwitterionic microgels based on poly(N-vinylcaprolactam) synthesized via RAFT precipitation polymerization. Eur. Polym. J. 118, 195–204 (2019)

    Article  CAS  Google Scholar 

  46. J. Tan, D. Liu, Y. Bai, C. Huang, X. Li, J. He, Q. Xu, X. Zhang, L. Zhang, An insight into aqueous photoinitiated polymerization-induced self-assembly (photo-PISA) for the preparation of diblock copolymer nano-objects. Polymer Chemistry 2017, 8 (8), 1315–1327

  47. J. Jacobs, D. Pavlovic, H. Prydderch, M.A. Moradi, E. Ibarboure, J.P.A. Heuts, S. Lecommandoux, A. Heise, Polypeptide nanoparticles obtained from Emulsion polymerization of amino acid N-Carboxyanhydrides. J. Am. Chem. Soc. 141(32), 12522–12526 (2019)

    Article  CAS  PubMed  Google Scholar 

  48. Z. Tajmoradi, H. Roghani-Mamaqani, M. Salami-Kalajahi, Cellulose nanocrystal-grafted multi-responsive copolymers containing cleavable o-nitrobenzyl ester units for stimuli-stabilization of oil-in-water droplets. Chem. Eng. J. 2021, 417

  49. S. Chatani, C.J. Kloxin, C.N. Bowman, The power of light in polymer science: photochemical processes to manipulate polymer formation, structure, and properties. Polym. Chem. 5(7), 2187–2201 (2014)

    Article  CAS  Google Scholar 

  50. A. Abdollahi, H. Roghani-Mamaqani, B. Razavi, M. Salami-Kalajahi, The light-controlling of temperature-responsivity in stimuli-responsive polymers. Polym. Chem 10(42), 5686–5720 (2019)

    Article  CAS  Google Scholar 

  51. A. Romano, I. Roppolo, E. Rossegger, S. Schlogl, M. Sangermano, Recent Trends in applying Rrtho-Nitrobenzyl Esters for the design of Photo-Responsive Polymer Networks. Materials (Basel) 2020, 13 (12)

  52. M. Tan, Y. Shi, Z. Fu, W. Yang, In situ synthesis of diblock copolymer nano-assemblies via dispersion RAFT polymerization induced self-assembly and Ag/copolymer composite nanoparticles thereof. Polymer Chemistry 2018, 9 (9), 1082–1094

  53. B. Liang, G. Zhang, Z. Zhong, T. Sato, A. Hozumi, Z. Su, Substrate-independent polyzwitterionic coating for oil/water separation membranes. Chem. Eng. J. 362, 126–135 (2019)

    Article  CAS  Google Scholar 

  54. Z. Lei, P. Wu, A supramolecular biomimetic skin combining a wide spectrum of mechanical properties and multiple sensory capabilities. Nat. Commun. 9(1), 1134 (2018)

    Article  PubMed  PubMed Central  Google Scholar 

  55. H. Wu, J. Dong, X. Zhan, H. Yang, Y. Zhao, S. Zhu, G. Wang, Triple stimuli-responsive crosslinked polymeric nanoparticles for controlled release. RSC Adv 4, (67) (2014)

    Google Scholar 

  56. G. Moad, Y.K. Chong, A. Postma, E. Rizzardo, S.H. Thang, Advances in RAFT polymerization: the synthesis of polymers with defined end-groups. Polymer 2005, 46 (19), 8458–8468

  57. A. Pourjavadi, S. Rahemipoor, M. Kohestanian, Synthesis and characterization of multi stimuli-responsive block copolymer-silica hybrid nanocomposite with core-shell structure via RAFT polymerization. Composites Science and Technology 2020, 188

  58. Q. Zhang, S. Zhu, Ionic liquids: versatile media for Preparation of vesicles from Polymerization-Induced Self-Assembly. ACS Macro Lett 4(7), 755–758 (2015)

    Article  CAS  PubMed  Google Scholar 

  59. Y. Qu, F. Huo, Q. Li, X. He, S. Li, W. Zhang, In situ synthesis of thermo-responsive ABC triblock terpolymer nano-objects by seeded RAFT polymerization. Polym. Chem. 5, 5569–5577 (2014)

    Article  CAS  Google Scholar 

  60. J.-M. Schumers, C.-A. Fustin, A. Can, R. Hoogenboom, U.S. Schubert, J.-F. Gohy, Areo-Nitrobenzyl (Meth)acrylate monomers polymerizable by controlled-radical polymerization? J. Polym. Science: Part A: Polym. Chem. 47, 6504–6513 (2009)

    Article  CAS  Google Scholar 

  61. H. Zhou, C. Liu, Y. Qu, C. Gao, K. Shi, W. Zhang, How the polymerization procedures affect the morphology of the Block Copolymer Nanoassemblies: comparison between Dispersion RAFT polymerization and seeded RAFT polymerization. Macromolecules 49, 8167–8176 (2016)

    Article  CAS  Google Scholar 

  62. P. Yang, L.P.D. Ratcliffe, S.P. Armes, Efficient synthesis of poly(methacrylic acid)-block-Poly(styrene-alt-Nphenylmaleimide) Diblock Copolymer Lamellae using RAFT dispersion polymerization. Macromolecules 2013, 46, 8545 – 8556

  63. Y. Zhang, G. Han, M. Cao, T. Guo, W. Zhang, Influence of Solvophilic Homopolymers on RAFT Polymerization-Induced Self-Assembly. Macromolecules 51, 4397–4406 (2018)

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 22201109 and 51473070) and Cultivating Fund of School of Materials Science & Engineering, Jiangsu University.

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  1. Research School of Polymeric Materials, School of Materials Sciences & Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang, 212013, Jiangsu, P. R. China

    Yuan Zhang, Peng Wang, Nan Li, Chunyan Guo, Yudie Liu & Songjun Li

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  1. Yuan Zhang
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Zhang, Y., Wang, P., Li, N. et al. RAFT Dispersion Polymerization of Nitrobenzene-based Monomer and Photo-response of its Polymer Nanoparticles. J Inorg Organomet Polym 33, 2368–2377 (2023). https://doi.org/10.1007/s10904-023-02629-5

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