Self-assembly Induced by Complexation of Diblock Copolyelectrolytes and Oppositely Charged Homopolymers

Ling Zhao; Zhi-Yuan Yin; Jia-Di Jiang; Er-Qiang Chen; Shuang Yang

doi:10.1007/s10118-024-3080-1

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Self-assembly Induced by Complexation of Diblock Copolyelectrolytes and Oppositely Charged Homopolymers

RESEARCH ARTICLE | Updated：2024-08-27

- Self-assembly Induced by Complexation of Diblock Copolyelectrolytes and Oppositely Charged Homopolymers
- Chinese Journal of Polymer Science Vol. 42, Issue 9, Pages: 1321-1332(2024)
- Affiliations：
  
  a.Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Center for Soft Mater Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
  b.Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
- Author bio：
  
  eqchen@pku.edu.cn (E.Q.C.)
  shuangyang@pku.edu.cn (S.Y.)
- Funds：
- DOI：10.1007/s10118-024-3080-1
  CLC：
- Received：31 October 2023，
  
  Revised：2023-11-30，
  
  Accepted：11 December 2023，
  
  Online First：26 January 2024，
  
  Published：01 September 2024
- Accepted：
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Zhao, L.; Yin, Z. Y.; Jiang, J. D.; Chen, E. Q.; Yang, S. Self-assembly induced by complexation of diblock copolyelectrolytes and oppositely charged homopolymers. Chinese J. Polym. Sci. 2024, 42, 1321–1332

Ling Zhao, Zhi-Yuan Yin, Jia-Di Jiang, et al. Self-assembly Induced by Complexation of Diblock Copolyelectrolytes and Oppositely Charged Homopolymers[J]. Chinese Journal of Polymer Science, 2024, 42(9): 1321-1332.
Zhao, L.; Yin, Z. Y.; Jiang, J. D.; Chen, E. Q.; Yang, S. Self-assembly induced by complexation of diblock copolyelectrolytes and oppositely charged homopolymers. Chinese J. Polym. Sci. 2024, 42, 1321–1332 DOI： 10.1007/s10118-024-3080-1.

Ling Zhao, Zhi-Yuan Yin, Jia-Di Jiang, et al. Self-assembly Induced by Complexation of Diblock Copolyelectrolytes and Oppositely Charged Homopolymers[J]. Chinese Journal of Polymer Science, 2024, 42(9): 1321-1332. DOI： 10.1007/s10118-024-3080-1.

摘要

We study the self-assembly of oppositely charged diblock copolymer and homopolymer based on ion-pair model. By use of self-consistent field theory

we investigate the influence of homopolymer content on the self-assembled structures systematically and calculate the phase diagrams under different conditions.

Abstract

We investigate the solution self-assembly of

a mixture of positively charged homopolymers and AB diblock copolymers

in which the A blocks are negatively charged

and the B blocks are neutral. The electrostatic complexation between oppositely charged polymers drives the formation of many ordered phases. The microstructures and phase diagrams are calculated using self-consistent field theory (SCFT) based on an ion-pair model with an equilibrium constant

$$ K $$

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=64482095&type=middle

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=64482095&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=64482095&type=small

to characterize the strength of binding between positively and negatively charged monomers. The effects of the charge ratio

representing the ratio of charges from the homopolymer over all charges from polymers in the system

on the ordered structure are systematically studied

both for hydrophobic and hydrophilic A blocks. The charge ratio plays an important role in determining the phase boundaries in the phase diagram of salt concentration versus polymer concentration. We also provide information about the varying tendency of the domain spacing and core size of the spherical phase when the charge ratio is changed

and the results are in good agreement with experiments. These studies provide a deep understanding of the self-assembled microstructures of oppositely charged diblock copolymer-homopolymer systems.

关键词

Keywords

references

Zhou, J.; Shi, A. C. Microphase separation induced by differential interactions in diblock copolymer/homopolymer blends. J. Chem. Phys. 2009 , 130, 234904..

Qian, H. J.; Lu, Z. Y.; Chen, L. J.; Li, Z. S.; Sun, C. C. Dissipative particle dynamics study on the interfaces in incompatible A/B homopolymer blends and with their block copolymers. J. Chem. Phys. 2005 , 122, 184907..

Hashimoto, T.; Koizumi, S.; Hasegawa, H.; Izumitani, T.; Hyde, S. T. Observation of "mesh" and "strut" structures in block copolymer/homopolymer mixtures. Macromolecules 1992 , 25, 1433−1439..

Han, C. D.; Baek, D. M.; Kim, J.; Kimishima, K.; Hashimoto, T. Viscoelastic behavior, phase equilibria, and microdomain morphology in mixtures of a block copolymer and a homopolymer. Macromolecules 1992 , 25, 3052−3067..

Spontak, R. J.; Smith, S. D.; Ashraf, A. Dependence of the OBDD morphology on diblock copolymer molecular weight in copolymer/homopolymer blends. Macromolecules 1993 , 26, 956−962..

Disko, M. M.; Liang, K. S.; Behal, S. K.; Roe, R. J.; Jeon, K. J. Catenoid-lamellar phase in blends of styrene-butadiene diblock copolymer and homopolymer. Macromolecules 1993 , 26, 2983−2986..

Je on, K. J.; Roe, R. J. Solubilization of a homopolymer in a block copolymer. Macromolecules 1994 , 27, 2439−2447..

Zin, W. C.; Roe, R. J. Phase equilibria and transition in mixtures of a homopolymer and a block copolymer. 1. Small-angle X-ray scattering study. Macromolecules 1984 , 17, 183−188..

Roe, R. J.; Zin, W. C. Phase equilibria and transition in mixtures of a homopolymer and a block copolymer. 2. Phase diagram. Macromolecules 1984 , 17, 189−194..

Kinning, D. J.; Winey, K. I.; Thomas, E. L. Structural transitions from spherical to nonspherical micelles in blends of poly(styrene-butadiene) diblock copolymer and polystyrene homopolymers. Macromolecules 1988 , 21, 3502−3506..

Owens, J. N.; Gancarz, I. S.; Koberstein, J. T.; Russell, T. P. Order-disorder transitions in mixtures of homopolymers with diblock copolymers. Macromolecules 1989 , 22, 3388−3394..

Hashimoto, T.; Tanaka, H.; Hasegawa, H. Ordered structure in mixtures of a block copolymer and homopolymers. 2. Effects of molecular weights of homopolymers. Macromolecules 1990 , 23, 4378−4386..

Kuo, S. W. Hydrogen bonding mediated self-assembled structures from block copolymer mixtures to mesoporous materials. Polymer International 2022 , 71, 393−410..

Matsen, M. W. Phase behavior of block copolymer/homopolymer blends. Macromolecules 1995 , 28, 5765−5773..

Matsen, M. W. Stabilizing new morphologies by blending homopolymer with block copolymer. Physical Review Letters 1995 , 74, 4225−4228..

Matsen, M. W. New fast SCFT algorithm applied to binary diblock copolymer/homopolymer blends. Macromolecules 2003 , 36, 9647−9657..

Lee, H. F.; Kuo, S. W.; Huang, C. F.; Lu, J. S.; Chan, S. C.; Wang, C. F.; Chang, F. C. Hydrogen-bonding interactions mediate the phase behavior of an A-B/C block copolymer/homopolymer blend comprising poly(methyl methacrylate- b -vinylpyrrolidone) and Poly(Vinylphenol). Macromolecules 2006 , 39, 5458−5465..

Chen, W. C.; Kuo , S. W.; Lu, C. H.; Jeng, U. S.; Chang, F. C. Self-assembly structures through competitive interactions of crystalline-amorphous diblock copolymer/homopolymer blends: poly( $$\epsilon$$ http://notExist.jpg http://notExist.jpg http://notExist.jpg -caprolactone- b -4-vinyl pyridine)/poly(vinyl phenol). Macromolecules 2009 , 42, 3580−3590..

Dobrosielska, K.; Wakao, S.; Suzuki, J.; Noda, K.; Takano, A.; Matsushita, Y. Effect of homopolymer molecular weight on nanophase-separated structures of AB block copolymer/C homopolymer blends with hydrogen-bonding interactions. Macromolecules 2009 , 42, 7098−7102..

Dehghan, A.; Shi, A. C. Modeling hydrogen bonding in diblock copolymer/homopolymer blends. Macromolecules 2013 , 46, 5796−5805..

Voets, I. K.; de Keizer, A.; de Waard, P.; Frederik, P. M.; Bomans, P. H. H.; Schmalz, H.; Walther, A.; King, S. M.; Leermakers, F. A. M.; Cohen Stuart, M. A. Double-faced micelles from water-soluble polymers. Angew. Chem., Int. Ed. 2006 , 45, 6673−6676..

Takahashi, R.; Sato, T.; Terao, K.; Yusa, S. I. Intermolecular interactions and self-assembly in aqueous solution of a mixture of anionic-neutral and cationic-neutral block copolymers. Macromolecules 2015 , 48, 7222−7229..

Yan, Y.; Harnau, L.; Besseling, N. A. M.; de Keizer, A.; Ballauff, M.; Rosenfeldt, S.; Cohen Stuart, M. A. Spherocylindrical coacervate core micelles formed by a supramolecular coordination polymer and a diblock copolymer. Soft Matter 2008 , 4, 2207−2212..

Oana, H.; Morinaga, M.; Kishimura, A.; Kataoka, K.; Washizu, M. Direct formation of giant unilamellar vesicles from microparticles of polyion complexes and investigation of their properties using a microfluidic chamber. Soft Matter 2013 , 9, 5448−5458..

Anraku, Y.; Kishimura, A.; Oba, M.; Yamasaki, Y.; Kataoka, K. Spontaneous formation of nanosized unilamellar polyion complex vesicles with tunable size and properties. J. Am. Chem. Soc. 2010 , 132, 1631−1636..

Perry, S. L.; Leon, L.; Hoffmann, K. Q.; Kade, M. J.; Priftis, D.; Black, K. A.; Wong, D.; Klein, R. A.; Pierce, C. F.; Margossian, K. O.; Whitmer, J. K.; Qin, J.; de Pablo, J. J.; Tirrell, M. Chirality-selected phase behaviour in ionic polypeptide complexes. Nat. Commun. 2015 , 6, 6052..

Elabd, Y. A.; Hickner, M. A. Block copolymers for fuel cells. Macromolecules 2011 , 44, 1−11..

Rubatat, L.; Shi, Z.; Diat, O.; Holdcroft, S.; Frisken, B. J. Structural study of proton-conducting fluorous block copolymer membranes. Macromolecules 2006 , 39, 720−730..

Wang, X.; Yakovlev, S.; Beers, K. M.; Park, M. J.; Mullin, S. A.; Downing, K. H.; Balsara, N. P. On the origin of slow changes in ionic conductivity of model block copolymer electrolyte membranes in contact with humid air. Macromolecules 2010 , 43, 5306−5314..

LimSoo, P.; Luo, L.; Maysinger, D.; Eisenberg, A. Incorporation and release of hydrophobic probes in biocompatible polycaprolactone-block-poly(ethylene oxide) micelles: implications for drug delivery. Langmuir 2002 , 18, 9996−10004..

Acar, H.; Ting, J. M.; Srivastava, S.; LaBelle, J. L.; Tirrell, M. V. Molecular engineering solutions for therapeutic peptide delivery. Chem. Soc. Rev 2017 , 46, 6553−6569..

Chassenieux, C.; Tsitsilianis, C. Recent trends in pH/thermo-responsive self-assembling hydrogels: from polyions to peptide-based polymeric gelators. Soft Matter 2016 , 12, 1344−1359..

Huo, H.; Zhao, W.; Duan, X.; Sun, Z. Y. Control of diblock copolyelectrolyte morphology through electric field application. Macromolecules 2023 , 56, 1065−1076..

Rahalkar, A.; Wei, G.; Nieuwendaal, R.; Prabhu, V. M.; Srivastava, S.; Levi, A. E.; Pablo, J. J. d.; Tirrell, M. V. Effect of temperature on the structure and dynamics of triblock polyelectrolyte gels. J. Chem. Phys. 2018 , 149, 163310..

Lemmers, M.; Sprakel, J.; Voets, I. K.; van der Gucht, J.; Cohen Stuart, M. A. Multiresponsive reversible gels based on charge-driven assembly. Angew. Chem., Int. Ed. 2010 , 49, 708−711..

Kramarenko, E. Y.; Khokhlov, A. R.; Reineker, P. Stoichiometric polyelectrolyte complexes of ionic block copolymers and oppositely charged polyions. J. Chem. Phys. 2006 , 125, 194902..

Duan, X.; Shi, A. C.; An, L. Form ation of ionomer microparticles via polyelectrolyte complexation. Macromolecules 2021 , 54, 9053−9062..

Hunt, J. N.; Feldman, K. E.; Lynd, N. A.; Deek, J.; Campos, L. M.; Spruell, J. M.; Hernandez, B. M.; Kramer, E. J.; Hawker, C. J. Tunable, high modulus hydrogels driven by ionic coacervation. Adv. Mater. 2011 , 23, 2327−2331..

Krogstad, D. V.; Lynd, N. A.; Choi, S. H.; Spruell, J. M.; Hawker, C. J.; Kramer, E. J.; Tirrell, M. V. Effects of polymer and salt concentration on the structure and properties of triblock copolymer coacervate hydrogels. Macromolecules 2013 , 46, 1512−1518..

Audus, D. J.; Gopez, J. D.; Krogstad, D. V.; Lynd, N. A.; Kramer, E. J.; Hawker, C. J.; Fredrickson, G. H. Phase behavior of electrostatically complexed polyelectrolyte gels using an embedded fluctuation model. Soft Matter 2015 , 11, 1214−1225..

Lytle, T. K.; Radhakrishna, M.; Sing, C. E. High charge density coacervate assembly via hybrid monte carlo single chain in mean field theory. Macromolecules 2016 , 49, 9693−9705..

Jiang, J.; Chen, X.; Yang, S.; Chen, E. Q. The size and affinity effect of counterions on self-assembly of chargedblock copolymers. J. Chem. Phys. 2020 , 152, 124901..

Jiang, J.; Chen, E. Q.; Yang, S. The effect of ion pairs on coacervate-driven self-assembly of block polyelectrolytes. J. Chem. Phys. 2021 , 154, 144903..

Holappa, S.; Andersson, T.; Kantonen, L.; Plattner, P.; Tenhu, H. Soluble polyelectrolyte complexes composed of poly(ethylene oxide)-block-poly(sodium methacrylate) and poly(methacryloyloxyethyl trimethylammonium chloride). Polymer 2003 , 44, 7907−7916..

Marras, A. E.; Vieregg, J. R.; Ting, J. M.; Rubien, J. D.; Tirrell, M. V. Polyelectrolyte complexation of oligonucleotides by charged hydrophobic-neutral hydrophilic block copolymers. Polymers 2019 , 11, 83..

ElJundi, A.; Buwalda, S. J.; Bakkour, Y.; Garric, X.; Nottelet, B. Double hydrophilic block copolymers self-assemblies in biomedical applications. Adv. Colloid Interface Sci. 2020 , 283, 102213..

Hofs, B.; de Keizer, A.; van der Burgh, S.; Leermakers, F. A. M.; Cohen Stuart, M. A.; Millard, P. E.; Müller, A. H. E. C omplex coacervate core micro-emulsions. Soft Matter 2008 , 4, 1473−1482..

Lindhoud, S.; de Vries, R.; Schweins, R.; Cohen Stuart, M. A.; Norde, W. Salt-induced release of lipase from polyelectrolyte complex micelles. Soft Matter 2009 , 5, 242−250..

Read, E.; Lonetti, B.; Gineste, S.; Sutton, A. T.; Di Cola, E.; Castignolles, P.; Gaborieau, M.; Mingotaud, A. F.; Destarac, M.; Marty, J. D. Mechanistic insights into the formation of polyion complex aggregates from cationic thermoresponsive diblock copolymers. J. Colloid Interface Sci. 2021 , 590, 268−276..

Rizis, G.; van de Ven, T. G. M.; Eisenberg, A. Homopolymers as structure-driving agents in semicrystalline block copolymer micelles. ACS Nano 2015 , 9, 3627−3640..

van der Burgh, S.; de Keizer, A.; Cohen Stuart, M. A. Complex coacervation core micelles. Colloidal stability and aggregation mechanism. Langmuir 2004 , 20, 1073−1084..

Weaver, J. V. M.; Armes, S. P.; Liu, S. A "holy trinit" of micellar aggregates in aqueous solution at ambient temperature: unprecedented self-assembly behavior from a binary m ixture of a neutral-cationic diblock copolymer and an anionic polyelectrolyte. Macromolecules 2003 , 36, 9994−9998..

Liu, J. Y.; Song, H. R.; Wang, M.; Jin, S. H.; Liang, Z.; Mao, X.; Li, W.; Deng, R. H.; Zhu, J. T. Asymmetric mesoporous carbon microparticles by 3D-confined self-assembly of block copolymer/homopolymer blends andselective carbonization. Chinese J. Polym. Sci. 2023 , 41, 787−793..

Zhang, X.; Chen, J.; Xu, L.; Liu, T. Supramolecular self-assembly behaviors of asymmetric diblock copolymer blends with hydrogen bonding interactions between shorter blocks modelled by Yukawa potentials. Chinese J. Polym. Sci. 2021 , 39, 1502−1509..

Kramarenko, E. Y.; Khokhlov, A. R.; Reineker, P. Micelle formation in a dilute solution of block copolymers with a polyelectrolyte block complexed with oppositely charged linear chains. J. Chem. Phys. 2003 , 119, 4945−4952..

Lemmers, M.; Voets, I. K.; Cohen Stuart, M. A.; der Gucht, J. V. Transient network topology of interconnected polyelectrolyte complex micelles. Soft Matter 2011 , 7, 1378−1389..

Bodrova, A. S.; Kramarenko, E. Y.; Potemkin, I. I. Microphase separation induced by complexation of ionic-non-ionic diblock copolymers with oppositely charged linear chains. Macromolecules 2010 , 43, 2622−2629..

Harada, A.; Kataoka, K. Formation of polyion complex micelles in an aqueous milieu from a pair of oppositely-charged block copolymers with poly(ethylene glycol) segments. Macromolecules 1995 , 28, 5294−5299..

CohenStuart, M. A.; Besseling, N. A. M.; Fokkink, R. G. Formation of micelles with complex coacervate cores. Langmuir 1998 , 14, 6846−6849..

Voets, I. K.; de Keizer, A.; Cohen Stuart, M. A.; Justynska, J.; Schlaad, H. Irreversible structural transitions in mixed micelles of oppositely charged diblock copolymers in aqueous solution. Macromolecules 2007 , 40, 2158−2164..

Lindhoud, S.; Norde, W.; Cohen Stuart, M. A. Reversibility and relaxation behavior of polyelectrolyte complex micelle formation. J. Phys. Chem. B 2009 , 113, 5431−5439..

Lemmers, M.; Spruijt, E.; Beun, L.; Fokkink, R.; Leermakers, F.; Portale, G.; Cohen Stuart, M. A.; van der Gucht, J. The influence of charge ratio on transient networks of polyelectrolyte complex micelles. Soft Matter 2012 , 8, 104−117..

Shi, A. C.; Noolandi, J. Theory of inhomogeneous weakly charged polyelectrolytes. Macromol. Theory Simul. 1999 , 8, 214−229..

Yan, Y.; Besseling, N. A. M.; de Keizer, A.; Marcelis, A. T. M.; Drechsler, M.; Cohen Stuart, M. A. Hierarchical self-assembly in solutions containing metal ions, ligand, and diblock copolymer. Angew. Chem., Int. Ed. 2007 , 46, 1807−1809..

Nakai, K.; Nishiuchi, M.; Inoue, M.; Ishihara, K.; Sanada, Y.; Sakurai, K.; Yusa, S. I. Preparation and characterization of polyion complex micelles with phosphobetaine shells. Langmuir 2013 , 29, 9651−9661..

Gohy, J. F.; Varshney, S. K.; Antoun, S.; Jérôme, R. Water-soluble complexes formed by sodium poly(4-styrenesulfonate) and a poly(2-vinylpyridinium)-block-poly(ethyleneoxide) copolymer. Macromolecules 2000 , 33, 9298−9305..

Hofs, B.; de Keizer, A.; Cohen Stuart, M. A. On the stability of (highly aggregated) polyelectrolyte complexes containing a charged-block-neutral dibloc k copolymer. J. Phys. Chem. B 2007 , 111, 5621−5627..

Yusa, S. I.; Fukuda, K.; Yamamoto, T.; Ishihara, K.; Morishima, Y. Synthesis of well-defined amphiphilic block copolymers having phospholipid polymer sequences as a novel biocompatible polymer micelle reagent. Biomacromolecules 2005 , 6, 663−670..

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