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Characterization of PMMA-b-PDMAEMA aggregates in aqueous solutions

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Abstract

Diblock amphiphilic copolymers form aggregates in some solvents. Such aggregates exhibit different morphologies, depending mainly on the polar/apolar block ratios. Aggregation of copolymers with polar block excess leads to micelle-like aggregates, known as polymeric micelles, which can be used as vehicles for drug and gene delivery, water decontamination, and catalysis. Here, we synthesized by RAFT polymerization three different polymers namely [dimethyl 2-(aminoethyl) methacrylate] (PDMAEMA), poly (methyl methacrylate) (PMMA) copolymers, and PDMAEMA-block-PMMA and characterized their aggregates by NMR spectroscopy and pH titrations. We investigated correlations between their chemical structure, aggregation behavior, protonation degree, and chain conformation in the corona. Decreased amine protonation in the copolymers reduced the electrostatic repulsion, and the apparent pKa of the amino groups approached that of isolated amine. These effects increased compactness and sizes of the polymers and their aggregates at higher pH as reflected by the increased NMR line widths.

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Acknowledgments

IMC, HC, and RKS are CNPq research scholars. GKVS acknowledges the Projeto Biocomputacional/CAPES (proc. no. 23038.004630/2014-35) and CNPq (proc. 457733/2014-4).

Funding

FAPESP (grant number 2013/08166-5 and 2016/07490-1). IMC has been supported by the INCT-FCx (Instituto Nacional de Ciência e Tecnologia de Fluidos Complexos (CNPq/CAPES/FINEP/FAPESP) and NAP-FCx (Núcleo de Apoio à Pesquisa de Fluidos Complexos da Universidade de São Paulo).

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Author notes

  1. L. Coutinho de Oliveira

    Present address: INRS-Institut Armand-Frappier, 531 boulevard des Prairies, Laval, Québec, H7V 1B7, Canada

  2. M. L. C. Noronha

    Present address: Centro Universitário de Itajubá, Itajubá, Brazil

Authors and Affiliations

  1. Departamento de Bioquímica, Instituto de Química, Universidade de São Paulo, São Paulo, Brazil

    G. K. V. Saraiva, V. V. de Souza, L. Coutinho de Oliveira, H. Chaimovich, R. K. Salinas & I. M. Cuccovia

  2. Instituto de Ciências Exatas, Universidade Federal de Alfenas, Alfenas, Brazil

    M. L. C. Noronha

  3. Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo, Brazil

    J. C. Masini

  4. Departamento de Engenharia de Materiais, Escola de Engenharia de Lorena, Universidade de São Paulo, Lorena, São Paulo, Brazil

    F. H. Florenzano

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  1. G. K. V. Saraiva
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Correspondence to F. H. Florenzano or I. M. Cuccovia.

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Saraiva, G.K.V., de Souza, V.V., de Oliveira, L.C. et al. Characterization of PMMA-b-PDMAEMA aggregates in aqueous solutions. Colloid Polym Sci 297, 557–569 (2019). https://doi.org/10.1007/s00396-019-04482-w

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  • DOI: https://doi.org/10.1007/s00396-019-04482-w

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