TY - JOUR
T1 - Modulation of Double Zwitterionic Block Copolymer Aggregates by Zwitterion-Specific Interactions
AU - Shimizu, Akane
AU - Hifumi, Emi
AU - Kojio, Ken
AU - Takahara, Atsushi
AU - Higaki, Yuji
N1 - Funding Information:
Y.H. gratefully acknowledges the Izumi Science and Technology Foundation (Grant 2019-J-027) and the KOSÉ Cosmetology Research Foundation (Grant 694) for their financial support. This work was performed under the Cooperative Research Program of “Network Joint Research Center for Materials and Devices”. This work was supported by Oita University President’s Strategic Discretionary Fund. The authors acknowledge Y. Saruwatari (Osaka Organic Chemical Industry Ltd.) for the kind donation of the carboxybetaine methacrylate monomer.
Publisher Copyright:
© 2021 American Chemical Society
PY - 2021/12/21
Y1 - 2021/12/21
N2 - Transformable double hydrophilic block copolymer assemblies are valid as a biocompatible smart macromolecular system. The molecular mechanisms in the spontaneous assembly of double zwitterionic diblock copolymers composed of a poly(carboxybetaine methacrylate) (PCB2) and a poly(sulfobetaine methacrylate) (PSB4) chains (PCB2-b-PSB4) were investigated by the modulation of the aggregates in response to nondetergent zwitterions. The PCB2-b-PSB4 diblock copolymers with a high degree of polymerization PSB4 block produced aggregates in salt-free water through “zwitterion-specific” interactions. The PCB2-b-PSB4 aggregates were dissociated by the addition of nondetergent sulfobetaine (SB4) and carboxybetaine (CB2) molecules, while the aggregates showed different aggregation modulation processes for SB4 and CB2. Zwitterions with different charged groups from SB4 and CB2, glycine and taurine, hardly disrupted the PCB2-b-PSB4 aggregates. The PCB2-b-PSB4 aggregate modulation efficiency of SBs associated with the intercharge hydrocarbon spacer length (CSL) rather than the symmetry with the SB in the PSB chain. These zwitterion-specific modulation behaviors were rationalized based on the nature of zwitterions including partial charge density, dipole moment, and hydrophobic interactions depending on the charged groups and CSL.
AB - Transformable double hydrophilic block copolymer assemblies are valid as a biocompatible smart macromolecular system. The molecular mechanisms in the spontaneous assembly of double zwitterionic diblock copolymers composed of a poly(carboxybetaine methacrylate) (PCB2) and a poly(sulfobetaine methacrylate) (PSB4) chains (PCB2-b-PSB4) were investigated by the modulation of the aggregates in response to nondetergent zwitterions. The PCB2-b-PSB4 diblock copolymers with a high degree of polymerization PSB4 block produced aggregates in salt-free water through “zwitterion-specific” interactions. The PCB2-b-PSB4 aggregates were dissociated by the addition of nondetergent sulfobetaine (SB4) and carboxybetaine (CB2) molecules, while the aggregates showed different aggregation modulation processes for SB4 and CB2. Zwitterions with different charged groups from SB4 and CB2, glycine and taurine, hardly disrupted the PCB2-b-PSB4 aggregates. The PCB2-b-PSB4 aggregate modulation efficiency of SBs associated with the intercharge hydrocarbon spacer length (CSL) rather than the symmetry with the SB in the PSB chain. These zwitterion-specific modulation behaviors were rationalized based on the nature of zwitterions including partial charge density, dipole moment, and hydrophobic interactions depending on the charged groups and CSL.
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U2 - 10.1021/acs.langmuir.1c02809
DO - 10.1021/acs.langmuir.1c02809
M3 - Article
C2 - 34889092
AN - SCOPUS:85121735550
SN - 0743-7463
VL - 37
SP - 14760
EP - 14766
JO - Langmuir
JF - Langmuir
IS - 50
ER -