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- W2020031791 abstract "It is known that the zwitterionic diblock copolymer, poly(4-vinylbenzoic acid)-b-poly(N-(morpholino)ethyl methacrylate) (VBA-b-MEMA), exhibits interesting “schizophrenic” micellization behavior (see: Liu, S.; Armes, S. P. Langmuir 2003, 19, 4432−4438). The kinetics of the pH-induced formation and dissociation of VBA−core micelles, the salt-induced formation and dilution-induced dissociation of MEMA−core micelles at pH 10, and the pH-induced micellar inversion between VBA− and MEMA−core micelles in the presence of 0.8 M Na2SO4 were studied in detail using stopped-flow apparatus equipped with a light scattering detector. A pH jump from 12 to 2 in the absence of salt leads to the formation of VBA−core micelles; upon a pH jump from 2 to 12, the breakup of VBA−core micelles into unimers occurs within the dead time of the stopped-flow apparatus (∼ 2−3 ms). At pH 10, addition of Na2SO4 (> 0.6 M) induces the formation of MEMA−core micelles. Compared to the pH-induced formation and dissociation of VBA−core micelles, the salt-induced formation of MEMA−core micelles is faster, while the dilution-induced dissociation of MEMA−core micelles into unimers is considerably slower. This partially reflects the block length asymmetry of this VBA-b-MEMA copolymer and also the fact that the MEMA−core micelles are denser and larger than the VBA−core micelles. The structural inversion from VBA−core micelles to MEMA−core micelles upon a pH jump from 2 to 12 in the presence of 0.8 M Na2SO4 proceeds first with the fusion of VBA−core micelles into lose aggregates due to the insolubility of MEMA shell immediately after pH jump, then the dissociation of VBA−core micelles into unimers and partial disintegration of initially formed loose aggregates, which is followed and/or accompanied by the reaggregation of unimer chains into MEMA core-micelles. The structural inversion from MEMA−core micelles to VBA−core micelles on jumping from pH 12 to 2 in the presence of 0.8 M Na2SO4 exhibits different kinetics. The scattering intensities decrease monotonically with time and then stabilize out. All the relaxation curves at different copolymer concentrations can be well-fitted using a single-exponential function and the characteristic relaxation time for the structural inversion of the micelles (τi) is ∼0.3 s, which slightly decreases with increasing copolymer concentrations. We tentatively propose that the structural inversion from MEMA−core to VBA−core micelles proceeds first with the splitting of large MEMA−core micelles into small VBA−core micelles, followed and/or accompanied by the redistribution of unimer chains between appearing small VBA−core micelles." @default.
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- W2020031791 date "2006-09-13" @default.
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- W2020031791 title "Micelle Formation and Inversion Kinetics of a Schizophrenic Diblock Copolymer" @default.
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- W2020031791 doi "https://doi.org/10.1021/ma061049d" @default.
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