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One-Dimensional Assembly of Silica Nanospheres: Effects of Nonionic Block Copolymers

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Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
*E-mail: [email protected]. Telephone: +81-3-5841-7348. Fax: +81-3-5800-3806.
Cite this: Langmuir 2012, 28, 37, 13181–13188
Publication Date (Web):August 30, 2012
https://doi.org/10.1021/la302443f
Copyright © 2012 American Chemical Society

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    Abstract

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    The effects of polymers on the one-dimensional assembly of silica nanospheres (SNSs) in the liquid phase are systematically investigated using nonionic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (abbreviated as PEO-PPO-PEO) triblock copolymers with varying hydrophilic–lipophilic balance (HLB) values. Scanning electron microscopy is employed for morphological observations of the polymer-mediated assemblies of SNSs on the basis of which the optimal pH for 1D assembly (pH1D) is determined. To clarify the polymers’ effects on the 1D assembly of SNSs, the relationships between pH1D and polymers’ HLB values, the numbers of hydrophilic EO and hydrophobic PO units, and the relative ratio of NPO/NEO are examined. Zeta potential measurements are conducted to investigate the electrostatic repulsion among the SNSs in the presence of block copolymers. It is found that the relative hydrophilicity of the block copolymers greatly affects the balance of interactions in the 1D assembly of SNSs. Block copolymers with large HLB values promote the 1D assembly of SNSs under near-neutral pH conditions, whereas the block copolymers with small HLB values promote 1D assembly under basic pH conditions. Therefore, the 1D assembly of SNSs is achieved over an extensive pH range (7.5–9.5) through the employment of block copolymers of different hydrophilic and hydrophobic block lengths.

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    TEM image of the chainlike structures. SEM images of the chainlike structures after different incubation times, before and after sonication, and after pH readjustment. CHN chemical analysis of the adsorbed amounts of polymers on SNSs. SEM images of the polymer-free SNS suspensions. This material is available free of charge via the Internet at http://pubs.acs.org.

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