Dynamics of end-grafted polystyrene brushes in theta solvents

The dynamics of the concentration fluctuations in end-grafted polystyrene brushes in a theta solvent (cyclohexane) are probed by evanescent wave dynamic light scattering at different wavevectors q and temperatures. When the solvent quality changes from marginal to poor, the relaxation function C(q, t) exhibits strong effects as compared with the smooth variation of the brush density profile. From a single exponential above 50 °C, C(q, t) becomes a two-step decay function. The fast decay is still assigned to the cooperative diffusion albeit slower than in the good solvent regime whereas the slow nonexponential and nondiffusive process might relate to microsegragated and/or chain dynamics in the present polydisperse brush. The relaxation function of the present three brushes with different grafting density reveals similarities and disparities between wet brushes and semidilute polymer solutions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3590–3597, 2006     

Poly(2-(dimethylamino)ethyl methacrylate) brushes fabricated by surface-mediated RAFT polymerization and their response to pH

In this study, well-defined, high density poly(2-(dimethylamino)ethyl methacrylate) [poly(DMAEMA)] brushes were fabricated by the combination of the self-assembly of a monolayer of RAFT agent and surface-mediated RAFT polymerization. The whole fabrication process of the poly(DMAEMA) was followed by water contact angles, grazing angle-Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. Kinetic studies revealed a linear increase in poly(DMAEMA) film thickness with polymerization time, indicating that the chain growth from the surface was a controlled process. Characterization of the poly(DMAEMA) brushes, such as molecular weight and thickness determination, were measured by gel permeation chromatography, and ellipsometry, and the grafting density was estimated. The pH response of the poly(DMAEMA) brushes was further investigated and the results verified the “brush-like” to “mushroom-like” transition of the poly(DMAEMA) chains due to the reversible protonation/deprotonation upon changing the solution pH.     

Binary hairy nanoparticles: Recent progress in theory and simulations

Binary polymer brushes, including mixed homopolymer brushes and diblock copolymer brushes, are an attractive class of environmentally responsive nanostructured materials. Owing to microphase separation of the two chemically distinct components in the brush, multifaceted nanomaterials with functionalized and patterned surfaces can be obtained. This review summarizes recent progress on the theory and simulations related to binary polymer brushes grafted to flat, spherical, and cylindrical substrates, with a focus on patterned morphologies of multifaceted hairy nanoparticles, an intriguing class of hybrid nanostructured particles (e.g., nanospheres and nanorods). In particular, powerful field theory and particle-based simulations suitable for revealing novel structures on these patterned surfaces, including self-consistent field theory and dissipative particle dynamics simulations, are emphasized. The unsolved yet critical issues in this research field, such as dynamic response of binary polymer brushes to environmental stimuli and the hierarchical self-assembly of binary hairy nanoparticles, are briefly discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1583–1599     

Growth of ZIF-8 MOF Films with Tunable Porosity by using Poly (1-vinylimidazole) Brushes as 3D Primers

This work reports on a novel and versatile approach to control the structure of metal–organic framework (MOFs) films by using polymeric brushes as 3D primers, suitable for triggering heterogeneous MOF nucleation. As a proof-of-concept, this work explores the use of poly(1-vinylimidazole) brushes primer obtained via surface-initiated atom transfer radical polymerization (SI-ATRP) for the synthesis of Zn-based ZIF-8 MOF films. By modifying the grafting density of the brushes, smooth porous films were obtained featuring inherently hydrophobic microporosity arising from ZIF-8 structure, and an additional constructional interparticle mesoporosity, which can be employed for differential adsorption of targeted adsorbates. It was found that the grafting density modulates the constructional porosity of the films obtained; higher grafting densities result in more compact structures, while lower grafting density generates increasingly inhomogeneous films with a higher proportion of interparticle constructional porosity.     

硅表面分子刷图案化及生长DNA纳米管

结合“自上而下”和“自下而上”技术构建微纳米器件是目前纳米科学和技术领域追逐的目标之一。本文首先采用硅氢化反应在硅表面共价偶联引发聚合的活性基团,接着实施表面原子转移自由基聚合（ATRP）反应形成高分子刷poly（PEGMA）,采用“自上而下”的光刻技术在硅表面制备功能化的图案,最后利用“自下而上”的DNA自组装技术在图案部分原位生长DNA纳米管。上述组装过程通过多次透射反射红外光谱、凝胶电泳、透射电镜和扫描电镜进行了检测,证实了硅芯片表面定位生长DNA纳米管的可行性。     

刺激响应型聚合物刷的研究进展

本文综述了刺激响应型聚合物刷的研究进展,阐述了刺激响应型聚合物刷的分类、与基体表面的连接方式以及常规制备方法,介绍了离子强度、温度、pH值、光、溶剂等刺激响应型聚合物刷及其研究现状,并对相应的刺激响应机理进行了探讨。此外,本文还综述了多重刺激响应型聚合物刷的制备设计思路及其刺激响应特性,概述了聚合物刷在响应外界刺激后对基体的弯曲作用以及利用该作用进行可控三维自组装,并对刺激响应型聚合物刷的应用前景进行了展望。