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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2020 · IF 3.99

Surface chain dependent arrangement and self-assembly of polyhedral oligomeric silsesquioxane for supramolecular gels

Huiwen He,Junnan Du,Hao Zheng,Meng Ma,Yanqin Shi,Zengliang Gao,Si Chen,Xu Wang

In this study, a series of amino acid grafted inorganic/organic hybrid POSS (Cn@POSS) were designed and synthesized. In order to investigate the surface chain dependent arrangement and self-assembly of POSS in supramolecular self-assembly, the molecular stacking, gelation abilities, thermal stability, morphology and mechanical properties of Cn@POSS gels were evaluated. From the obtained self-assembly mechanism of hybrid POSS, we discovered that the arrangement of hybrid POSS regularly stacking on a hexagonal columnar pathway and assembled into fibrous networks to form the gel in colloid self-assembly. The peripheral segments on the surface of hybrid POSS in a loosely extended state instead the collapse which provide a better position for the closely stacking and oriented aggregation of POSS. As the hierarchical assembled fibrous network, the length of surface chain ( L S ) induced bending of assembled nano-fibers helps the efficient gelation by entanglement of surface chains, but weaken the self-recovery of gels. In contrast, in bulk self-assembly, the stacking of hybrid POSS were obviously affected and perturbed by the length of surface chain, with the shorter L S the closer packing of POSS. This fundamental research helps the understanding of hierarchical self-assembly behaviours of nano-building block POSS in supramolecular gels and inspire the discovering on the applications of POSS based organic-inorganic hybrid molecules in functional soft materials.

研究领域: 材料科学 · 化学
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JOURNAL OF RAMAN SPECTROSCOPY · 2013 ·Vol. 44 ·期 8 ·1136-1143 · IF 2.679

SERS study on surface chain geometry of atactic poly (methyl methacrylate) film and nanosphere

Chenglong Hu,Shaoyun Chen,Weihong Zhang,Fangyan Xie,Jian Chen,Xudong Chen

The surface chain geometry of atactic poly (methyl methacrylate) (a-PMMA) film and nanosphere (NS) was revealed by surface-enhanced Raman scattering (SERS) spectra. The Ag nanoparticles and nanoplates were prepared by electrochemical deposition and chemical synthesis for SERS substrates. The experimental results suggested that the molecular chain axis of a-PMMA film adopted a trans-conformation on bonding to Ag surface ascribed to the short-range chemical (CHEM) effect according to the SERS selection rules. However, for the well-coated monolayer of a-PMMA NSs, the α-CH 3 in polymer chains stood vertically to the Ag surface due to the giant local electromagnetic effect, then the chain conformation presented in the interface between a-PMMA NSs and Ag metal was adopted the opposite orientation compared with a-PMMA film. The Raman enhancement of the Ag nanoparticles was more prominent than that of the Ag nanoplates due to the free energies of face-centered cubic crystal faces in nanoparticles, but the single crystals with (111) plane of Ag nanoplates could improve the stability of SERS signals when the annealed temperature was above T g of a-PMMA NSs. The present work can provide some useful information of surface chain geometry and conformation of NSs for designing various materials with well-defined structure via a-PMMA NSs template. Copyright © 2013 John Wiley & Sons, Ltd.

研究领域: 材料科学 · 光谱学
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