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POLYMER JOURNAL · 2023 ·Vol. 55 ·期 3 ·203-211 · IF 2.8

Novel synthesis of porous one-handed helical poly(substituted phenylacetylene) bearing betulin derivatives pendant groups

Shi Zhichun,Wen Jiaxiang,Zhao Yingnan,Wang Jianjun,Li Jun,Zhao Ming,Teraguchi Masahiro,Aoki Toshiki,Kaneko Takashi

A novel substituted phenylacetylene with a pendant betulin derivative group was designed and synthesized successfully, and the chemical structure of the monomer was confirmed by nuclear magnetic resonance spectroscopy (NMR, 1 H, 13 C), high-resolution mass spectrometry (HRMS) and Fourier transform infrared spectroscopy (FTIR). The obtained monomer was further polymerized in an achiral [Rh(nbd)Cl] 2 /triethylamine (TEA) catalytic system, and the resulting polymer exhibited a strong Cotton effect at the main-chain absorption regions in the circular dichroism (CD) spectra. This one-handed helical backbone was induced by the chiral source on the side chain and maintained by the rigid betulin derivative pendant flats. Furthermore, the rigid betulin derivatives also contributed to the porous morphology and perfect thermal stability of the polymer. This study will provide a new method for preparing porous chiral polymers as efficient separation materials to solve practical issues.

研究领域: 材料化学 · 有机合成 · 高分子科学
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RSC Advances · 2015 ·Vol. 5 ·期 107 ·88548-88555 · IF 3.84

Novel design, facile synthesis and low infrared emissivity properties of single-handed helical polysilanes

Muyang Zhang,Yuming Zhou,Man He,Tao Zhang,Xiaohai Bu

The novel single-handed helical polysilanes (HPS), poly[di-n-hexylsilane-co-(methoxycarbonyl ethyl propyl ether)methylsilane] were synthesized by the Wurtz-type coupling of the chiral functional monomer, dichloro(methoxycarbonyl ethyl propyl ether)methylsilane (DCMMS). The monomer was prepared by the hydrosilylation reaction of methyl (S)-2-(allyloxy)propanoate. The chemical structure of HPS was confirmed by 1H, 13C and 29Si nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-Vis) and circular dichroism (CD). The weight distributions and crystallinity of the polysilanes were demonstrated by gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and polarized light microscopy (POM), respectively. The single-handed helical characterization and polymerization degree of the new-typed polysilanes could be controlled by the co-monomers of DCMMS and di-n-hexyldichlorosilane (DCDHS), respectively. Furthermore, the infrared emissivity values (0.598 at 8–14 μm) of HPS were investigated by an Infrared Emissometer.

研究领域: 材料化学 · 高分子科学
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2017 ·Vol. 55 ·期 12 ·2092-2103 · IF 2.952

Grafting polymerization of single-handed helical poly(phenyl isocyanide)s on graphene oxide and their application in enantioselective separation

Yi Xiao,Hui-Qing Wang,Hao Zhang,Zhi-Qiang Jiang,Ya-Qi Wang,Hai Li,Jun Yin,Yuan-Yuan Zhu,Zong-Quan Wu

We herein report a “grafting from” strategy to immobilize optically active helical poly(phenyl isocyanide)s onto graphene oxide (GO) nanosheets. After covalently bounding alkyne-Pd(II) initiator onto GO nanosheets, the designed GO/polymer composites P1 @GO and P1 - b - P2 @GO featuring single-handed helical poly(phenyl isocyanide)s growing from GO nanosheets were prepared by sequential addition of the chiral and achiral isocyanide monomers. Post-synthetic hydrolysis rendered P1 - b - P3 @GO to improve the hydrophilicity. The successful covalent bonding of poly(phenyl isocyanide)s chains onto GO nanosheets was certified by several cross evidences including scan emission microscopy, atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Circular dichroism spectra proved that the chiral information was introduced through the grafted single-handed helical polymer chains successfully. In addition, the resulting GO/polymer composites were explored as a chiral additive to induce enantioselective crystallization of racemic organic molecules. Preferential formation of rod-like L -alanine crystals was induced by composites bearing right-handed helical poly(phenyl isocyanide)s. The enantiomeric excess value of the induced crystals reached 76%, displaying the potential in future applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2092–2103

研究领域: 材料科学 · 高分子化学 · 手性化学
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