This article reports a novel type of polymeric microspheres derived from a renewable biomass, eugenol, via a facile and effective suspension polymerization approach. On the basis of eugenol and methacryloyl chloride, we first synthesized and then structurally identified the monomer eugenyl methacrylate (E-MA). By using E-MA as the sole monomer and simultaneously as the cross-linking agent, we successfully prepared cross-linked polymeric microspheres through suspension polymerization in aqueous media with 2,2-azoisobutyronitrile (AIBN) as the initiator and poly(vinyl alcohol) (PVA) as the stabilizer. The resulting microspheres were obtained in high yield with diameters ranging 500−800 μm and exhibited remarkably large oil absorbency in a relatively high speed. The microspheres can be reused for at least five times with little change in maximum absorption. The preparative strategy for the polymeric microspheres can be taken as a versatile platform for preparing more functional polymeric microspheres, which are expected to find significant applications in environmental protection and other fields.

This article reports an original, versatile strategy to chirally functionalize graphene oxide (GO) with optically active helical-substituted polyacetylene. GO was first converted into alkynyl-GO containing polymerizable -C≡C moieties, which took part in the polymerization of another chiral acetylenic monomer, yielding the expected GO hybrid covalently grafted with chiral helical polyacetylene chains. Transmission electron microscopy, atomic force microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analyses verified the successful attachment of substituted polyacetylene chains on GO by covalent chemical bonding. Moreover, circular dichroism effects and UV-vis absorption demonstrated that the GO hybrid possessed fascinating optical activity. It also largely improved the dispersibility of GO in tetrahydrofuran. The GO-derived hybrid was further used as a chiral inducer toward enantioselective crystallization of alanine enantiomers. l-Alanine was preferably induced to crystallize, forming rodlike crystals.

Chiral molecularly imprinted polymer microspheres (MIPMs) reported so far are majorly limited to being constructed by using achiral polymer together with chiral template. The present contribution reports on a unique type of chiral MIPMs consisting of chirally helical substituted polyacetylene, which are prepared through suspension polymerization by using (a)chiral acetylenics as monomer and chiral Boc-d/l-proline as template. The resulting MIPMs after removing the template show optical activity that is derived from the chirally helical structures of substituted polyacetylene. The microspheres demonstrate enantio-differentiating ability in releasing the enantiopure templates. A complete release of the template provides the chiral MIPMs. Worthy to mention is that the two chiral sources (chirally helical conformation and chiral template configuration) work in a synergistic way, obviously increasing the MIPMs' enantiodiscrimination ability. The present study develops a strategy for preparing chiral MIPMs, which are expected to find significant applications in chiral separation, enantioselective release of chiral drugs, etc.

A new type of chiral porous hybrid particle was successfully prepared and applied in enantioselective release.

This article reports the first optically active macroporous materials constructed by helical substituted polyacetylene and prepared by a high internal phase emulsion (HIPE) technique. The macroporous (∼3 μm) materials were fabricated simply through polymerization of the continuous phase in HIPEs. The porous structures of the resulting materials can be adjusted by varying the fraction of the dispersed phase. The obtained materials were characterized by regular pore morphology, high porosity, and low density. Circular dichroism and UV−vis absorption spectra demonstrated that the substituted polyacetylene forming the materials adopted chirally helical conformations, which endowed the materials with considerable optical activity. The optically active porous materials were used as chiral inducers and efficiently induced enantioselective crystallization of threonine and alanine racemates. L-Threonine and L-alanine were preferably induced to form crystals from the respective racemic solutions. The prepared materials open a new type of functional chiral materials with potential applications in asymmetric catalysis, chiral resolution, etc. C hiral porous materials have recently constituted an active research area in materials science. 1 They combine two important concepts, "chirality" and "porosity", in one entity. This distinctive feature renders the materials with intriguing properties, e.g., optical activity, low density, and high specific surface area. They have found significant applications in asymmetric catalysis, 2 enantioselective release, 3 chiral resolution, 4 etc. Unfortunately, chiral porous materials reported to date were primarily limited to inorganics (silica 5 and metals 6 ) and organic−inorganic hybrids. 7 For chiral porous architectures solely constructed by organic polymers (chiral POPs), there have been only a few reports in the literature. 8−12 In particular notably, the chirality of such chiral POPs exclusively originated from configurational chirality (chiral small molecular units). Therefore, it still remains as a big challenge to construct chiral POPs by using synthetic helical polymers, in which the chirality is primarily contributed by conformational chirality (chiral helical structures).In the present study, we prepared chiral POPs consisting of optically active helical substituted polyacetylenes through a straightforward technique, i.e., the high internal phase emulsion (HIPE) polymerization approach. 13,14 A variety of achiral advanced materials have been fabricated through HIPE and exhibited potential applications such as biomaterials 15 and separation materials. 16 Chiral helical substituted polyacetylenes are remarkably attractive as typical synthetic helical polymers 17−19 that show interesting chiral amplification effects. 20−23 Nowadays new synthetic helical polymers have been continuously established. 24−27 Our group has constructed chiral porous (or hollow) nano-and microscaled particles by helical substituted polyacetylenes. 8,28−30 On the basis of the previous studies, we further e...