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脂相作为新型纳米反应支架用于有机催化剂:受限水中的非均相催化不对称Aldol 反应。

Lipidic Mesophases as Novel Nanoreactor Scaffolds for Organocatalysts: Heterogeneously Catalyzed Asymmetric Aldol Reactions in Confined Water.

机构信息

Department of Chemistry, University of Zurich , Winterthurerstrasse 190, 8057 Zürich, Switzerland.

Department of Health Science & Technology, ETH Zurich , Schmelzbergstrasse 9, 8092 Zürich, Switzerland.

出版信息

ACS Appl Mater Interfaces. 2018 Feb 7;10(5):5114-5124. doi: 10.1021/acsami.7b19740. Epub 2018 Jan 19.

DOI:10.1021/acsami.7b19740
PMID:29313658
Abstract

The unique molecular architecture of lipidic cubic phases (LCPs) and their cubosome dispersions comprise a well-defined, curved bilayer that spans the entire three-dimensional (3-D) material space, encompassing a network of two periodic, curved, and nonintersecting 3-D aqueous channels. The ensuing large lipid/water interfacial area makes these biomaterials an interesting matrix for the lateral immobilization of organocatalysts to catalyze organic reactions in confined water. Herein, we report for the first time the design, synthesis, assembly, and characterization of catalytically active LCPs and cubosomes and demonstrate their applicability as self-assembled, biomimetic, and recyclable nanoreactor scaffolds. Small-angle X-ray scattering, cryo-transmission electron microscopy, and dynamic light scattering were applied for the characterization of the mesophases. These mesophases can be recycled and enable efficient catalytic activity as well as modulation of the diastereo- and enantioselectivity for the aldol reaction of several benzaldehyde derivatives and cyclohexanone in water.

摘要

脂质立方相 (LCP) 的独特分子结构及其立方体分散体包含一个明确的、弯曲的双层结构,跨越整个三维 (3-D) 材料空间,包含一个由两个周期性、弯曲且不相交的三维含水通道组成的网络。由此产生的大的脂质/水界面使这些生物材料成为有机催化剂横向固定化以在受限水中催化有机反应的有趣基质。在这里,我们首次设计、合成、组装和表征了催化活性的 LCP 和立方体,并证明了它们作为自组装、仿生和可回收纳米反应器支架的适用性。小角 X 射线散射、低温传输电子显微镜和动态光散射用于介相的表征。这些中间相可以回收,并具有高效的催化活性以及调节几种苯甲醛衍生物和环己酮在水中的羟醛反应的非对映选择性和对映选择性。

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