Division of Chemical Sciences, Lawrence Berkeley National Laboratory, and Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
Nat Chem. 2013 Feb;5(2):100-3. doi: 10.1038/nchem.1531. Epub 2013 Jan 6.
The ability of supramolecular host-guest complexes to catalyse organic reactions collaboratively with an enzyme is an important goal in the research and discovery of synthetic enzyme mimics. Herein we present a variety of catalytic tandem reactions that employ esterases, lipases or alcohol dehydrogenases and gold(I) or ruthenium(II) complexes encapsulated in a Ga(4)L(6) tetrahedral supramolecular cluster. The host-guest complexes are tolerated well by the enzymes and, in the case of the gold(I) host-guest complex, show improved reactivity relative to the free cationic guest. We propose that supramolecular encapsulation of organometallic complexes prevents their diffusion into the bulk solution, where they can bind amino-acid residues on the proteins and potentially compromise their activity. Our observations underline the advantages of the supramolecular approach and suggest that encapsulation of reactive complexes may provide a general strategy for carrying out classic organic reactions in the presence of biocatalysts.
超分子主客体配合物与酶协同催化有机反应是合成酶模拟物研究和发现的重要目标。在此，我们展示了各种催化串联反应，这些反应采用酯酶、脂肪酶或醇脱氢酶以及包封在 Ga(4)L(6)四面体超分子簇中的金（I）或钌（II）配合物。这些主体-客体配合物能够很好地被酶耐受，并且在金（I）主体-客体配合物的情况下，与游离的阳离子客体相比，显示出提高的反应性。我们提出，将金属有机配合物超分子封装可以防止它们扩散到本体溶液中，在本体溶液中，它们可以与蛋白质上的氨基酸残基结合，并可能损害其活性。我们的观察结果强调了超分子方法的优势，并表明封装反应性配合物可能为在生物催化剂存在下进行经典有机反应提供一种通用策略。
