Enzyme-Inspired Assembly: Incorporating Multivariate Interactions to Optimize the Host–Guest Configuration for High-Speed Enantioselective Catalysis

Abstract

To achieve a rapid asymmetry conversion, the substrate objects suffer from accelerated kinetic velocity and random rotation at the cost of selectivity. Inspired by natural enzymes, optimizing the host–guest configuration will realize the high-performance enantioselective conversion of chemical reactions. Herein, multivariate binding interactions were introduced into the 1D channel of a chiral catalyst to simulate the enzymatic action. An imidazolium group was used to electrophilically activate the CO unit of a ketone substrate, and the counterion binds the hydrogen donor isopropanol. This binding effect around the catalytic center produces strong stereo-induction, resulting in high conversion (99.5% yield) and enantioselectivity (99.5% ee) for the asymmetric hydrogenation of biomass-derived acetophenone. In addition, the turnover frequency of the resulting catalyst (5160 h–1 TOF) is more than 58 times that of a homogeneous Ru-TsDPEN catalyst (88 h–1 TOF) under the same condition, which corresponds to the best performance reported till date among all existing catalysts for the considered reaction.

Modifying Enzymatic Substrate Binding within a Metal–Organic Capsule for Supramolecular Catalysis

“…The NH group of phenylhydrazine forms a hydrogen bond with an amide O atom in H1 (N···O separation of 3.0 Å and N–H···O angle of 175.6°), which is important for the stabilization of the substrate-bonded clathration intermediate (Figure S8). Furthermore, the formation of the host–guest complex enlarged the Co–O bonds, suggesting that the capsule shows the potential to adapt its structure with the recognized substrate, forming stable and spatially allowed complexation species. , …”

“…The NH group of phenylhydrazine forms a hydrogen S8). 46 Furthermore, the formation of the host−guest complex enlarged the Co−O bonds, suggesting that the capsule shows the potential to adapt its structure with the recognized substrate, 47 forming stable and spatially allowed complexation species. 48,49 To deeply explore the mechanism of the new approach, a reported analogue, 50 H2, Co 6 (H 9 L 4 2 )•(ClO 4 ) 9 , was used as a reference host, where H 3 L 2 = tri(isoquinolin-3-ylmethylene) benzene-1,3,5-trihydrazide.…”

Research progress of multi-enzyme complexes based on the design of scaffold protein

“…Compared with other co-localization techniques, protein scaffolds have some advantages. First, the minimum distance between the active site on the protein scaffold allows for effective substrate channels, because metabolic intermediates are more likely to undergo sequential reaction steps rather than diffusion (Deng et al 2020 ). When expressed within cells, the protein scaffold maintains a high local concentration, while the total cell level remains relatively low.…”

Branched-Chain-Induced Host–Guest Assembly in Covalent-Organic Frameworks for Efficient Separation of No-Carrier-Added 177Lu

“…Hydrogen bonds have been further demonstrated to have significant impacts on the structure and property of the overall skeleton of nitrile-linked COFs recently. , Additionally, electron-donating motifs at the side chains can weaken polarization effects and enhance interlayer interactions of COFs, also leading to much more stable frameworks . Second, different from other porous solid-state materials, COFs featuring with dynamic covalent bonds and highly available modifiability are versatile to accommodate gaseous compounds, small organic molecules, inorganic clusters, etc., resulting in host–guest complexes with feasibility in the fields of catalysis, biomedicines, and sensor. − Third, noncovalent bonds with self-healing availability and dynamic reversibility enable the corresponding functional COFs to adapt to the strict conditions in radionuclide separation. The only concern appears as to whether COFs with an ordered porous structure can provide suitable nanoconfinement space for growing stable functional complexes in real application scenarios.…”