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151.
Yasmine S. Zubi Bingqing Liu Yifan Gu Dipankar Sahoo Jared C. Lewis 《Chemical science》2022,13(5):1459
Visible light photocatalysis enables a broad range of organic transformations that proceed via single electron or energy transfer. Metal polypyridyl complexes are among the most commonly employed visible light photocatalysts. The photophysical properties of these complexes have been extensively studied and can be tuned by modifying the substituents on the pyridine ligands. On the other hand, ligand modifications that enable substrate binding to control reaction selectivity remain rare. Given the exquisite control that enzymes exert over electron and energy transfer processes in nature, we envisioned that artificial metalloenzymes (ArMs) created by incorporating Ru(ii) polypyridyl complexes into a suitable protein scaffold could provide a means to control photocatalyst properties. This study describes approaches to create covalent and non-covalent ArMs from a variety of Ru(ii) polypyridyl cofactors and a prolyl oligopeptidase scaffold. A panel of ArMs with enhanced photophysical properties were engineered, and the nature of the scaffold/cofactor interactions in these systems was investigated. These ArMs provided higher yields and rates than Ru(Bpy)32+ for the reductive cyclization of dienones and the [2 + 2] photocycloaddition between C-cinnamoyl imidazole and 4-methoxystyrene, suggesting that protein scaffolds could provide a means to improve the efficiency of visible light photocatalysts.Artificial metalloenzyme visible light photocatalysts possess enhanced optical properties and are competent towards single electron and energy transfer organic transformations. 相似文献
152.
William N. Setzer Shahrara Afshar Norman L. Burns Lucille A. Ferrante Amy M. Hester Edward J. Meehan Gregory J. Grant Saju M. Isaac Christopher P. Laudeman Charles M. Lewis Donald G. VanDerveer 《Heteroatom Chemistry》1990,1(5):375-387
The mesocyclic trithioethers, 1,4,7-trithiacyclodecane, 1,4,7-trithiacycloundecane, 1,4,8-trithiacycloundecane, and 1,5,9-trithiacyclododecane; the mesocyclic trithioether ketones, 1,4,7-trithiacyclodecan-9-one; 1,4,8-trithiacycloundecan-6-one, and 1,5,9-trithiacyclododecan-3-one; and the mesocyclic trithioether alcohols, 1,4,7-trithiacyclodecan-9-ol, 1,4,8-trithiacycloundecan-6-ol, and 1,5,9-trithiacyclododecan-3-ol, have been synthesized using the cesium dithiolate technique. In some cases, the corresponding macrocyclic hexathioether was isolated from the reaction mixture in addition to the mesocyclic trithioether; 1,4,7,11,14,17-hexathiacycloeicosane, 1,4,7,11,14,17-hexathiacycloeicosan-9,19-dione, 1,4,7,12,15,18-hexathiacyclodocosane, and 1,5,9,13,17,21-hexathiacyclotetracosane. Single-crystal X-ray structures have been determined for 1,5,9-trithiacyclododecan-3-ol and 1,4,7,12,15,18-hexathiacyclodocosane. For 1,5,9-trithiacyclododecane-3-ol, the compound crystallizes in the monoclinic space group, C2/c, with a = 10.5926( 9 ) Å, b = 15.582(2) Å, c = 13.6015(8) Å, β = 98.186(6)0, Z = 8, and R = 0.038. The macrocycle, 1,4,7,12,15,18-hexathiacyclodocosane, crystallizes in the orthorhombic space group, Pbca, with a = 21.406(5) Å, b = 9.810(2) Å, c = 10.225(2) Å, Z = 4, and R = 0.020. 相似文献
153.
Highly Active Electrocatalysis of the Hydrogen Evolution Reaction by Cobalt Phosphide Nanoparticles
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Eric J. Popczun Carlos G. Read Christopher W. Roske Prof. Nathan S. Lewis Prof. Raymond E. Schaak 《Angewandte Chemie (International ed. in English)》2014,53(21):5427-5430
Nanoparticles of cobalt phosphide, CoP, have been prepared and evaluated as electrocatalysts for the hydrogen evolution reaction (HER) under strongly acidic conditions (0.50 M H2SO4, pH 0.3). Uniform, multi‐faceted CoP nanoparticles were synthesized by reacting Co nanoparticles with trioctylphosphine. Electrodes comprised of CoP nanoparticles on a Ti support (2 mg cm?2 mass loading) produced a cathodic current density of 20 mA cm?2 at an overpotential of ?85 mV. The CoP/Ti electrodes were stable over 24 h of sustained hydrogen production in 0.50 M H2SO4. The activity was essentially unchanged after 400 cyclic voltammetric sweeps, suggesting long‐term viability under operating conditions. CoP is therefore amongst the most active, acid‐stable, earth‐abundant HER electrocatalysts reported to date. 相似文献
154.
Phase pure AlPO4 with the AlPO4-18 (AEI) structure was synthesised using N,N-diisopropylethyla-mine as a template. Using a combination of X-ray powder diffraction and computational methods, the location and orientation of the N,N-diisopropylethylamine molecules inside the cages of the AEI structure were determined. Thermogravimetric analysis confirmed that the number of template molecules per unit cell was consistent with the diffraction study. We unequivocally show that only one template molecule is present in each cage of the crystalline AEI material. Our work demon-strates that a combined approach enables accurate structure resolution of such complex materials. 相似文献
155.
Gas hydrate single-crystal structure analyses 总被引:4,自引:0,他引:4
Kirchner MT Boese R Billups WE Norman LR 《Journal of the American Chemical Society》2004,126(30):9407-9412
The first single-crystal diffraction studies on methane, propane, methane/propane, and adamantane gas hydrates SI, SII, and SH have been performed. To circumvent the problem of very slow crystal growth, a novel technique of in situ cocrystallization of gases and liquids resulting in oligocrystalline material in a capillary has been developed. With special data treatment, termed oligo diffractometry, structural data of the gas hydrates of methane, acetylene, propane, a propane/ethanol/methane-mixture and an adamantane/methane-mixture were obtained. Cell parameters are in accord with reported values. Host network and guest are subject to extensive disorder, reducing the reliability of structural information. It was found that most cages are fully occupied by a guest molecule with the exception of the dodecahedral cage in the acetylene hydrate which is only filled to 60%. For adamantane in the icosahedral cage a disordered model is proposed. 相似文献
156.
Transport in Porous Media - We develop an analytical model describing the flow of NaCl– $$\hbox {H}_2\hbox {O}$$ in a saturated porous medium adjacent to a hot vertical wall and apply the... 相似文献
157.
Simon R. Drake Brian F. G. Johnson Jack Lewis 《Journal of organometallic chemistry》1988,340(3):C31-C36
The heteronuclear clusters [Os10C(CO)24(MPR3nm− (n = 1, m = 1; 2: M = Au; 3: M = Ag; 4: M = Cu; 5 n = 2, m = 0, M = Ag) have been prepared. These clusters undergo molecular rearrangements in solution, and two isomeric forms of 2, 3, 4, 5 and 6 have been identified. This interconversion is thought to involve a cap [lrarr2] edge bridge [lrarr2] cap pathway. 相似文献
158.
For a group G,we produce upper and lower bounds for the sum of the entries of the Brauer character table of G and the projective indecomposable character table of G.When G is a π-separable group,we show that the sum of the entries in the table of Isaacs' partial characters is a real number,and we obtain upper and lower bounds for this sum. 相似文献
159.
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