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排序方式: 共有1111条查询结果,搜索用时 15 毫秒
1.
Jrme Canivet Elise Bernoud Jonathan Bonnefoy Alexandre Legrand Tanya K. Todorova Elsje Alessandra Quadrelli Caroline Mellot-Draznieks 《Chemical science》2020,11(33):8800
Understanding and controlling molecular recognition mechanisms at a chiral solid interface is a continuously addressed challenge in heterogeneous catalysis. Here, the molecular recognition of a chiral peptide-functionalized metal–organic framework (MOF) catalyst towards a pro-chiral substrate is evaluated experimentally and in silico. The MIL-101 metal–organic framework is used as a macroligand for hosting a Noyori-type chiral ruthenium molecular catalyst, namely (benzene)Ru@MIL-101-NH-Gly-Pro. Its catalytic perfomance toward the asymmetric transfer hydrogenation (ATH) of acetophenone into R- and S-phenylethanol are assessed. The excellent match between the experimentally obtained enantiomeric excesses and the computational outcomes provides a robust atomic-level rationale for the observed product selectivities. The unprecedented role of the MOF in confining the molecular Ru-catalyst and in determining the access of the prochiral substrate to the active site is revealed in terms of highly face-specific host–guest interactions. The predicted surface-specific face differentiation of the prochiral substrate is experimentally corroborated since a three-fold increase in enantiomeric excess is obtained with the heterogeneous MOF-based catalyst when compared to its homogeneous molecular counterpart.Understanding and controlling molecular recognition mechanisms at a chiral solid interface has been addressed in metal–organic framework catalysts for the asymmetric transfer hydrogenation reaction. 相似文献
2.
Natalie Hell Peter Beiersdorfer Gregory V. Brown Megan E. Eckart Richard L. Kelley Caroline A. Kilbourne Maurice A. Leutenegger Thomas E. Lockard F. Scott Porter Jörn Wilms 《X射线光谱测定》2020,49(1):218-233
X-ray astronomy and ground-based atomic physics have a long history of fruitful collaboration: Sound understanding of the underlying atomic physics is the key to reliable interpretation of the spectra from celestial sources; conversely, astronomical spectra have been used to benchmark and advance atomic physics. This interplay is about to become even more important as we enter a new era of high-resolution X-ray astrophysics with large effective collection area. Although high-resolution observations with the gratings on the Chandra and XMM-Newton observatories continue to drive new science, upcoming planned and proposed missions will open up new discovery space in the near future that is currently challenging to access: high-resolution spectroscopy on extended sources, in the Fe K band, and on short time scales. This review summarizes open questions in these areas and the design parameters for the Hitomi, XRISM, Athena, and Arcus observatories. The expected high quality of spectra taken with these observatories puts new constraints on the accuracy of atomic reference data required to take full advantage of the diagnostic potential of these spectra. 相似文献
3.
Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light 下载免费PDF全文
Dr. Jiale Wang Dr. Fabiane J. Trindade Caroline B. de Aquino Joana C. Pieretti Prof. Dr. Sergio H. Domingues Prof. Dr. Romulo A. Ando Prof. Dr. Pedro H. C. Camargo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9889-9894
Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl4?(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O2 through the transfer of SPR‐excited hot electrons to O2 molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O2 molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O2 charge‐transfer process. 相似文献
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Vieira Renata Leia Demario Gaglieri Caroline de Oliveira Cristina Soltovski Ferreira Laura Teófilo Schnitzler Egon Bannach Gilbert 《Journal of Thermal Analysis and Calorimetry》2021,144(3):689-697
Journal of Thermal Analysis and Calorimetry - Buckwheat starch is an alternative source to supply the high global demand for starch. The properties of starch can be modified through chemical and... 相似文献
7.
Dr. Jagadeesh Yerri Dr. José Dias Dr. Mallikajurna Reddy Nimmakayala Franck Razafindrainibe Charlotte Courageux Anne-Julie Gastellier Johanne Jegoux Dr. Caroline Coisne Dr. Christophe Landry Dr. Fabien Gosselet Johan Hachani Dr. Jean-François Goossens Prof. Marie-Pierre Dehouck Dr. Florian Nachon Dr. Rachid Baati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):15035-15044
Novel 6-alkyl- and 6-alkenyl-3-fluoro-2-pyridinaldoximes have been synthesised by using a mild and efficient chemoselective hydrogenation of 6-alkynyl-3-fluoro-2-pyridinaldoxime scaffolds, without altering the reducible, unprotected, sensitive oxime functionality and the C−F bond. These novel 6-alkyl-3-fluoro-2-pyridinaldoximes may find medicinal application as antidotes to organophosphate poisoning. Indeed, one low-molecular-weight compound exhibited increased affinity for sarin-inhibited acetylcholinesterase (hAChE) and greater reactivation efficiency or resurrection for sarin-inhibited hAChE, compared with those of 2-pyridinaldoxime (2-PAM) and 1-({[4-(aminocarbonyl)pyridinio]methoxy}methyl)-2-[(hydroxyimino)methyl]pyridinium chloride (HI-6), two pyridinium salts currently used as antidote by several countries. In addition, the uncharged 3-fluorinated bifunctional hybrid showed increased in vitro blood–brain barrier permeability compared with those of 2-PAM, HI-6 and obidoxime. These promising features of novel low-molecular-weight alkylfluoropyridinaldoxime open up a new era for the design, synthesis and discovery of central non-quaternary broad spectrum reactivators for organophosphate-inhibited cholinesterases. 相似文献
8.
Prof. Dr. Shina Caroline Lynn Kamerlin Prof. Dr. Pernilla Wittung-Stafshede 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(38):8319-8323
Despite slow ongoing progress in increasing the representation of women in academia, women remain significantly under-represented at senior levels, in particular in the natural sciences and engineering. Not infrequently, this is downplayed by bringing forth arguments such as inherent biological differences between genders, that current policies are adequate to address the issue, or by deflecting this as being “not my problem” among other examples. In this piece we present scientific evidence that counters these claims, as well as a best-practice example, Genie, from Chalmers University of Technology, where one of the authors is currently employed. We also highlight particular challenges caused by the current COVID-19 pandemic. Finally, we conclude by proposing some possible solutions to the situation and emphasize that we need to all do our part, to ensure that the next generation of academics experience a more diverse, inclusive, and equitable working environment. 相似文献
9.
Dr. Sarah Lopez Dr. Caroline Marchi-Delapierre Dr. Christine Cavazza Dr. Stéphane Ménage 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16633-16638
Performing a heterogeneous catalysis with proteins is still a challenge. Herein, we demonstrate the importance of cross-linked crystals for sulfoxide oxidation by an artificial enzyme. The biohybrid consists of the insertion of an iron complex into a NikA protein crystal. The heterogeneous catalysts displays a better efficiency-with higher reaction kinetics, a better stability and expand the substrate scope compared to its solution counterpart. Designing crystalline artificial enzymes represents a good alternative to soluble or supported enzymes for the future of synthetic biology. 相似文献
10.
The chalcogenido indates K6In2Q6 (Q = S, Se, Te) were synthesized from melts of the pure elements at a maximum temperature of 700 °C. All three potassium salts contain dinuclear units [In2Q6]6– of two edge-sharing [InQ4] tetrahedra. The sulfido and the selenido indate are isotypic and crystallize in the K6Mn2O6-type structure [monoclinic, space group P21/c, a = 784.32(9)/809.32(3), b = 1274.58(14)/1322.37(4), c = 836.48(9)/870.53(3) pm, β = 97.900(2)/97.5877(8)°, Z = 2, R1 = 0.0123/0.0109; for Q = S/Se]. The tellurido indate K6In2Te6 crystallizes in a new orthorhombic structure type [space group Pnma, a = 1793.70(12), b = 1491.55(11), c = 837.40(6) pm, Z = 4, R1 = 0.0157]. In this structure, the telluride anions form a hexagonal close packing, in which K+ cations occupy all octahedral voids; the In3+ ions take 1/6 (but always adjacent) tetrahedral voids. This structure-chemical relation to the h.c.p. packing, which is similarly found for most of the sodium dimetallates (e.g. Na6Fe2S6), is substantiated by a full crystallographic group-subgroup tree. The crystal chemistry of the new indates is discussed and compared with that of alkali chalcogenido metallates(III) of Fe, Al and Ga containing [M2Q6]6– dimers, which overall form as many as ten different structure types. DFT band structure calculations of the three title compounds exhibit bandgaps, which continuously decrease from the S to the Te compound and which are also in accordance with the pale yellow (S), bright yellow (Se) and red-brown (Te) color of the compounds. The chemical bonding in the salts and within the metallate anion is discussed on the basis of the partial DOS and a Bader analysis of the calculated electron density. 相似文献