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81.
Eyal Tzur Anna Szadkowska Amos Ben‐Asuly Dr. Anna Makal Israel Goldberg Prof. Krzysztof Woźniak Prof. Karol Grela Prof. N. Gabriel Lemcoff Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(29):8726-8737
A short overview on the structural design of the Hoveyda–Grubbs‐type ruthenium initiators chelated through oxygen, nitrogen or sulfur atoms is presented. Our aim was to compare and contrast O‐, N‐ and S‐chelated ruthenium complexes to better understand the impact of electron‐withdrawing and ‐donating substituents on the geometry and activity of the ruthenium complexes and to gain further insight into the trans–cis isomerisation process of the S‐chelated complexes. To evaluate the different effects of chelating heteroatoms and to probe electronic effects on sulfur‐ and nitrogen‐chelated latent catalysts, we synthesised a series of novel complexes. These catalysts were compared against two well‐known oxygen‐chelated initiators and a sulfoxide‐chelated complex. The structures of the new complexes have been determined by single‐crystal X‐ray diffraction and analysed to search for correlations between the structural features and activity. The replacement of the oxygen‐chelating atom by a sulfur or nitrogen atom resulted in catalysts that were inert at room temperature for typical ring‐closing metathesis (RCM) and cross‐metathesis reactions and showed catalytic activity only at higher temperatures. Furthermore, one nitrogen‐chelated initiator demonstrated thermo‐switchable behaviour in RCM reactions, similar to its sulfur‐chelated counterparts. 相似文献
82.
83.
Ben-Ari E Leitus G Shimon LJ Milstein D 《Journal of the American Chemical Society》2006,128(48):15390-15391
Unusual reactions are reported, in which the aromatic PNP ligand (PNP = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine) acts in concert with the metal in the activation of H2 and benzene, via facile aromatization/dearomatization processes of the ligand. A new, dearomatized electron-rich (PNP*)Ir(I) complex 2 (PNP* = deprotonated PNP) activates benzene to form the aromatic (PNP)Ir(I)Ph 4, which upon treatment with CO undergoes a surprising oxidation process to form (PNP*)Ir(III)(H)CO 6, involving proton migration from the ligand "arm" to the metal, with concomitant dearomatization. 4 undergoes stereoselective activation of H2 to exclusively form the trans-dihydride 7, rather than the expected cis-dihydride complex. Our evidence, including D-labeling, suggests the possibility that the Ir(I)-Ph complex is transformed to the dearomatized Ir(III)(Ph)(H) (independently prepared at low temperature), which may be the actual intermediate undergoing H2 activation. 相似文献
84.
Yuwei Hu Fuan Wang Chun‐Hua Lu Julia Girsh Eyal Golub Prof. Itamar Willner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(49):16203-16209
Mimicking cellular transformations and signal transduction pathways by means of biocatalytic cascades proceeding in organized media is a scientific challenge. We describe two DNA machines that enable the “ON/OFF” switchable activation and deactivation of three‐component biocatalytic cascades. One system consists of a reconfigurable DNA tweezers‐type structure, whereas in the second system the catalytic cascade proceeds on a switchable DNA clamp scaffold. The three‐component catalytic cascades consist of β‐galactosidase (β‐Gal), glucose oxidase (GOx), and the K+‐ion‐stabilized hemin‐G‐quadruplex horseradish peroxidase (HRP)‐mimicking DNAzyme. The hemin‐G‐quadruplex‐bridged closed structure of the tweezers or clamp allows the biocatalytic cascades to operate (switched “ON′′), whereas separation of the hemin‐G‐quadruplex by means of 18‐crown‐6‐ether opens the tweezers/clamp structures, thus blocking the catalytic cascade (switched ”OFF“). This study is complemented by two‐component, switchable biocatalytic cascades composed of GOx and hemin‐G‐quadruplex assembled on hairpin‐bridged DNA tweezers or clamp nanostructures. 相似文献
85.
Cerium(IV) ammonium nitrate (CAN)-catalyzed oxidation of alkyl aromatics with potassium bromate affords aldehydes, ketones acids or alcohols in high yields. 相似文献
86.
Alexander G. Shtukenberg Ran Drori Elena V. Sturm Netta Vidavsky Asaf Haddad Jason Zheng Lara A. Estroff Haim Weissman Sharon G. Wolf Eyal Shimoni Chao Li Noalle Fellah Efi Efrati Bart Kahr 《Angewandte Chemie (International ed. in English)》2020,59(34):14593-14601
The growth of spontaneously twisted crystals is a common but poorly understood phenomenon. An analysis of the formation of twisted crystals of a metastable benzamide polymorph (form II ) crystallizing from highly supersaturated aqueous and ethanol solutions is given here. Benzamide, the first polymorphic molecular crystal reported (1832), would have been the first helicoidal crystal observed had the original authors undertaken an analysis by light microscopy. Polymorphism and twisting frequently concur as they are both associated with high thermodynamic driving forces for crystallization. Optical and electron microscopies as well as electron and powder X‐ray diffraction reveal a complex lamellar structure of benzamide form II needle‐like crystals. The internal stress produced by the overgrowth of lamellae is shown to be able to create a twist moment that is responsible for the observed non‐classical morphologies. 相似文献
87.
Dr. Alexander G. Shtukenberg Prof. Ran Drori Dr. Elena V. Sturm Dr. Netta Vidavsky Asaf Haddad Jason Zheng Prof. Lara A. Estroff Dr. Haim Weissman Dr. Sharon G. Wolf Dr. Eyal Shimoni Chao Li Noalle Fellah Prof. Efi Efrati Prof. Bart Kahr 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14701-14709
The growth of spontaneously twisted crystals is a common but poorly understood phenomenon. An analysis of the formation of twisted crystals of a metastable benzamide polymorph (form II ) crystallizing from highly supersaturated aqueous and ethanol solutions is given here. Benzamide, the first polymorphic molecular crystal reported (1832), would have been the first helicoidal crystal observed had the original authors undertaken an analysis by light microscopy. Polymorphism and twisting frequently concur as they are both associated with high thermodynamic driving forces for crystallization. Optical and electron microscopies as well as electron and powder X-ray diffraction reveal a complex lamellar structure of benzamide form II needle-like crystals. The internal stress produced by the overgrowth of lamellae is shown to be able to create a twist moment that is responsible for the observed non-classical morphologies. 相似文献
88.
We exploit nonlinearity in NbN superconducting stripline resonators, which originates from local thermal instability, for studying stochastic resonance. As the resonators are driven into instability, small amplitude modulation (AM) signals are amplified with the aid of injected white noise. Simulation results based on the equations of motion for the system yield a good agreement with the experimental data both in the frequency and time domains. 相似文献
89.
90.
The degenerate crossing number ${\text{ cr}^{*}}(G)$ of a graph $G$ is the minimum number of crossing points of edges in any drawing of $G$ as a simple topological graph in the plane. This notion was introduced by Pach and Tóth who showed that for a graph $G$ with $n$ vertices and $e \ge 4n$ edges ${\text{ cr}^{*}}(G)=\Omega \big (e^4 / n^4\big )$ . In this paper we completely resolve the main open question about degenerate crossing numbers and show that ${\text{ cr}^{*}}(G)=\Omega \big (e^3 / n^2 \big )$ , provided that $e \ge 4n$ . This bound is best possible (apart for the multiplicative constant) as it matches the tight lower bound for the standard crossing number of a graph. 相似文献