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771.
772.
In this article we present recent developments in (3+2) cycloadditions with special emphasis on 1,3-dipolar reactions involving azomethine ylides and alkenes possessing electron withdrawing groups. It is found that there is not a general mechanism for these reactions since both concerted aromatic [(π)4(s)+(π)2(s)] mechanisms and stepwise processes involving zwitterionic intermediates can be found. These computational models can be extended to analyse the role of chiral catalysts in these reactions in order to understand the nature of the catalytic cycle and the origins of chiral induction. 相似文献
773.
774.
Nanosecond laser flash photolysis employing transient detection of emission and absorption in combination with pulse radiolysis and quantum theory has been employed to shed light into the kinetics, quantum yields, and mechanisms of the deactivation of the first excited singlet state of 1- and 2-thionaphthols (NpSH(S(1))). In contrast to thiophenols (ArSH(S(1))), the results revealed that the decay of the first excited singlet state of 1- and 2-thionaphthols (NpSH(S(1))) is governed by radiationless internal conversion (Φ(IC) = 0.29-0.46; 0.016-0.190) and intersystem crossing (Φ(ISC) = 0.14-0.15; 0.4-0.6), respectively, with pronounced S-H photodissociation (Φ(D) = 0.40-0.55; 0.35-0.40). Fluorescence as a deactivation channel plays a minor role (Φ(F) = 0.001-0.010; 0.010-0.034). Quantum chemical calculations helped in understanding the formation of naphthylthiyl radicals and rationalizing the differences in the efficiency of intersystem crossing of the 1- and 2-thionaphthol systems. 相似文献
775.
A. D. Averin T. Yu. Baranova A. S. Abel V. V. Kovalev A. K. Buryak G. M. Butov E. N. Savelyev B. S. Orlinson I. A. Novakov I. P. Beletskaya 《Russian Journal of Organic Chemistry》2013,49(1):1-7
Palladium-catalyzed amination of 3-bromopyridine with amines of the adamantane series in the presence of Pd(dba)2/L [L = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl or 2-dimethylamino-2′-dicyclohexylphosphinobiphenyl] gave the desired N-(pyridin-3-yl)-substituted amines in 74–97% yields. Diamines of the adamantane series reacted with 2 equiv of 3-bromopyridine in a complicated fashion to produce mono- and triaryl-substituted derivatives as by-products, while the yields of N,N′-diarylation products were 18–56%. 相似文献
776.
Let A be an associative and unital K-algebra sheaf, where K is a commutative ring sheaf, and ε an (A, A)-bimodule, that is, a sheaf of (A, A)-bimodules. We construct an (A, A)-bimodulc which is K-isomorphic with the K-module D K (A, ε) of germs of K-derivations. A similar isomorphism is obtained, this time around with respect to A, between the K-module D K (A, ε) with the A-module Hom A (Ω K (A), ε). where A, in addition of being associative and unital, is assumed to be commutative, and Ω K (A) denotes the A-module of germs of Kähler differentials. Finally, we expound on functoriality of Kähler differentials. 相似文献
777.
Bermejo A Ros A Fernández R Lassaletta JM 《Journal of the American Chemical Society》2008,130(47):15798-15799
Glyoxal bis-hydrazone derived from (S,S)-1-amino-2,5-diphenylpyrrolidine behaves as an excellent ligand for phosphine-free, asymmetric Suzuki-Miyaura cross couplings, thereby affording a variety of enantiomerically enriched biaryls with different substitution patterns. The high catalytic activity of the [PdCl2(bis-hydrazone)] complex allows reactions to be performed at room temperature, affording products with excellent enantioselectivities in all cases. 相似文献
778.
Borisenko KB Evangelou EA Zhao Q Abel EW 《Journal of colloid and interface science》2008,326(2):329-332
The influence of surrounding electrolyte type and concentration on the contact angle of hydrophobic diiodomethane on silicon-doped diamond-like carbon (DLC) coatings was examined to provide insight into how the presence of electrolytes in the solution influences adhesion of hydrophobic material to doped DLC surfaces. There was a small but statistically significant increase of contact angle with increasing electrolyte concentration over the range from 0 to approximately 0.01 M, after which the contact angle was virtually unaffected by further increase in the concentration of electrolyte. It was shown that CaCl(2) has a stronger influence on the change of the contact angle than NaCl, and that an increase in Si content in the DLC coatings increased the change in the contact angle of diiodomethane for all types of electrolyte. These observations suggest that the adhesion to the Si-doped DLC surfaces is reduced by addition of the electrolytes to the surrounding solvent. This could be explained by increased ion adsorption on the DLC surface with increase in silicon doping, causing the surfaces to be more hydrophilic. 相似文献
779.
Amrit Venkatesh Gilles Casano Yu Rao Federico De Biasi Frédéric A. Perras Dominik J. Kubicki Didier Siri Sébastien Abel Hakim Karoui Maxim Yulikov Olivier Ouari Lyndon Emsley 《Angewandte Chemie (International ed. in English)》2023,62(31):e202304844
The sensitivity of NMR spectroscopy is considerably enhanced by dynamic nuclear polarization (DNP). In DNP polarization is transferred from unpaired electrons of a polarizing agent to nearby proton spins. In solids, this transfer is followed by the transport of hyperpolarization to the bulk via 1H-1H spin diffusion. The efficiency of these steps is critical to obtain high sensitivity gains, but the pathways for polarization transfer in the region near the unpaired electron spins are unclear. Here we report a series of seven deuterated and one fluorinated TEKPol biradicals to probe the effect of deprotonation on MAS DNP at 9.4 T. The experimental results are interpreted with numerical simulations, and our findings support that strong hyperfine couplings to nearby protons determine high transfer rates across the spin diffusion barrier to achieve short build-up times and high enhancements. Specifically, 1H DNP build-up times increase substantially with TEKPol isotopologues that have fewer hydrogen atoms in the phenyl rings, suggesting that these protons play a crucial role transferring the polarization to the bulk. Based on this new understanding, we have designed a new biradical, NaphPol, which yields significantly increased NMR sensitivity, making it the best performing DNP polarizing agent in organic solvents to date. 相似文献
780.
Reduction of bacterial adhesion on modified DLC coatings 总被引:1,自引:0,他引:1
The high incidence of infections caused by the use of implanted biomedical devices, including catheters, bone fracture fixation pins and heart valves, etc. has a severe impact on human health and health care costs. Diamond-like carbon (DLC) films as biomaterial for medical devices have been attracting great interest due to their excellent properties such as low friction and chemical inertness. It has been demonstrated that the properties of DLC films can be further improved by the addition of selective elements into DLC films. In this paper Si- and N-doped DLC coatings with various silicon and nitrogen contents on 316 stainless steel substrates were prepared by a magnetron sputtering technique. Bacterial adhesion to the modified DLC coatings was evaluated with Pseudomonas aeruginosa (ATCC 33347) which frequently cause medical device infections. The results showed that the addition of N or Si in DLC coatings had a significant influence on bacterial adhesion. In general the modified DLC coatings with N or Si performed better than the pure DLC coatings in inhibiting bacterial adhesion. The bacterial adhesion mechanism on the modified DLC coatings was explained with thermodynamic theory. 相似文献