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排序方式: 共有218条查询结果,搜索用时 484 毫秒
41.
Hoi KH Çalimsiz S Froese RD Hopkinson AC Organ MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(1):145-151
The amination of aryl chlorides with various aniline derivatives using the N-heterocyclic carbene-based Pd complexes Pd-PEPPSI-IPr and Pd-PEPPSI-IPent (PEPPSI=pyridine, enhanced precatalyst, preparation, stabilization, and initiation; IPr=diisopropylphenylimidazolium derivative; IPent= diisopentylphenylimidazolium derivative) has been studied. Rate studies have shown a reliance on the aryl chloride to be electron poor, although oxidative addition is not rate limiting. Anilines couple best when they are electron rich, which would seem to discount deprotonation of the intermediate metal ammonium complex as being rate limiting in favour of reductive elimination. In previous studies with secondary amines using PEPPSI complexes, deprotonation was proposed to be the slow step in the cycle. These experimental findings relating to mechanism were corroborated by computation. Pd-PEPPSI-IPr and the more hindered Pd-PEPPSI-IPent catalysts were used to couple deactivated aryl chlorides with electron poor anilines; while the IPr catalysis was sluggish, the IPent catalyst performed extremely well, again showing the high reactivity of this broadly useful catalyst. 相似文献
42.
Hong Kui Chen Guo Qiang Fu Yu Peter Hoi Zhang Guang Liu Ye Chua Hong 《Applied biochemistry and biotechnology》2000,84(1-9):971-980
Polyhydroxyalkanoates (PHAs) are biodegradable polymers produced by bacteria. In this study, the effect of C∶N molar ratio
on the monomer composition of PHAs was investigated, including medium chain length PHA produced by Pseudomonas mendocina 0806 and PHA blends consisting of monomers of 3-hydroxybutyrate and medium chain length hydroxyalkan⇘te produced by Pseudomonas pseudoalkaligenus YS1. It was observed that there were some fixed ranges of C∶N molar ratio that affect the monomer composition of PHA independently
of the substrate. For strain 0806, the ranges were C∶N <20, 20<C∶N<200, and C∶N>200. The monomer composition was constant
among these ranges when using glucose and octanoate as the sole substrate. For strain YS1, the ranges were C∶N<20, 20<C∶N<45,
and C∶N>45. These results are useful for controlling monomer composition in PHA production. 相似文献
43.
Seongwoo Kim Jooyeon Lee Dr. Sungeun Jeoung Prof. Dr. Hoi Ri Moon Prof. Dr. Min Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(34):7568-7572
Metal–organic frameworks (MOFs) are an attractive catalyst support for stable immobilization of the active sites in their scaffold due to the high tunability of organic ligands. The active site-functionalized ligands can be easily employed to construct MOFs as porous heterogeneous catalysts. However, the existence of active sites on the external surfaces as well as internal pores of MOFs seriously impedes the selective reaction in the pore. Herein, through a simple post-synthetic ligand exchange (PSE) method we synthesized surface-deactivated (only core-active) core–shell-type MOF catalysts, which contain 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) groups on the ligand as active sites for aerobic oxidation of alcohols. The porous but catalytically inactive shell ensured the size-selective permeability by sieving effects and induced all reactions to take place in the pores of the catalytically active core. Because PSE is a facile and universal approach, this can be rapidly applied to a variety of MOF-based catalysts for enhancing reaction selectivity. 相似文献
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46.
A 3D porous metal-organic framework generating 1D channels, [Mn(NDC)(DEF)]n (1), has been prepared from the solvothermal reaction of Mn(II) and 2,6-naphthalenedicarboxylic acid (H2NDC) in diethylformamide (DEF). When DEF molecules coordinating Mn(II), which occupy the channels, are removed from 1 by heating the crystal of 1 at 250 degrees C under vacuum for 18 h, structural change occurs as evidenced by X-ray powder diffraction patterns. Desolvated solid [Mn(NDC)]n (2), which contains coordinatively unsaturated Mn(II) sites, reveals remarkable sorption capabilities for N2, H2, CO2, and CH4 gases and exhibits type I sorption behavior indicative of permanent microporosity. 相似文献
47.
To facilitate the analysis of frequency-structure correlations in the amide I vibrational spectroscopy of proteins, we investigate visualization methods and spatial correlation functions that describe delocalized vibrations of proteins and protein secondary structures. To study those vibrational modes revealed in infrared spectroscopy, we characterize frequency-dependent bright states obtained from doorway mode analysis. Our visualization methods pictorially color code amplitude and phase of each oscillator within the structure to reveal spatially varying patterns characteristic of excitations within sheets and helices. Spatial correlation functions in the amplitude and phase of amide I oscillators quantitatively address the extent of delocalization and the alpha helical and beta sheet character of these modes. Specifically, we investigate the vibrations of idealized antiparallel beta sheets and alpha helices and perform case studies on three proteins: concanavalin A, myoglobin, and ubiquitin. 相似文献
48.
A novel method for light coupling between single-mode fibers (SMFs) and small-core photonic crystal fibers (PCFs) is demonstrated. The method is based on growing photopolymer microtips directly on the end faces of SMFs. The shape and size of the tips can be controlled by adjusting the laser power and the exposure time for polymerization to match the mode field to the small-core PCFs. A 5 dB improvement in coupling efficiency between a SMF and a commercial small-core, highly nonlinear PCF is experimentally demonstrated. This compact and efficient butt-coupling method is particularly suitable for PCF gas sensor applications. 相似文献
49.
This paper investigates the robust optimal pairs trading using the concept of equivalent probability measures and a penalty function associated with the confidence in parameter estimates when the parameters in the drift term of the continuous-time cointegration model are estimated with errors. A closed-form solution is derived for the robust pairs trading rule. We compare the robust pairs trading rule against its non-robust counterpart using simulations and real data. The robust strategy is empirically more stable and less volatile. 相似文献
50.
Li Z Dong Y Mi B Tang Y Häussler M Tong H Dong Y Lam JW Ren Y Sung HH Wong KS Gao P Williams ID Kwok HS Tang BZ 《The journal of physical chemistry. B》2005,109(20):10061-10066
We synthesized a group of silole regioisomers 1(x,y), whose photoluminescence varied dramatically with its regiostructure. By internally hindering the intramolecular rotation, we succeeded in creating a novel silole (1(3,4)) that is strongly luminescent in solutions and whose fluorescence quantum yield in acetone is as high as 83%. We revealed that 1(3,4) was a sensitive chemosensor capable of optically discriminating nitroaromatic regioisomers of p-, o-, and m-nitroanilines. Against general belief, crystal formation of 1(2,4) blue-shifted its emission color and boosted its emission efficiency. The light-emitting diode based on the crystal of 1(2,4) emitted a strong blue light (464 nm) in a high current efficiency (5.86 cd/A). 相似文献