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91.
We introduce an energy-momentum density vector which is independent of the affine structure of the manifold and whose conservation is linked to observers. Integrating this quantity over time-like surfaces we can define Hamiltonian and momentum for the system which coincide with the corresponding ADM definitions for the case of irrotational Riemannian manifolds. As a consequence of our formalism, a Weak Equivalence Principle version for manifolds with torsion appears as the natural extension to non-Riemannian geometries from the Equivalence Principle of General Relativity. 相似文献
92.
93.
A kinetic study is reported for aminolysis of aryl diphenylphosphinothioates (2a-i). The phosphinothioates 2a-i are less reactive than aryl diphenylphosphinates (1a-i), the oxygen analogues of 2a-i, regardless of the basicity of the leaving aryloxides or the attacking amines. The Yukawa-Tsuno plot for the reactions of 2b-i with piperidine exhibits good linearity with a small r value (r=0.28), indicating that the leaving group departs at the rate-determining step with a small degree of bond fission. Reactions of 2,4-dinitrophenyl diphenylphosphinothioate (2a) with alicyclic secondary amines result in a good linear Br?nsted-type plot with betanuc=0.52, implying that the reactions proceed through a concerted mechanism. The betanuc value determined for the reactions of 2a is slightly larger than that reported for the corresponding reactions of 2,4-dinitrophenyl diphenylphosphinate (1a, i.e., betanuc=0.38), suggesting that reactions of 2a proceed through a tighter transition state (TS) than that of 1a. The reaction of 2a with piperidine exhibits a ca. 0.4 kcal/mol more favorable enthalpy of activation (DeltaH) than that of 1a. On the contrary, the entropy of activation at 25.0 degrees C (TDeltaS) is ca. 1.5 kcal/mol more unfavorable for the reaction of 2a than for that of 1a. This result supports the proposal that the reaction of 2a proceeds through a tighter TS than that of 1a and explains why 2a-i are less reactive than 1a-i. 相似文献
94.
Alkali‐Metal Ion Catalysis and Inhibition in SNAr Displacement: Relative Stabilization of Ground State and Transition State Determines Catalysis and Inhibition in SNAr Reactivity
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Prof. Ik‐Hwan Um Hyo‐Jin Cho Min‐Young Kim Prof. Erwin Buncel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13337-13344
We report here the first observation of alkali‐metal ion catalysis and inhibition in SNAr reactions. The plot of kobsd versus [alkali‐metal ethoxide] exhibits downward curvature for the reactions of 1‐(4‐nitrophenoxy)‐2,4‐dinitrobenzene with EtOLi, EtONa, and EtOK, but upward curvature for the corresponding reaction with EtOK in the presence of 18‐crown‐6‐ether (18C6). Dissection of kobsd into the second‐order rate constants for the reactions with the dissociated EtO? and the ion‐paired EtOM (i.e., k and kEtOM, respectively) has revealed that the reactivity increases in the order EtOLi<EtONa<EtOK<EtO?<EtOK/18C6. This indicates that the reaction is inhibited by Li+, Na+, and K+ ions but is catalyzed by 18C6 K+ ion. The reactions of 1‐(Y‐substituted‐phenoxy)‐2,4‐dinitrobenzenes have been proposed to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs after the rate‐determining step based on the kinetic result that σo constants exhibit a much better Hammett correlation than σ? constants. Alkali‐metal ion catalysis or inhibition has been discussed in terms of differential stabilization of ground‐state and transition‐state complexes through a qualitative energy profile. A π‐complexed transition‐state structure is proposed to account for the kinetic results. 相似文献
95.
Hye Jung Park Jung-Ho Sohn Yoon-Ju Kim Yoon Hee Park Heejae Han Kyung Hee Park Kangtaek Lee Hoon Choi Kiju Um In-Hong Choi Jung-Won Park Jae-Hyun Lee 《Experimental & molecular medicine》2015,47(7):e173
Silica nanoparticles (SNPs) are widely used in many scientific and industrial fields despite the lack of proper evaluation of their potential toxicity. This study examined the effects of acute exposure to SNPs, either alone or in conjunction with ovalbumin (OVA), by studying the respiratory systems in exposed mouse models. Three types of SNPs were used: spherical SNPs (S-SNPs), mesoporous SNPs (M-SNPs), and PEGylated SNPs (P-SNPs). In the acute SNP exposure model performed, 6-week-old BALB/c female mice were intranasally inoculated with SNPs for 3 consecutive days. In the OVA/SNPs asthma model, the mice were sensitized two times via the peritoneal route with OVA. Additionally, the mice endured OVA with or without SNP challenges intranasally. Acute SNP exposure induced significant airway inflammation and airway hyper-responsiveness, particularly in the S-SNP group. In OVA/SNPs asthma models, OVA with SNP-treated group showed significant airway inflammation, more than those treated with only OVA and without SNPs. In these models, the P-SNP group induced lower levels of inflammation on airways than both the S-SNP or M-SNP groups. Interleukin (IL)-5, IL-13, IL-1β and interferon-γ levels correlated with airway inflammation in the tested models, without statistical significance. In the mouse models studied, increased airway inflammation was associated with acute SNPs exposure, whether exposed solely to SNPs or SNPs in conjunction with OVA. P-SNPs appear to be relatively safer for clinical use than S-SNPs and M-SNPs, as determined by lower observed toxicity and airway system inflammation. 相似文献
96.
In this study, we investigated the enlargement of liquid crystal (LC) blue-phase (BP) temperature range using the rod-like low-molecular-weight cyano phenyl-type chiral nematic LC with various core group and chiral dopant concentrations. Also, the electro-optic response time was investigated for them. We found that the BP temperature range was strongly dependent upon the core structure and the chiral dopant concentration for the chiral nematic LC mixtures having the same terminal group. Also, we found a stable BP with a wide temperature range (more than 6 K), including a BP-isotropic coexistence state over 13.5 K upon heating and cooling processes and very fast response time (less than 1 ms), by using the cyano phenyl-type chiral nematic LC mixture with a high molecular aspect ratio and a high chiral dopant concentration. 相似文献
97.
Sun-Mi Lee Min Ok Cho Youngsoon Um Byoung-In Sang 《Applied biochemistry and biotechnology》2010,161(1-8):75-83
Degeneration is one of the limiting factors in butanol fermentation, and it must be monitored and prevented for stable butanol production. In Clostridium acetobutylicum ATCC 824, the most well-known butanol-producing microorganism, degeneration is caused by the loss of the pSOL1 plasmid that carries essential genes involved in solvent production. In this study, we designed two specific primer and probe sets for real-time qPCR (RT-qPCR) detection of C. acetobutylicum ATCC 824 (the C. aceto set) and pSOL1-possessing C. acetobutylicum ATCC 824 (the DGS set). Specific primer and probe sets were designed on the basis of the 16S rDNA sequence and pSOL1 sequence. The number of degenerated C. acetobutylicum could be quantified by subtracting the number of C. acetobutylicum ATCC 824 containing pSOL1 from the total number of C. acetobutylicum ATCC 824. The primer and probe sets permitted the specific detection and quantification of degenerated C. acetobutylicum and total butanol-producing C. acetobutylicum by RT-qPCR. 相似文献
98.
This research was done on the basis of prediction that there is a relationship between welding parameters and geometry of the back-bead in arc welding which is a gap. Multiple regression analysis and artificial neural network were used as methods for predicting the geometry of the back-bead. The multiple regression analysis and the artificial neural network were formed, and the analysis data or verification data which were used in the formation process of the multiple regression, and the training data or test data which were used in the formation process of the artificial neural network, were used to perform the prediction of the back-bead. Through this research, it was found that the error rate predicted by the artificial neural network was smaller than that predicted by the multiple regression analysis, in terms of the width and depth of the back-bead. It was also found that between the two predictions, the prediction of the width of the back-bead was superior to the prediction of the depth in both methods. 相似文献
99.
Second-order rate constants have been measured spectrophotometrically for the nucleophilic reactions of three substituted phenyl acetates with butane-2,3-dione monoximate (Ox(-)) as an alpha-nucleophile and p-chlorophenoxide (ClPhO(-)) as corresponding normal nucleophile, in MeCN-H2O mixtures of varying compositions at 25.0 +/- 0.1 degrees C. The reactivity of Ox(-) toward the aryl acetates decreases upon addition of MeCN to the reaction medium up to ca. 30 mol % MeCN, followed by a gradual increase in rate upon further addition of MeCN. A similar result has been obtained for the reaction of ClPhO(-) with the aryl acetates. However, the decrease in rate is more significant for the less reactive ClPhO(-) than for the more reactive Ox(-). Thus, for all the aryl acetates studied, Ox(-) exhibits a sizable alpha-effect (k(Ox)-/k(ClPhO)-) whose magnitude increases as the mol % MeCN in the reaction medium increases. The relative basicities (DeltapK(a)) of Ox(-) and ClPhO(-) have been determined spectrophotometrically using piperazine as a reference base. The DeltapK(a) values increase on increasing the mol % MeCN in the medium for both Ox(-) and ClPhO(-). The difference in the relative basicities of these nucleophiles (DeltaDeltapK(a)) becomes larger with increasing mol % MeCN. The plots of log k(Ox)-/k(ClPhO)- vs DeltaDeltapK(a) for the three substrates are linear with near-unit slope, indicating that the difference in the relative basicity of the nucleophiles is largely responsible for the increasing alpha-effect with medium composition in this system. 相似文献
100.
BalSang Lee In Hyeok Jang Jong Wook Bae Soong Ho Um Pil J. Yoo Myung-June Park Yong Chul Lee Ki-Won Jun 《Catalysis Surveys from Asia》2012,16(3):121-137
The present paper represents the promising ways to improve catalytic performance by introducing zirconium phosphate (ZP) on Ru/Co/SiO2 catalysts and the related kinetic models using the optimized Fischer?CTropsch synthesis (FTS) catalyst. A lot of works has been reported using cobalt-based catalyst for FTS reaction, and many authors have continuously tried to find out highly efficient FTS catalyst by modifying support as well as by introducing promoters. Silica is one of the excellent candidates as catalytic supports, and the present works intensively represents how to modify SiO2 support for a high catalytic performance by using ZP species. The effect of ZP-modification of SiO2 support with respect to cobalt aggregation and catalytic deactivation was mainly investigated for FTS reaction. The surface modification at P/(Zr?+?P) molar ratio between 0.029 and 0.134, enhanced the spatial confinement effect of cobalt clusters, and resulted in high catalytic stability with the help of well-dispersed ZP particle formation. The enhanced catalytic performance, in terms of CO conversion, C5+ selectivity and catalytic stability, is mainly attributed to the suppressed aggregation, a homogeneous distribution of cobalt clusters with a proper size and a low mobility of cobalt clusters at an optimum molar ratio of P/(Zr?+?P) because of the formation of thermally stable ZP particles. The kinetic parameters and rate equations on the optimized catalyst are also derived in terms of CO conversion and product distribution. 相似文献