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101.
Noora Virtanen Ville Nevalainen Taru Lehtinen Satu Mikkola 《Journal of Physical Organic Chemistry》2007,20(1):72-82
Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H2O and D2O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pKa), as the buffer concentration increases. The kinetic solvent deuterium isotope effect kH/kD, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
102.
A. I. Golovashkin G. N. Izmaïlov G. V. Kuleshova T. Q. Khánh A. M. Tskhovrebov L. N. Zherikhina 《The European Physical Journal B - Condensed Matter and Complex Systems》2007,58(3):243-249
A scheme of magnetic calorimeter for registration of rare events
characterized by small energy release (cosmic rays, WIMPs, solitary X-ray
quanta) is proposed. The calorimeter is brought to operation by adiabatic
demagnetization, and its magnetic response is measured by a quantum
interferometer (SQUID, A. Barone and G. Paterno, Physics and applications of Josephson Effect). Special consideration is given to the specific
features of calorimeter operation in the ferromagnetic transition region.
The trigger registration of ultrasmall energy release by a ferromagnetic
system in the metastable state is described. 相似文献
103.
In this paper we apply linear control theory to study the effect of various inventory policies on order and inventory variability, which are key drivers of supply chain performance. In particular, we study a two-echelon supply chain with a stationary demand pattern under the influence of three inventory policies: an inventory-on-hand policy that bases orders on the visible inventory at an installation, an installation-stock policy that bases orders on the inventory position (on-hand plus on-order inventory) at an installation, and an echelon-stock policy that bases orders on the inventory position at that installation and all downstream installations. We prove analytically that the inventory-on-hand policy is unstable in practical settings, confirming analytically what has been observed in experimental settings and in practice. We also prove that the installation-stock and echelon-stock policies are stable and analyze their effect on order and inventory fluctuation. Specifically, we show the general superiority of the echelon-stock in our setting and demonstrate analytically the effect of forecasting parameters on order and inventory fluctuations, confirming the results in other research. 相似文献
104.
Vicenç Branchadell Roser Pleixats Claude Commandeur Max Malacria 《Journal of organometallic chemistry》2003,687(2):337-345
Regioselectivity of the Tsuji-Trost reaction on allyl acetates and carbonates substituted with silyl groups at the olefinic moiety has been analyzed. Silicon atom in the central carbon atom increases the stability of the intermediate π-allylpalladium cation with respect to the isomeric π-allylpalladium cation featuring the silicon in a terminal carbon atom. 相似文献
105.
氯代5-氟脲嘧啶卟啉的红外光谱特性的研究 总被引:6,自引:0,他引:6
本文对新合成的对位及间位两类氯代苯基 5 氟脲嘧啶卟啉的红外光谱吸收峰进行了归属和总结 ,讨论了其红外吸收频率随取代基位置变化的规律。指出了苯环上的取代基为电负性强的基团时 ,由于场效应的存在 ,使被测化合物的羰基伸缩振动吸收峰的相对强度发生改变。同时 ,表明了嘧啶环上N原子发生了取代 ,形成单、双取代 5 氟脲嘧啶卟啉化合物的红外光谱特性。 相似文献
106.
Marta Gimnez-Pedrs Ali Aghmiz Carmen Claver Anna M. Masdeu-Bult Denis Sinou 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):157-163
High linear alkenes (1-octene and 1-decene) have been hydroformylated using water-soluble rhodium complexes associated with sulfonated diphosphines in the presence of ionic surfactants or methanol. In all cases, the hydroformylation activities were higher than in experiments without additives. The selectivity in aldehydes was higher when we used cetyltrimethylammonium hydrogensulfate (CTAHSO4) as the surfactant or methanol as the co-solvent. 相似文献
107.
108.
By means of improved ligand-field theory, the "pure electronic" pressure-induced shifts (PS's) and the PS's due to electron-phonon interaction (EPI) of R1 line and R2 line of YAG:Cr3 have been calculated, respectively.The calculated results are in very good agreement with the experimental data. It is demonstrated that the admixture of |t22(3T1)e4T2> and |t322E> bases in the wavefunction of R1 level of YAG:Cr3 and its change with pressure play a key role for the PS of R1 line. The behaviors of the "pure electronic" PS of R1 line and the PS of R1 line due to EPI are different. It is the combined effect of them that gives rise to the total PS of R1 line, which has satisfactorily explained the experimental results. The systematic analyses and comparisons between the feature of R1-line PS of YAG:Cr3 and the ones of three laser crystals (GSGG:Cr3 , GGG:Cr3 and ruby) have been made, and the origin of the difference between them has been revealed. 相似文献
109.
110.