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181.
Chiral α,ω-diesters react under high-pressure conditions (10 kbar) with α,ω-diamines to give chiral cyclic tetraamides of C2-symmetry. The complexation properties of tetraamides towards alkali metal cations (Li+, Na+, K+, Rb+ and Cs+) were estimated on the basis of ESI-MS spectra. 相似文献
182.
183.
T. Sato F. Ambe K. Endo M. Katada H. Sano 《Journal of Radioanalytical and Nuclear Chemistry》1995,190(2):257-261
The crystal structures of oxo-centered trineclear cobalt-iron chloroacetate complex [CoIIFe
2
III
O(CH2ClCO2)6(H2O)3]·3H2O (1) was compared with that of previously reported trinuclear iron complex [FeIIFe
2
III
O(CH2ClCO2)6(H2O)3]·3H2O (2) which has an isomorphous structure to 1. Compound 1 crystallizes in space group P21/n with Z=4 in a unit cell of a=14.826 (4) Å, b=4.536 (8) Å, c=14.000 (4) Å, =100.32 (2)0 and V=2968 (11) Å3. The structure was refined to R=0.75 and Rw=0.82. The coordination geometries of the three iron atoms are observed equivalent in 1 indicating a static disorder of the position among cobalt and iron atoms. Two distinct FeIII doublets observed in Mössbauer spectra of 1 become an indistinguishable broad doublet by dehydration of crystal water. On the other hand, no significant line-broadening is observed after the dehydration in complex 2. The results indicate that the dehydration in 2 induces a local environmental change reordering of an electronic configuration around iron atoms, whereas the remaining disordering is reflected in Mössbauer spectrum after the dehydration in 1. 相似文献
184.
Conversion reactions of n-butenes over zeolites and amorphous catalysts have been investigated to deduce the factor that determines the selectivity
for the skeletal isomerization producing isobutene. The effects of pore structure and acid site concentration on the selectivity
for the skeletal isomerization are discussed on various catalysts. The pore structures of FER and CLI zeolites induce the
distant locations of butene molecules, accelerating monomolecular skeletal isomerization. On the other hand, acid site concentration
determines the preferred reaction path of n-butenes on amorphous catalysts. Oligomerization followed by cracking that produces various hydrocarbons is suppressed on
the catalyst with low acid site concentration, resulting in high selectivity for isobutene. The feasibility of monomolecular
skeletal isomerization on zeolites and amorphous catalysts is confirmed by its reversibility with high selectivity. 相似文献
185.
The ethanol effect on the Trichoderma reesei cellulases was studied to quantify and clarify this inhibition type. To determine inhibition parameters of crude cellulase
and purified exoglucanase Cel7A, integrated Michaelis-Menten equations were used assuming the presence of two inhibitors:
cellobiose as the reaction product and ethanol as a possible bioproduct of cellulose fermentation.
It was found that hydrolysis of cellulose by crude enzyme follows a model that considers noncompetitive inhibition by ethanol,
whereas Cel7A is very slightly competitively inhibited. Crude cellulase is much more inhibited (K
iul=K
icl=151.9 mM) than exoglucanase Cel7A (K
icl=1.6 × 1015 mM). Also, calculated inhibition constants showed that cellobiose inhibition is more potent than ethanol inhibition both for
the crude enzyme as well as exoglucanase Cel7A. 相似文献
186.
Sébastien Fiorucci Jer?me Golebiowski Daniel Cabrol-Bass Serge Antonczak 《Chemphyschem》2004,5(11):1726-1733
Flavonoids are naturally occurring phenol derivatives present in substantial amounts in a large variety of plants, fruits and vegetables daily eaten by humans. Most of these compounds exhibit several interesting biological activities, such as antiradical and antioxidant actions. Indeed, by complexation with specific enzymes, flavonoids are notably liable to metabolize molecular dioxygen. On the basis of experimental results describing oxygenolysis of the flavonoid quercetin, activated by the enzyme quercetin 2,3-dioxygenase (2,3-QD),ur attention has focused on the role of metal center in the activation of the substrate quercetin. Thus, in the present study, by means of DFT calculations at the B3LYP/ 6-31(+)G* level on model molecular systems, we describe different mechanisms for dioxygen metabolization by quercetin. Stationary points are described, and energetic and structural analyses along the reaction paths are reported. Our calculations show that the copper cation must act as an oxidant towards the substrate and that the reaction proceeds through a 1,3-cycloaddition. 相似文献
187.
The thermal stress around the sodium level of the LMFBR reactor vessel, caused by the axial temperature distribution during heat-up and cool-down transient conditions, is one of the most important problems for a reactor vessel designer, especially in a conceptual design stage. Key parameters relating to plant operating transient conditions and reactor vessel main configuration should be settled carefully, thermal stresses not being allowed to exceed design stress limits. In order to examine the sodium level thermal stress easily and economically, a simple computer program for parameter survey has been developed. This program uses a one-dimensional Fourier series solution in transient temperature distribution analysis, and an analytical stress solution based on shell theory in stress value estimation. This paper presents a simplified and economical calculation method for the axial temperature distribution and stress value in the LMFBR operating transient conditions, and analysis examples obtained with this computer program.
Paper presented at the World Conference on Thermal Analysis, Madeira (Portugal) 1986. 相似文献
Zusammenfassung Der durch die axiale Temperaturverteilung während der Übergangsphase von Aufheizen und Abkühlen verursachte thermische Streß rund um den Natriumfüllstand des LMFBR-Reaktorkessels ist für den Reaktorkesselkonstrukteur, besonders im Entwurfstadiuni eines der wichtigsten Probleme. Die mit den transienten Operationsbedingungen der Anlage und der Gestaltung des Reaktorkessels in Beziehung stehenden Grundparameter müssen sorgfältig ermittelt werden, um zu verhindern, daß der thermische Streß die geplanten Streßgrenzen nicht überschreitet. Um den thermischen Streß um den Natriumfüllstand, leicht und ökonomisch zu bestimmen, wurde ein Komputerprogramm für die Parameterübersicht aufgestellt. In diesem Programm wird von einer eindimensionalen Fourrierreihe zur Analyse der transienten Temperaturverteilung und einer auf der Schalentheorie von Streßwertbestimmungen basierende analytische Lösung Gebrauch gemacht. Im vorliegenden Artikel werden eine vereinfachte und wirtschaftliche Berechnungsmethode für die axiale Temperaturverteilung und Streßwerte bei transienten Arbeitsbedingungen mitgeteilt und mit diesem Komputerprogramm ausgeführte Analysenbeispiele angegeben.
, - () , , , . , , , . , , - , . , , .
Paper presented at the World Conference on Thermal Analysis, Madeira (Portugal) 1986. 相似文献
188.
Trace analysis of rapamycin in human blood by micellar electrokinetic chromatography 总被引:1,自引:0,他引:1
A capillary electrophoretic method with UV detection at 278 nm has been developed for analysis of the immunosuppressant rapamycin (sirolimus) in human blood at low microgram per liter levels. Separation has been achieved in an acidic carrier electrolyte containing sodium dodecylsulfate and 30% (v/v) acetonitrile. For sample clean-up and preconcentration, an off-line solid-phase extraction step using a silica-based reversed-phase material and an on-capillary focussing technique were employed. The latter allows the injection of increased sample volumes without excessive band broadening. Although this new method is less sensitive than existing liquid chromatographic procedures combined with mass spectrometry, it is fully suited to routine analysis of rapamycin in blood from patients treated with this drug. Last but not least the low costs make it an attractive alternative to established methods. 相似文献
189.
190.
The discovery of selective cyclooxygenase-2 (COX-2) inhibitors represents a major achievement of the efforts over the past few decades to develop therapeutic treatments for inflammation. To gain insights into designing new COX-2-selective inhibitors, we address the energetic and structural basis for the selective inhibition of COX isozymes by means of a combined computational protocol involving docking experiment, force field design for the heme prothetic group, and free energy perturbation (FEP) simulation. We consider both COX-2- and COX-1-selective inhibitors taking the V523I mutant of COX-2 to be a relevant structural model for COX-1 as confirmed by a variety of experimental and theoretical evidences. For all COX-2-selective inhibitors under consideration, we find that free energies of binding become less favorable as the receptor changes from COX-2 to COX-1, due to the weakening and/or loss of hydrogen bond and hydrophobic interactions that stabilize the inhibitors in the COX-2 active site. On the other hand, COX-1-selective oxicam inhibitors gain extra stabilization energy with the change of residue 523 from valine to isoleucine because of the formations of new hydrogen bonds in the enzyme-inhibitor complexes. The utility of the combined computational approach, as a valuable tool for in silico screening of COX-2-selective inhibitors, is further exemplified by identifying the physicochemical origins of the enantiospecific selective inhibition of COX-2 by -substituted indomethacin ethanolamide inhibitors. 相似文献