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991.
Feng G Mareque-Rivas JC Torres Martín de Rosales R Williams NH 《Journal of the American Chemical Society》2005,127(39):13470-13471
The activity of a Zn(II) complex of a tetradentate, tripodal ligand for catalyzing phosphodiester cleavage is enhanced 750-fold by introducing three hydrogen bond donors to the ligand. Inhibition studies show that the Zn-aqua complex is the kinetically active form and that it binds the transition state with a formal dissociation constant of 3 x 108 M-1. The effect of these ligand modifications on the transition-state affinity is comparable to the rate acceleration provided by the metal ion itself. Overall, this mononuclear complex is more active than the most reactive dinuclear Zn(II) complexes reported to date. 相似文献
992.
García-Martín J López-Garzón R Godino-Salido ML Gutiérrez-Valero MD Arranz-Mascarós P Cuesta R Carrasco-Marín F 《Langmuir : the ACS journal of surfaces and colloids》2005,21(15):6908-6914
The results presented in this work are related to the design of a guideline to develop specific properties at the surface of an activated carbon (AC). For this, two model aromatic compounds have been synthesized and their electrolytic behavior in aqueous solutions was studied by a potentiometric method. The textural characteristics of the activated carbon were determined by porosimetry methods. The nature of oxygen-carrying functions and the acid-base behavior of the AC surface were characterized by TPD and potentiometric titration methods, respectively. The adsorption and desorption equilibria of the aromatic compounds on activated carbon were measured in aqueous solutions, and the hysteresis between adsorption and desorption, which reveals irreversible adsorption, was discussed on the basis of the frontier orbital theory. HOMO and LUMO orbitals of the adsorbent and adsorbates were calculated, and irreversible adsorption was attributed to the small energy difference between HOMO and LUMO of the aromatic adsorbates and the adsorbent. Adsorption equilibria of K2CrO4 in aqueous solution on the AC alone and on the AC-aromatic ligand adsorbents, respectively, prove the efficient development of specific chemical functions at the carbon surface provided by the adsorbed aromatic compounds. 相似文献
993.
An efficient reversed-phase high-performance liquid chromatographic method has been developed for the determination of ethyl biscoumacetate (EBA) and its metabolite in human serum, using the mu Bondapak C18 column and methanol-water-phosphoric acid (56:46.8:0.2, v/v/v) as the mobile phase. This method permitted the determination of both EBA and a metabolite in human serum. The latter has been mentioned by other authors only in urine samples, where significant concentrations were found. Identification of the metabolite as 7-hydroxyethyl biscoumacetate was based on its chromatographic separation, followed by isolation from the eluate and direct mass spectrometric identification. It has been found that the higher EBA concentrations in human serum described by Brodie et al. [J. Pharmacol. Exp. Ther., 106 (1952) 453] were caused by the insufficient resolving power of the spectrophotometric method used, leading to overlapping of the UV spectra of the parent drug and its metabolite. 相似文献
994.
I. Moullet José Luís Martins F. Reuse J. Buttet 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1989,12(1-4):353-356
We present pseudopotential local-spin-density calculations of the static electric polarizability of sodium dimers and trimers and their respective cations. The electronic polarizabilities are obtained from self-consistent calculations in the presence of an external electric field, which is kept sufficiently small to avoid non-linear effects. The calculated polarizability tensor has a strong anisotropy directly related to the geometric and electronic structures of the molecules, the anisotropy being larger for the neutral clusters. The polarizabilities are averaged over the vibrational motion and rotations of the aggregates in order to be compared with the experimental measurements. The obtained values show an improvement in the agreement with experiment with respect to the values calculated in the spherical approximation. 相似文献
995.
The synthesis of CF(3)OC(O)OOC(O)F is accomplished by the photolysis of a mixture of (CF(3)CO)(2)O, FC(O)C(O)F, CO, and O(2) at -15 degrees C using a low-pressure mercury lamp. The new peroxide is obtained in pure form in low yield after repeated trap-to-trap condensation and is characterized by NMR, IR, Raman, and UV spectroscopy. Geometrical parameters were studied by ab initio methods [B3LYP/6-311+G(d)]. At room temperature, CF(3)OC(O)OOC(O)F is stable for many days in the liquid or gaseous state. The melting point is -87 degrees C, and the boiling point is extrapolated to 45 degrees C from the vapor pressure curve log p = 8.384 - 1715/T (p/mbar, T/K). A possible mechanism for the formation of CF(3)OC(O)OOC(O)F is discussed, and its properties are compared with those of related compounds. 相似文献
996.
Fandos R Hernández C Otero A Rodríguez A Ruiz MJ Terreros P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(3):671-677
Titanium complexes with chelating alkoxide ligands [TiCp*(O(2)Bz)(OBzOH)] (1) and [TiCp*(Me)((OCH(2))(2)Py)] (2) were synthesised by reaction of [TiCp*Me(3)] (Cp*=eta(5)-C(5)Me(5)) with 2-hydroxybenzyl alcohol ((HO)(2)Bz) and 2,6-pyridinedimethanol ((HOCH(2))(2)Py), respectively. Complex 1 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) to yield the early-late heterobimetallic complexes [TiCp*(O(2)Bz)(2)M(cod)] [M=Rh (3), Ir (4)]. Carbon monoxide readily replaces the COD ligand in 3 to give the rhodium dicarbonyl derivative [TiCp*(O(2)Bz)(2)Rh(CO)(2)] (5). Compound 2 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) with protonolysis of a Tibond;Me bond to give [TiCp*((OCH(2))(2)Py)(mu-O)M(cod)] [M=Rh (6), Ir (7)]. The molecular structures of complexes 3, 5 and 7 were established by single-crystal X-ray diffraction studies. 相似文献
997.
The effects of cholesterol, a lipid mostly found in the sarcolemmal membranes, on the interaction of amiodarone with synthetic
models of dimyristoylphosphatidylcholine (DMPC) and with native models of mitochondria and brain microsomes was studied. Alterations
on the structural order of lipids were assessed by fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) probing
the bilayer core, and of the propionic acid derivative 3-(p-(6-phenyl)-1,3,5-hexatrienyl)phenylpropionic acid (DPH-PA) probing the outer regions of the bilayer. As detected by the probes
and according to classic observations, cholesterol progressively increased the molecular order in the fluid phase of DMPC.
Additionally, it modulated the type and extension of amiodarone effects. For low cholesterol concentrations (≤10–15 mol%),
amiodarone (50 μM) ordered DMPC bilayers and the effects were almost identical to those observed in pure DMPC. For higher cholesterol concentrations,
amiodarone ordering effects decreased slightly and faded for cholesterol concentrations as high as 25 and 30 mol%, when detected
by DPH-PA and DPH, respectively. Above these high cholesterol concentrations, a crossover from ordering to disordering effects
of amiodarone was apparent, either in the upper region of the bilayer or the hydrophobic core. The effects of amiodarone in
native membranes of mitochondria and brain microsomes, in which "native" cholesterol accounts for about 0 and 25 mol%, respectively,
correlated reasonably with the results in models of synthetic lipids. There is a close relationship between cholesterol concentration
and amiodarone effects, in either synthetic models or native model membranes. Therefore, it may be predicted that the lipid
physicochemical properties regulated by cholesterol concentration will also modulate the effects of amiodarone in sarcolemma. 相似文献
998.
A solid-phase microextraction (SPME) sampling method is developed to evaluate indoor exposure to benzene, toluene, ethylbenzene, xylene, and styrene with gas chromatography and flame ionization detection for quantitative analysis. An SPME holder with a 100-pm polydimethylsiloxane (PDMS) and 65-pm PDMS-divinylbenzene fiber coating is tested in different air relative humidity conditions. The method gives good resolution, shows a linear response, is repeatable, and presents high sensitivity. This method is compared with National Institute of Occupational Safety and Health (NIOSH) active sampling. 相似文献
999.
J. Doménech E. Brillas J. A. Garrido R. M. Rodríguez 《Monatshefte für Chemie / Chemical Monthly》1987,118(2):197-202
Viscosities and densities of lithium perchlorate solutions in different ethylene glycol-water compositions have been measured at 25.0 and 35.0 °C. From these data, the correspondingB-coefficients of theJones-Dole equation have been determined. TheB-value depends on the solvent composition and it reaches a maximum in the water-rich region. This behaviour is analysed in terms of ionic solvation and solvent structure.
Viskositäts-B-Koeffizienten für Lösungen von Lithiumperchlorat in Ethylenglykol-Wasser-Mischungen
Zusammenfassung Es wurden die Dichten und Viskositäten für Lösungen von Lithiumperchlorat in verschieden zusammengesetzten Ethylenglykol-Wasser-Mischungen bei 25 °C und 35 °C gemessen. Auf Grund der erhaltenen Daten wurden dieB-Koeffizienten in den entsprechendenJones-Dole-Gleichungen für die relative Viskosität bestimmt. DieB-Werte hängen von der Zusammensetzung des Lösungsmittels ab und erreichen im wasserreichen Konzentrationsgebiet ein Maximum. Dieses Verhalten wird in Hinblick auf die Ionensolvatation und die Struktur des Lösungsmittels analysiert.相似文献
1000.
In the two-hase water-nitrobenzene extraction system, a method for gradual separation of Cs+, Sr2+ and Ba2+ from the mixture of cations forming stable non-extractable complexes with ethylenediamine-N, N, N,N-tetraacetic acid in the presence of the sodium salt of dicarbollylcobaltate anion {[-(3)-1, 2-B9C2H11]2 Co(III)}– and polyethylene glycol ligand with a mean relative molecular mass of 400 (PEG 400), respectively, was developed. In the first extraction step, Cs+ was extracted into the organic phase while the other cations studied (Ca2+, Sr2+, Ba2+, Zn2+, Co2+, Ce3+) remained in the aqueous phase. In the second extraction step, Sr2+ and Ba2+ were extracted into the nitrobenzene phase. Finally, in the following reextraction step, Sr2+ was transferred into the aqueous phase while Ba2+ remained in the organic phase. 相似文献