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151.
Density functional theory (DFT) calculations have been performed on the terminal dihalogallyl complexes of iron, ruthenium, and osmium (η(5)-C(5)H(5))(Me(3)P)(2)M(GaX(2)) (M = Fe, Ru, Os; X = Cl, Br, I) and (η(5)-C(5)H(5))(OC)(2)Fe(GaX(2)) (X = Cl, Br, I) at the BP86/TZ2P/ZORA level of theory. On the basis of analyses suggested by Pauling, the M-Ga bonds in all of the dihalogallyl complexes are shorter than M-Ga single bonds; moreover, on going from X = Cl to X = I, the optimized M-Ga bond distances are found to increase. From the perspective of covalent bonding, however, π-symmetry contributions are, in all complexes, significantly smaller than the corresponding σ-bonding contribution, representing only 4-10% of the total orbital interaction. Thus, in these GaX(2) complexes, the gallyl ligand behaves predominantly as a σ donor, and the short M-Ga bond lengths can be attributed to high gallium s-orbital character in the M-Ga σ-bonding orbitals. The natural population analysis (NPA) charge distributions indicate that the group 8 metal atom carries a negative charge (from -1.38 to -1.62) and the gallium atom carries a significant positive charge in all cases (from +0.76 to +1.18). Moreover, the contributions of the electrostatic interaction terms (ΔE(elstat)) are significantly larger in all gallyl complexes than the covalent bonding term (ΔE(orb)); thus, the M-Ga bonds have predominantly ionic character (60-72%). The magnitude of the charge separation is greatest for dichlorogallyl complexes (compared to the corresponding GaBr(2) and GaI(2) systems), leading to a larger attractive ΔE(elstat) term and to M-Ga bonds that are stronger and marginally shorter than in the dibromo and diiodo analogues. 相似文献
152.
Reetz MT Soni P Fernández L Gumulya Y Carballeira JD 《Chemical communications (Cambridge, England)》2010,46(45):8657-8658
Mutants of the lipase from Bacillus subtilis, previously engineered for enhanced thermostability using directed evolution based on the B-FIT method, show significantly increased tolerance to hostile organic solvents. 相似文献
153.
Gupta AK Pardasani D Kanaujia PK Tak V Dubey DK 《European journal of mass spectrometry (Chichester, England)》2006,12(4):271-277
The detection and identification of markers of scheduled chemicals plays an important role in verification analysis of Chemical Weapons Convention (CWC). This paper describes the gas chromatography electron ionization mass spectrometric (GC/EI-MS) analysis of N,N-dialkylaminoethyl-2-methoxyethyl ethers (DAEMEs), which are identified as characteristic degradation markers of N,N-dialkylaminoethyl-2-chlorides. N,N-dialkylaminoethyl-2-chlorides produced DAEMEs on reacting with the universally used decontamination solution (DS-2). DAEMEs were prepared by condensation of N,N-dialkylaminoethyl-2-chlorides with 2-methoxy ethanol the active ingredient of DS-2. Based on the GC/EI-MS analysis of DAEMEs the generalized fragmentation routes are proposed which rationalize most of the characteristic ions in EI-MS. 相似文献
154.
Pair of weights u, v is characterized so that the Hardy-Steklov operator is compact between weighted Lebesgue spaces Lp(u) and Lq(v), where 1<p,q<∞, a,b are certain increasing functions and f?0. The compactness of the conjugate operator is also studied. 相似文献
155.
156.
[Ru(1,10-phenanthroline)(2)(4,4,4',4'-tetramethyl-2,2'-bisoxazoline)](PF(6))(2).H(2)O (1) shows a (3)MC emission in CH(3)CN and CH(3)OH at room temperature around 590 nm with radiative lifetimes of 1.22 x 10(-4) and 1.40 x 10(-4) s, respectively. The X-ray crystal structure of 1 has been determined. 相似文献
157.
A concise, highly efficient formal total synthesis of dl-physostigmine is described, using a relatively simple method that should be adaptable to the synthesis of homologous members of this type of alkaloid. The key step in the synthesis is a new vicarious nucleophilic substitution reaction between p-nitroanisole and a C-silylated derivative of N-methylpyrrolidinone. Subsequent conversion of the initial adduct to the tricyclic framework of physostigmine follows a well-established protocol and provides the key intermediate 8 in high yield. The vicarious nucleophilic substitution reaction has also been extended to six-membered lactams, with encouraging results. 相似文献
158.
William H. Mullen Fiona H. Keedy Stephen J. Churchouse Pankaj M. Vadgama 《Analytica chimica acta》1986
An enzyme electrodes is described for glucose determination in unstirred, undiluted whole blood. The system comprises an H2O2-detecting electrode upon which is placed a membrane laminate incorporating glucose oxidase. The external membrane was pretreated with methyltrichlorosilane. The electrode response was linearly dependent on glucose concentration up to 50 mmol l?1 glucose, it had a decreased dependence on dissolved oxygen concentrations and gave response times of 30–90 s. Whole blood glucose measurements correlated well with a routine spectrophotometric method. 相似文献
159.
Oliveira-Brett AM Silva LA Farace G Vadgama P Brett CM 《Bioelectrochemistry (Amsterdam, Netherlands)》2003,59(1-2):49-56
The oxidation mechanism and adsorption of inosine 5'-monophosphate and hypoxanthine were investigated in solutions of different pH using voltammetric and impedance methods at glassy carbon electrodes. For both compounds, the pH dependence from differential pulse voltammetry showed that the same number of electrons and protons are involved in the rate-determining step of the electrochemical reaction. In the case of hypoxanthine, it was also possible to study the effect of different concentrations. At high concentrations of hypoxanthine, two oxidation peaks were observed, the first due to hypoxanthine oxidation with formation of oligomers and the second due to hypoxanthine oligomer oxidation, both compounds adsorbing strongly. Impedance measurements corroborated the voltammetric results and enabled the study of the adsorption of hypoxanthine on glassy carbon. 相似文献
160.
A model is developed to study diffusive mass transfer of hydrocarbon vapor through a flexible foam blanket. The model accounts for the diffusion of hydrocarbon vapor through gas-phase and liquid lamellae, the combined gravity and capillary drainage from the plateau border, the thinning of foam lamellae caused by the forces of capillary suction, London-van der Waals attraction, and electrostatic double-layer repulsion, and foam collapse. Uniform bubble size is assumed, and hence, interbubble gas diffusion arising out of variation in bubble sizes alone is not incorporated into the model. A high-stability aqueous foam formulation that remains stable in the presence of oil (hexane) at foam-oil contact was developed using surfactants, stabilizers, and viscosifiers. Emission of hexane vapor through the foam was measured. The model predicts that the initially taller foam columns collapse faster. Their mass-transfer resistance is higher before the onset of collapse but not very different from that of the shorter foam columns at long times. If the solubility and diffusivity of the hexane gas in the foam liquid are unaffected, the foams with higher viscosities persist longer and provide greater diffusive mass-transfer resistance. Foam bubble size does not significantly impact the mass-transfer resistance of the foam column before the onset of foam collapse. However, the foams with smaller bubbles collapse earlier, and their ability to act as a mass-transfer barrier to the diffusing hydrocarbon vapor diminishes rapidly. The experimental results compared reasonably with the model for varying initial foam heights and bubble sizes. 相似文献