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111.
Boźenna Golankiewicz Piotr Januszczyk Maria Gdaniec Zofia Kosturkiewicz 《Tetrahedron》1985,41(24):5989-5994
2-Acylamino-2-cyanoacetic acid ethyl esters react with 2,4-bis (4-methoxyphenyl)-1, 3, 2, 4-dithiadiphosphetane 2,4-disulfide in refluxing benzene with formation of 2-alkyl(aryl)-5-aminothiazole-4-carboxylic acid ethyl esters . Structure was established by spectroscopic means and an X ray crystallographic investigation of . X-Ray analysis revealed that the thiazole ring, exocyclic nitrogen and carbonyl group forming a hydrogen-bonded cycle are nearly coplanar. A resonance interaction is manifested by distinctly shortened /1.447 (3)/ C(carbonyl)-C(thiazole) distance. 相似文献
112.
Zofia Borkowska 《Journal of Electroanalytical Chemistry》1975,63(3):379-392
The adsorption of acetone on a mercury electrode from (CH3)2CO+H2O+HCl solutions has been studied using a thermodynamically rigorous procedure. The chemical potential of the supporting electrolyte has been kept constant by using the concentrations corresponding to the constant e.m.f. of the cell with electrodes reversible to each of the ions in the solutions. It is suggested that the molecule is to some extent oriented with the hydrocarbon part towards mercury. The composition of the surface layer has been calculated. 相似文献
113.
Summary A procedure is proposed for determination of small amounts of silver in copper ores and processed products. The samples are dissolved in a Teflon bomb in a mixture of hydrofluoric and nitric acids, then evaporated in the presence of nitric and boric acids. Silver is extracted from the sample solution with a solution of triphenylphosphine in methyl isobutyl ketone, then determined by atomic-absorption spectrophotometry. The method is precise and accurate. The relative standard deviation for a silver content of 10–4% is about 4%.
Zusammenfassung Ein Verfahren zur Bestimmung kleiner Mengen Silber in Kupfererzen und daraus hergestellten Produkten wurde vorgeschlagen. Die Proben werden in einer Teflonbombe in einem Gemisch aus Flußsäure und Salpetersäure gelöst und dann in Gegenwart von Salpetersäure und Borsäure eingeengt. Das Silber wird mit Triphenylphosphin, gelöst in Isobutylmethylketon, aus der Probelösung extrahiert und dann mit Hilfe der AAS bestimmt. Das Verfahren ist genau, die relative Standardabweichung beträgt bei einem Silbergehalt von 10–4% ungefähr 4%.相似文献
114.
Katarzyna Michalik Zofia Drzazga Anna Michnik M. Kaszuba 《Journal of Thermal Analysis and Calorimetry》2007,88(2):401-404
A thermal
and kinetic analysis of two protease inhibitors: nelfinavir mesylate and atazanavir
sulfate, were carried out to find their thermal stability. DSC curves of both
drugs showed exothermic transition. This observed process resulted in two
steps. Obtained apparent activation energy pointed at low stability of studied
protease inhibitors in water solutions. 相似文献
115.
Equilibrium constants have been determined both potentiometrically and spectrophotometrically for reactions of the type M2++Cl??MCl+ using aqueous solutions of the corresponding metal perchlorates as the reaction media (M=Mn, Co, Ni, and Zn). The variation in the quotient of the activity coefficients of these reactions with increasing molality of the reaction medium has been found to be approximately the same for the CuCl+ (previously studied), MnCl+, and ZnCl+ complexes, while a different dependence is observed for the CoCl+ and NiCl+ complexes. The results are interpreted as indicating equilibrium coexistence of the [MCl(OH2)5]+ and {[M(OH2)6]Cl}+ species in the latter two cases. Approximate values of the corresponding equilibrium constants are estimated in addition to the derived overall thermodynamic stability constants of the MCl+ formal complexes. The latter are found to follow a partly inverted Irving-Williams series, the fact being accountable in terms of the ligand field stabilization energy. 相似文献
116.
Density functional calculations for the [(RS)xFe(NO)4−x]− (R=CH3) compounds are carried out using the DFT method with the B3LYP functional. The results can be verified by the experimental data only in the case of the [(RS)2Fe(NO)2]− complex. The experimentally characterised molecular structure of [(RS)2Fe(NO)2]− (where (RS)2=(SCH2CH2NMeCH2CH2CH2NMeCH2CH2S) is properly reproduced by the RB3LYP method. The discrepancy between the calculated spin densities with the integral spin observed experimentally is interpreted in terms of antiferromagnetic coupling between the Fe(III) centre and the NO− ligands. The theoretical analysis gives a good account of some properties observed in these compounds. In particular, the electronic spectrum calculated by the TDDFT method for [(CH3S)2Fe(NO)2]− is similar in shape to the experimental one, although is hypsochromically shifted. The LLCT (Sπ→π*NO), LMCT (Sπ→d) or (π*NO→d+Sπ→d) and MLCT (d→π*NO) transitions are mostly responsible for absorption of the [(RS)xFe(NO)4−x]− complexes within UV-Vis. The chemical reactivity of [(RS)2Fe(NO)2]− is interpreted basing on the calculated effect of a polar solvent on the ligand polarity and on the character of the HOMO and LUMO orbitals. 相似文献
117.
N-Glyoxyloyl-(2R)-bornane-10,2-sultam and (1R)-8-phenylmenthyl glyoxylate react stereoselectively with simple nitro compounds giving diastereoisomeric nitroalcohols with high asymmetric induction. N-Glyoxyloyl-(2R)-bornane-10,2-sultam 1a is shown to be a highly efficient chiral inducer, superior to (1R)-8-phenylmenthyl glyoxylate 1b. In all cases, the absolute (2S) configuration at the center bearing the hydroxy group and the relative syn configuration for the major diastereoisomers were determined. 相似文献
118.
All proteins contain groups capable of exchanging protons with their environment. We present here an approach, based on a rigorous thermodynamic cycle and the partition functions for energy levels characterizing protonation states of the associating proteins and their complex, to compute the electrostatic pH-dependent contribution to the free energy of protein-protein binding. The computed electrostatic binding free energies include the pH of the solution as the variable of state, mutual "polarization" of associating proteins reflected as changes in the distribution of their protonation states upon binding and fluctuations between available protonation states. The only fixed property of both proteins is the conformation; the structure of the monomers is kept in the same conformation as they have in the complex structure. As a reference, we use the electrostatic binding free energies obtained from the traditional Poisson-Boltzmann model, computed for a single macromolecular conformation fixed in a given protonation state, appropriate for given solution conditions. The new approach was tested for 12 protein-protein complexes. It is shown that explicit inclusion of protonation degrees of freedom might lead to a substantially different estimation of the electrostatic contribution to the binding free energy than that based on the traditional Poisson-Boltzmann model. This has important implications for the balancing of different contributions to the energetics of protein-protein binding and other related problems, for example, the choice of protein models for Brownian dynamics simulations of their association. Our procedure can be generalized to include conformational degrees of freedom by combining it with molecular dynamics simulations at constant pH. Unfortunately, in practice, a prohibitive factor is an enormous requirement for computer time and power. However, there may be some hope for solving this problem by combining existing constant pH molecular dynamics algorithms with so-called accelerated molecular dynamics algorithms. 相似文献
119.
Anna Pasternak Ryszard Kierzek Zofia Gdaniec Maria Gdaniec 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(8):o467-o470
The title compound [systematic name: (1S,3S,4R,7S)‐3‐(4‐amino‐1H‐pyrazolo[3,4‐d]pyrimidin‐1‐yl)‐1‐hydroxymethyl‐2,5‐dioxabicyclo[2.2.1]heptan‐7‐ol], C11H13N5O4, belongs to a family of nucleosides with modifications in both the sugar and nucleobase moieties: these modifications are known to increase the thermodynamic stability of DNA and RNA duplexes. There are two symmetry‐independent molecules in the asymmetric unit that differ significantly in conformation, and both exhibit a high‐anti conformation about the N‐glycosidic bond, with χ torsion angles of −85.4 (3) and −87.4 (3)°. The sugar C atom attached to the nucleobase N atom is −0.201 (4) and 0.209 (4) Å from the 8‐aza‐7‐deazaadenine skeleton plane in the two molecules. The molecules are assembled into layers via hydrogen bonds and π–π stacking interactions between the modified nucleobases. 相似文献
120.
Monomethylated alkanes have been proposed to be contained in exhaled breath, their concentration pattern serving for identification of lung carcinoma, breast carcinoma and rejection of foreign tissue after heart transplant rejection. Improving the accuracy of identification for monomethylated alkanes will enhance work on their biochemical background which presently is unknown. The programmed temperature linear retention indices of all 196 C(4)-C(30) monomethylalkanes on OV-1 stationary phase were measured with an average repeatability of +/-0.07 index units (i.u.). The mixture of C(9)-C(30) monomethylalkanes was prepared by methylene insertion reaction to C(8)-C(29)n-alkanes mixture. The preliminary identification of monomethylalkanes was performed on the basis of the dependence of homomorphy factors on the number of carbon atoms of individual homologous series of monomethylalkanes (retention indices extrapolated with s=0.15 i.u.). The prediction of retention of isomers with new position of methyl group beginning at higher carbon atoms number, as well as for second, third, fourth, etc., member of homologous series allowed the dependence H(P)=f(C(n)) for first, second, third, etc., members of beginning homologous of monomethylalkane series (retention indices extrapolated with s=0.17 i.u.). The identification was confirmed by mass spectrometry. All gas chromatographic unseparated monomethylalkane isomers with methyl-group near the middle of molecule carbon chain were resoluted by mass spectrometric deconvolution. Obtained regular dependences H(P)=f(C(n)) allow precise retention prediction of monomethylalkanes C(30). 相似文献