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841.
H. Langfelderová L'. Macášková K. Otrubová J. Gažo 《Journal of Thermal Analysis and Calorimetry》1986,31(5):1143-1151
The thermal decompositions of Cu(en)2(NCS)X. where X–=Cl–, Br–, NO
3
–
, BF
4
–
and ClO
4
–
, have been studied in comparison with the courses of Cu(en)2(SCN)2 and Cu(en)2X2 decomposition. It is shown that the presence of the thiocyanate group in the complexes Cu(en)2(NCS)X is the most important factor in the decomposition course, in agreement with the fact that the anions X– are not coordinated. or are only semicoordinated. Significant differences were found in the courses of thermal decomposition of two forms of Cu(en)2(NCS)(BF4) differing in the structure of their coordination polyhedra.
Zusammenfassung Die thermische Zersetzung von Cu(en)2(NCS)X (X=Cl Br, NO3, BF4 und ClO4) wurde untersucht und mit der von Cu(en2(SCN)2 und Cu(en)2X2 verglichem. Der den Verlauf der Zersetzung entscheidend bestimmende Faktor isi die Anw esenheit der Thiocyanat-Gruppe in den Cu(en)2(NCS)X-Komplexen, was in Übereinstimmung damit steht,. daß die Anionen X nicht oder nur teilweise koordiniert sind. Es wurden signifikante Unterschiedeim Verlauf der thermischen Zersetzung von zwei sich in der Struktur ihrer Kordinationspolyeder unter-, heidenden Formen von Cu(en)2(NCS)(BF4) gefunden.
Cu(en)2(NCS)X (X–=Cl–, Br–, NO 4 – , NO 3 – , BF4 ClO4, Cu(en)2(SCN)2 Cu(en)2(X)2. , Cu(en)2(NCS)X X Cu(en) (NCS)BF4 i .相似文献
842.
The solubility products for some rare earth hydroxides and their temperature dependence have been shown. Greater solubility is shown for larger atomic radii and for lower temperature. 相似文献
843.
María Luisa Moyá Setefilla Escalera Cristina Martín Amalia Rodríguez María Mu?oz María del Mar Graciani 《Reaction Kinetics and Catalysis Letters》2006,89(1):177-182
Summary The reaction methyl 4-nitrobenzenesulfonate + Br- was studied in water-formamide tetradecyltrimethylammonium bromide micellar solutions. A pseudophase kinetic model was used
to quantitatively rationalize the kinetic micellar effects observed 相似文献
844.
Aviñó A Cubero E González C Eritja R Orozco M 《Journal of the American Chemical Society》2003,125(51):16127-16138
The structural, dynamical, and recognition properties of antiparallel DNA triplexes formed by the antiparallel d(G#G.C), d(A#A.T), and d(T#A.T) motifs (the pound sign and dot mean reverse-Hoogsteen and Watson-Crick hydrogen bonds, respectively) are studied by means of "state of the art" molecular dynamics simulations. Once the characteristics of the helix are defined, molecular dynamics and thermodynamic integration calculations are used to determine the expected stabilization of the antiparallel triplex caused by the introduction of 8-aminopurines. Finally, oligonucleotides containing 8-aminopurine derivatives are synthesized and tested experimentally using several approaches in a variety of systems. A very large stabilization of the triplex is found experimentally, as predicted by simulations. These results open the possibility for the use of oligonucleotides carrying 8-aminopurines to bind single-stranded nucleic acids by formation of antiparallel triplexes. 相似文献
845.
J. J. Galán J. L. Del Castillo A. González-Pérez J. Czapkiewicz J. R. Rodríguez 《Journal of solution chemistry》2003,32(10):919-927
The density and ultrasound velocity of aqueous solutions of tetradecyltrimethylammonium nitrate were measured in the temperature range of 15 to 35°C in 5°C intervals. The concentration range covered the premicellar and micellar regimes. By assuming a pseudophase separation model for the micellar system, we applied the densitometric data to estimate the apparent molar volumes and the apparent thermal expansibility coefficients of the surfactant in monomeric and micellar forms. Ultrasound velocity and density data enabled us to estimate the isentropic compressibility of the surfactant in both forms. The results are compared with relevant literature data for alkyltrimethylammonium bromides. 相似文献
846.
Simplistic modeling approach to heterogeneous dilute-acid hydrolysis of cellulose microcrystallites 总被引:9,自引:0,他引:9
Pär O. Pettersson Robert W. Torget Robert Eklund Qian Xiang Y. Y. Lee Guido Zacchi 《Applied biochemistry and biotechnology》2003,106(1-3):451-455
The classic kinetic model for cellulose hydrolysis is often referred to as pseudo-homogeneous, a term revealing the insight that the process is actually heterogeneous. During the past 10–15 yr, the shortcomings of this
model have been demonstrated in various studies and the interest in the heterogeneous aspects has increased. The present work
presents a simplistic model in which the intrinsic, heterogeneous hydrolysis and transport rates are coupled by the assumption
of a constant glucosidic surface concentration. The mechanisms affecting these two rates are largely unknown, but the model
serves as a guideline for further exploration of the process. 相似文献
847.
The performance of a recently developed method to generate representative atomistic models of amorphous polymers has been investigated. This method, which is denoted SuSi, can be defined as a random generator of energy minima. The effects produced by different parameters used to define the size of the system and the characteristics of the generation algorithm have been examined. Calculations have been performed on poly(L,D-lactic) acid (rho = 1.25 g/cm3) and nylon 6 (rho = 1.084 g/cm(3)), which are important commercial polymers. 相似文献
848.
A new method for the speciation of inorganic [Sb(III) and Sb(V)] and organic (Me3SbCl2) antimony species by using a polystyrene-divinylbenzene-based anion-exchange HPLC column (Hamilton PRP-X100) coupled to hydride generation atomic fluorescence spectrometry (HG-AFS) is presented. Several mobile phases were tested for the baseline separation of these three antimony species, investigating in detail experimental parameters such as concentration and pH. The best efficiency and resolution was achieved by using a gradient elution between diammonium tartrate 250 mmol l(-1) pH 5.5 (A) and KOH 20 mmol l(-1) pH 12 (B). The gradient programme used was 100% B for 1.5 min, decreasing to 0% B in 0.1 min and maintained the elution with 100% A for 5.5 min. Analysis time was less than 7 min. Equilibration of the column with the complexing mobile phase was found to be critical in order to avoid Sb(III) double peak formation. Dilution in diammonium tartrate medium was necessary in order to avoid Sb(III) oxidation at microg l(-1) concentration level. Detection limits of 0.06 microg l(-1) for Sb(V), 0.09 microg l(-1) for Me3SbCl2 and 0.04 microg l(-1) for Sb(III) as well as repeatability and reproducibility better than 5% R.S.D. (n = 10) and 9% R.S.D. (n = 30) (for 1 and 5 microg l(-1) of Sb(V) and Sb(III) and 5 and 10 microg l(-1) of Me3SbCl2) were obtained. Accuracy and recovery studies were carried out by analysing one river freshwater sample and two water certified reference materials. The proposed methodology can be considered reliable and straightforward for antimony speciation in fresh water samples. 相似文献
849.
Rubio-Hernández FJ Gómez-Merino AI Ruiz-Reina E 《Journal of colloid and interface science》2000,222(1):103-106
A study on the electroviscous effect of alumina suspensions has been made. At the low volume fraction of the particles studied here only a first-order effect was detected. Ubbelohde-type capillary viscometers have been used. A simple method to determine the hydrodynamic constant k(1) has been proposed. The experimental primary electroviscous coefficients corresponding to different electrolyte concentrations have been compared with two different theoretical approachs (I. G. Watterson, and L. R. White, J. Chem. Soc. Faraday Trans. 2 77, 1115 (1981); F. J. Rubio-Hernández, E. Ruiz-Reina, and A. I. Gómez-Merino, J. Colloid Interface Sci. 206, 334 (1998)) and the results suggest that the presence of a dynamic Stern layer plays a certain role in this effect. Copyright 2000 Academic Press. 相似文献
850.
π-electron energies and bond orders of benzenoid hydrocarbons with up to five fused hexagons have been considered by the simple
Bond Orbital Resonance Theory (BORT) approach. The corresponding ground states were determined according to four BORT models.
In the first three models a diagonalisation of the Hückel-type Hamiltonian was performed in the bases of Kekulé, of Kekulé
and mono-Claus and of Kekulé and Claus resonance structures, respectively. In the fourth model a simple BORT ansatz was used.
According to this ansatz, the ground state is a linear combination of the positive Kekulé structures, all with equal coefficients.
It was shown that π-electron energies and bond orders obtained by these models correlate much better with the PPP energies
and bond orders than with the Hückel energies and bond orders. This indicates that a simple BORT approach is quite reliable
in predicting the more sophisticated PPP results. Concerning the relative performance of the four BORT models, the best results
were obtained with the BORT ansatz. The performance deteriorates with the expansion of the basis set. This is attributed to
the fact that in these models the improvement of the basis set is not accompanied with the corresponding improvement of the
Hamiltonian. Comparing the BORT-ansatz bond orders with the Pauling bond orders, it was shown that BORT-ansatz bond orders
correlate much better with the PPP bond orders.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献