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141.
Thomas C. Amu 《Journal of solution chemistry》1981,10(1):69-78
Interdiffusion coefficient have been measured for 1,1,2,2-tetrabromoethane in 21 organic solvents in order to ascertain the influence of shape, size, viscosity, nature and degree of branching, of the solvent molecules on transport properties. None of the existing correlations for diffusion in binary liquid systems appear to fit all the experimental data. Steric effects due to the solvent molecules are shown to be very important in the interpretation of the diffusion process. 相似文献
142.
Medical grade PVC plasticised with polycaprolactone–polycarbonate (PCL–PC) was subjected to aqueous environments at different temperatures. The release profile during ageing was determined by solid phase microextraction (SPME) and GC–MS. At the same time changes in the surface composition due to, for example, migration of PCL–PC from the blend were followed by FTIR. Almost no changes in the material or its surface composition were observed during 98 days at 37 °C in water or phosphate buffer. Only trace amount of 6-hydroxyhexanoic acid the final hydrolysis product of PCL–PC was detected in the GC–MS chromatograms and the weight loss was negligible. Even when the ageing temperature was raised to 70 °C only minor increase in the amount of 6-hydroxyhexanoic acid was observed and the weight loss after 98 days was under 1%. Changes in the FTIR spectra indicating migration of PCL–PC towards the surface of the PVC/PCL–PC tubing were observed first after 70 days at 70 °C. Large increase in the hydrolysis rate of PCL–PC and almost complete depletion of PCL–PC from the blend was observed when the ageing temperature was raised to 100 °C. 相似文献
143.
144.
145.
The molecular complex formation reactions of uridine (Urd) with adenosine (Ado), cytidine (Cyd), thymidine (Thd), adenosine 5-monophosphate (AMP) and cytidine 5-monophosphate (CMP) have been studied at 20°C. It was found that the main positive noncovalent centers of ion–dipole and dipole–dipole type interactions are the protonated N(3) atoms of Urd, whereas the negative centers are the endocyclic atoms of the bases characterized by high electron density from the second molecule involved in the reaction. Moreover, NMR results indicate the occurrence of stacking in the complex (Urd)H(Cyd), whereas in the complex, (Urd)H2(Thd), it is the only type of interaction. Deprotonation of the latter species brings about a change in the character of the reaction and ion–dipole interactions have been detected in the adduct, (Urd)H(Thd). Interestingly, no involvement of the phosphate groups in the formation of AMP and CMP adducts has been evidenced and the main centers of the reactions were found to be the N(7)and N(1) atoms of AMP, or the N(3) atoms of CMP and Urd. Moreover, in the Urd/CMP system the NMR results suggest stacking-type interactions. 相似文献
146.
E. A. Zheligovskaya 《Journal of Structural Chemistry》2003,44(5):827-835
A computer simulation of proton-ordered ice IX and its proton-disordered analog III (768 molecules, 90 K) was carried out by the molecular dynamics method using Poltev–Malenkov's potential. For ice IX, the differences in the dynamic characteristics of molecules with O(1) and O(2) are much wider than those in the case of ice III. The libration spectrum of ice IX has a number of distinct acute peaks, and the spectrum of ice III is strongly smoothed. These peculiarities are explained by the proton ordering of ice IX and disordering of ice III. The latter is responsible for the great differences in the short- and especially long-range environment of water molecules in ice crystals and hence for the presence of many molecules with different dynamic characteristics. Thus averaging over a large number of different vibrational spectra of molecules leads to a smoothed total spectrum in the case of the proton-disordered crystal modification of ice. 相似文献
147.
V. A. Pankratov Ts. M. Frenkel A. E. Shvorak S. V. Lindeman Yu. T. Struchkov 《Russian Chemical Bulletin》1993,42(1):81-87
A 11-complex of trinitrophenol with benzyldimethylamine (1) and a 111-complex, the product of the interaction of benzyldimethylamine, glycidyl phenyl ether, and phenol (2), have been synthesized and characterized by means of X-ray analysis. Complex1 is a precursor for the catalysts of selective isocyanate cyclotrimerization, while complex2 is one of those catalysts. In the crystal structure complex1 forms H-bonded cationic-anionic aggregates with proton transfer from phenol to the N-atom of the tertiary amine. Complex2 crystallizes as a monohydrate (2a) with a strong H-bond between the quaternary ammonium and phenolic components, and exists in crystals in the form of globular H-bonded dimeric hydrates. Possible pathways of dissociation of complex2a are discussed. The data obtained may be used as a basis for further interpretation of the regularities of cyclotrimerization of isocyanates catalyzed by complexes of this type.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 92–97, January, 1993. 相似文献
148.
O. S. Filipenko S. M. Aldoshin G. V. Shilov N. I. Makarova V. A. Kharlanov M. I. Knyazhanskii 《Russian Chemical Bulletin》1995,44(2):287-292
The molecular structures of the initial compounds and the products of photocyclization involving amino and azomethine groups in perchlorates ofN-amino (1) andN-azomethine (2) derivatives of 2,4,6-triphenylpyridinium cations were studied. Cations1 and2 have an essentially non-coplanar arrangement of the -Ph rings, and the product of photocyclization of2, cation3, is characterized by a flattened structure. It was found that the orientation of the lone electron pair of the N atom with respect to one of the planes of the -Ph rings in molecule1 is more favorable for monocyclization involving the amino group. The structure of molecule2 allows two routes of the photoreaction,viz., O N proton transfer and monocyclization with an -Ph ring. However, the structural features of molecule2 are more favorable for photocyclization.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 296–301, February, 1995. 相似文献
149.
Summary The concept of a diffusion-averaged molecular weight, Md is presented, and Md is defined for polydisperse samples. It is shown via oligostyrene mixtures that Md can be determined in 20 minutes with common chromatographic equipment. If Md is measured and Mn or Mw is known, the polydispersity can be obtained. 相似文献
150.
Viscometric method has been used to study the interaction between the weak interacting systems such as benzene-CCl4-cyclohexane, toluene-CCl4-cyclohexane ando- xylene-CCl4-cyclohexane. The equilibrium constants and other thermodynamic parameters have been reported and compared with literature
data. 相似文献