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941.
By irradiating (365 nm) an aqueous liquid solution of 4,5'-dimethylangelicin. a monofunctional photosensitizing furocoumarin, in the presence of an excess of thymine, two new compounds, I and II, have been obtained; they do not show fluorescence when observed with Wood's light. The nuclear magnetic resonance data, the marked similarity of UV absorption and fluorescence spectra of these compounds with those of synthetic 3.4-dihydro-4,5'-dimethylangelicin and their capacity to undergo photodissociation (254 nm) yielding the starting thymine and 4,5'-dimethylangelicin in equimolecular amounts, are consistent with C4-cycloadducts between the 3,4-double bond of the furocoumarin and 5,6-double bond of thymine. Nuclear magnetic resonance data indicate for I and II a head-to-head and a head-to-tail structure, respectively. When irradiation is carried out in the frozen state, two adducts. III and IV, fluorescent at Wood's light, have been obtained other than the two above-mentioned compounds I and II. Compounds III and IV have been identified as 4'.5'-fluorescent adducts between the 4',5'-double bond of the furocoumarin and the 5.6-double bond of thymine; one of them (III) is identical to that formed in the photoreaction between DNA and 4,5'-dimethylangelicin; for this last compound a cis head-to-head structure has been suggested.  相似文献   
942.
The reaction kinetics between O2? and C6H5CH2Br has been investigated in N,N′-dimethylformamide by electroanalytical techniques. A mechanism is proposed in which two molecules of the primary electrode product regenerate, via a following chemical reaction, one molecule of the original electroactive species. Furthermore, evidence for a SN2 reaction mechanism between O2? and C6H5CH2Br has been obtained. Second order rate constants resulted to be 11000 M?1s?1 and 3000 M?1s?1at room temperature and 0°C, respectively. The main products of the reaction were found to be benzylalcohol, benzaldehyde, benzene and biphenyl.  相似文献   
943.
Conclusions The partial hydrolysis of the pectin ofPanax ginseng C. A. Mey gives a polygalacturonide which has a linear carbohydrate chain consisting of residues of D-galacturonic acid in the pyranose form linked by -(1 4)-bonds.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 201–203, 1969  相似文献   
944.
A preferential solvation model that relates solute properties with solvent composition in binary mixtures has been applied to the dissociation pKa values of a set of 28 substituted phenols in methanol-water mixtures. The parameters of the model allow estimation of the pKa value of each phenol for any methanol-water composition. Moreover, it is demonstrated that the pKa values of the whole set of phenols at any methanol-water composition are linearly related to the pKa values of the phenols in water. Equations that relate the correlations' slope and intercept values with the solvent composition have been derived and tested with the set of phenols. The general parameters obtained for these equations allow an accurate calculation of the pKa value of any phenol, even of those not included in the original set, at any methanol-water composition solely from the pKa value of the phenol in water. These calculated pKa values can be used for quantitative structure-HPLC retention relationships. The method is tested by comparison of the calculated pKa values with the HPLC determined pKa values of 26 phenols in a polymeric column with a 50% methanol as mobile phase.  相似文献   
945.
The redox reaction between the ferric complex of hydrophobic porphyrin and sodium dithionite in two different phases occurring at the interface between two immiscible liquids has been investigated by Volta potential measurements and spectroscopy. The reduction of the ferric complex of hydrophobic porphyrin adsorbed at the interface was found to be accompanied by a potential shift in the negative direction and to depend significantly on the nature of the anion and the ionic strength of the supporting electrolyte. Specifically adsorbed halogen anions inhibited the redox reaction in the sequence: Cl?, Br?, I?. Depending on pH, the ferric complex of hydrophobic porphyrin exists in the uncharged (FeP-O-PFe) form or in the cation FeP+ form. The interaction between the ferric complex hydrophobic porphyrin and water has also been investigated.  相似文献   
946.
The five-membered ring of the indene system in 2,8-dioxo-3a-hydroxy-8a-R-1,2,3a,8a-tetrahydro-8H-indeno[1,2-d]imidazoles is hydrolytically cleaved in concentrated sulfuric acid solutions. Depending on the reaction conditions, compounds for which substituted 4-(o-carboxyphenyl)imidazol-2-one (II), 1,8-dioxo-1,2-dihydro-8H-imidazo[4,3-a]isoindole (III), and spiro[imidazolidine-4,3′-phthalide] structures were assumed were isolated.  相似文献   
947.
A series of symmetrically and asymmetrically substituted s-triazines was synthesized by condensation of fluorocarbon nitriles (Scheme II, compounds 1a-c ) and by cyclodehydration of a fluorocarbon imidoylamidine utilizing a fluorocarbon anhydride (Scheme III, compounds 2a-e ). Among the new nitriles prepared for incorporation in these reaction paths were 11-H-4,9-dioxahexadecylfluoroundecanenitrile ( 3 ) and 6-chloro-6-H-4-oxaheptafluorohexanenitrile ( 4 ), prepared by Scheme 1.  相似文献   
948.
The ionization and solution enthalpies of o-methoxybenzoic acid have been measured in H2O-DMSO mixtures. In the same solutions, the ΔG0 values for the ionization process have been determined by potentiometric measurements. A study of the ortho effects by means of a linear combination of the ordinary polar, proximity polar, and steric effects was also performed. The CH3O group seems to undergo a partial steric inhibition of resonance. Finally, the proton transfer process from the ortho derivative to benzoic acid, compared with the same process in the gaseous phase, is presented.  相似文献   
949.
F W Wang 《Macromolecules》1976,9(1):97-101
An equation for the translational diffusion coefficient of block copolymers in dilute solution has been obtained by modifying Zimm's equation for homopolymers to take into account the existence of dissimilar segments in block copolymers. Illustrative calculations for homopolymers and block copolymers have been made and the results for homopolymers have been compared with experiments and with the calculations of Yamakawa and Fujii. A procedure has been proposed to determine the molecular weight of a block copolymer from measurements of its limiting viscosity number and its sedimentation coefficient or translational diffusion coefficient.  相似文献   
950.
Fluorescence of the Xe2 continuum between 1460 and 1800 Å has been observed during excitation of Xe2 molecules with CO fourth positive bands from a microwave discharge lamp. Fluorescence spectra at different Xe and added gas pressures show that in collisions with Xe or Kr atoms, the excited Xe2 diatoms are efficiently relaxed to low vibrational levels of the 1Σu+ and 3Σu+ potentials without being quenched noticeably. With Kr the rate constant for relaxation out of the primarily excited high vibrational levels is found to be about 3×10?11 cm3 molecule?1 s?1.  相似文献   
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