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31.
Chemical, structural, and thermal properties of Zn(II)-Cr(III) layered double hydroxides intercalated with sulfated and sulfonated surfactants 总被引:1,自引:0,他引:1
Crepaldi EL Pavan PC Tronto J Valim JB 《Journal of colloid and interface science》2002,248(2):429-442
Zn(II)-Cr(III)-LDHs (layered double hydroxides) containing sulfated or sulfonated surfactants as the interlamellar anion were synthesized by the coprecipitation method. The syntheses were conducted under various different experimental conditions, such as the Zn : Cr ratio, pH, and aging time. In each of the prepared materials, unlike previously reported data, the interlayer anion arrangement did not change, being consistent with a perpendicular monolayer. The thermal decomposition process of the prepared materials was studied by a set of analysis methods, such as TG/DTA, TG/MS, PXRD, and FT-IR. From the results obtained it was possible to conclude that, in an air atmosphere, the anions decomposed by a partial combustion, leading to the formation of sulfide. The results also showed that sulfonated surfactants containing LDHs are much more stable than those containing sulfated surfactants. A mechanism was proposed for the thermal decomposition of such LDHs based on the experimental results. 相似文献
32.
VISIBLE CHEMILUMINESCENCE ASSOCIATED WITH THE REACTION BETWEEN METHEMOGLOBIN OR OXYHEMOGLOBIN WITH HYDROGEN PEROXIDE 总被引:1,自引:0,他引:1
Eduardo A. Lissi Jorge Escobar Carlos Pascual Maria del Castillo Tais H. Schmitt Paolo Di Mascio 《Photochemistry and photobiology》1994,60(5):405-411
Abstract Visible chemiluminescence is emitted in the irreversible deactivation of hemoglobin or methemoglobin with excess H2 O2 . The emission takes place in two phases. The most intense one lasts a few seconds and is followed by a second phase of lower intensity that remains for longer periods. This second phase presents chaotic or sustained oscillations. Free radicals are implicated in the luminescent process since the emission can be reduced by free radical scavengers such as 6-hydroxy-2,5,7,8,-tetramethylchroman-2-carboxylic acid (Trolox) or ascorbic acid. These additives lead to a delay in reaching the maximum intensity, which can be related to their consumption, implying substantial recycling of the hemoprotein. Chemiluminescence is also observed in the oxidation of hemin by H2 O2 , suggesting a role for the heme group in the processes leading to the excited state production. The lower intensity observed in the presence of hemin can be related to the contribution of the globin chains. 相似文献
33.
Miguel A. Vzquez Segura Josefa Donoso Francisco Muoz INS Fernandez
de
Pirola Francisco Garcia Blanco Gerardo R. Echevarria 《Photochemistry and photobiology》1993,57(Z1):923-928
Abstract— Absorption and fluorescence spectra of 5′-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (fN, fz) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δv), fluorescence quantum yield of the neutral form (QN), fluorescence ratio of the neutral to the zwitterionic form (øN/øZ) and the rate constant of tautomerization (k1) from Z to N in the excited state. Some of these parameters (fN, Δv, QN, k1) were found to depend on the proton donor character of the solvent, whereas others (øN/øZ) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment. 相似文献
34.
Oscar E. Piro Eduardo E. Castellano Roberto C. V. Piatti Agustín E. Bolzn Alejandro J. Arvia 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m252-m255
The crystal structures of two salts of bis(thiourea)gold(I) complexes, namely bis(thiourea‐κS)gold(I) chloride, [Au(CH4N2S)2]Cl, (I), and bis[bis(thiourea‐κS)gold(I)] sulfate, [Au(CH4N2S)2]2SO4, (II), have been determined. The chloride salt, (I), is isomorphous with the corresponding bromide salt, although there are differences in the bonding. The AuI ion is located on an inversion centre and coordinated by two symmetry‐related thiourea ligands through the lone pairs on their S atoms [Au—S 2.278 (2) Å and Au—S—C 105.3 (2)°]. The sulfate salt, (II), crystallizes with four independent [Au(CH4N2S)2]+ cations per asymmetric unit, all with nearly linear S—Au—S bonding. The cations in (II) have similar conformations to that found for (I). The Au—S distances range from 2.276 (3) to 2.287 (3) Å and the Au—S—C angles from 173.5 (1) to 177.7 (1)°. These data are relevant in interpreting different electrochemical processes where gold–thiourea species are formed. 相似文献
35.
Calculations involving molecular orbitals have appeared in the chemical literature over the past few years, but all have used smalltrans-polyenes. We now report extended Huckel molecular orbital calculations ontrans-polyenes of up to 18 double bonds (36 carbons and 38 hydrogen atoms). Information obtained from these calculations include total energies, bond gaps, and net charges on each atom. Also found is that the band gap approaches 1.41 eV as the number of double bonds approaches infinity. This value is quite close to reported experimental values. Data are also presented for polyenes assuming equal C-C bond lengths. 相似文献
36.
M. J. Fernandez E. Galvez A. Lorente I. Iriepa J. A. Soler 《Journal of heterocyclic chemistry》1989,26(2):307-312
1-Azatricyclo[3.3.1.13-7]decan-4-one (4-oxo-1-azaadamantane) and 1-azatricyclo[3.3.1.13-7]decane-4-α(β)-ol (4-α-(β)-hydroxy-1-azaadamantane) have been studied by 1H and 13C nmr methods. From this study several stereo and stereoelectronic effects have been deduced. The complete proton and carbon chemical shift assignments for the title compounds have been made, with the aid of two-dimensional nmr techniques. 相似文献
37.
Mafra L Paz FA Shi FN Rocha J Trindade T Fernandez C Makal A Wozniak K Klinowski J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(2):363-375
A compound formulated as (C4H12N2)[Ge2(pmida)2(OH)2] x 4 H2O (where pmida(4-) = N-(phosphonomethyl)iminodiacetate and C4H12N2(2+) = piperazinedium cation), containing the anionic [Ge2(pmida)2(OH)2]2- complex, has been synthesised by the hydrothermal approach and its structure determined by single-crystal X-ray diffraction analysis. Several high-resolution solid-state magic-angle spinning (MAS) NMR techniques, in particular two-dimensional 1H-X(13C,31P) heteronuclear correlation (HETCOR) and 1H-1H homonuclear correlation (HOMCOR) experiments incorporating a frequency-switched Lee-Goldburg (FS-LG) decoupling scheme, have been employed for the first time in such a material. Using these tools in tandem affords an excellent general approach to study the structure of other inorganic-organic hybrids. We assigned the NMR resonances with the help of C...H and P...H internuclear distances obtained through systematic statistical analyses of the crystallographic data. The compound was further characterised by powder X-ray diffraction techniques, IR and Raman spectroscopy, and by elemental and thermal analyses (thermogravimetric analysis and differential scanning calorimetry). 相似文献
38.
Garcia Ruano JL Alcudia A del Prado M Barros D Maestro MC Fernandez I 《The Journal of organic chemistry》2000,65(10):2856-2862
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported. 相似文献
39.
Martinez Alvarez R Herrera Fernandez A Chioua M Ramiro Perez P Villalba Vilchez N Guzman Torres F 《Rapid communications in mass spectrometry : RCM》1999,13(24):2480-2488
Several 5,6-dialkyl-2,4-diarylpyrimidines were prepared and their electron ionization (EI) mass spectra reported. The benzylic cleavage takes place easily together with an important McLafferty rearrangement. The involvement of the nitrogen atom appears to be important in the fragmentation of 5-methyl-substituted pyrimidines. In contrast, the 6-methyl-substituted pyrimidines undergo benzylic cleavage without hydrogen transfer. Thus, the difference in the mass spectrometric behaviour allows the identification of these isomeric compounds which, in contrast, exhibit only small differences in their NMR spectra. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
40.
Low temperature infrared spectra of light induced metastable states MS1 and MS2 of the nitroprusside anion in Na(2)[Fe(CN)(5)NO].2H(2)O, isotopically normal and substituted with (15)NO and N(18)O, are presented and discussed. As a consequence of the relatively high population of the MS2 state achieved by further irradiation with 1064 nm light of samples previously irradiated with 488.0 nm light, new bands were seen for the first time, and others, previously reported, were confirmed. The comparison of the spectral data obtained for the FeNO moiety of the isotopically normal as well as of the (15)NO and N(18)O substituted anion with the results of quantum chemical (DFT) calculations support the assignment of the bands which appear after successive irradiations to MS1, the linear Fe(eta(1)-ON) linkage isomer, and to MS2, the side-bound Fe(eta(2)-NO) isomer. 相似文献