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101.
Rodella Cristiane B. Franco Roberto W.A. Magon Claudio J. Donoso Jose P. Nunes Luis A.O. Saeki Margarida J. Aegerter Michel A. Sargentelli Vagner Florentino Ariovaldo O. 《Journal of Sol-Gel Science and Technology》2002,25(1):83-88
Raman spectroscopy and Electron Paramagnetic Resonance (EPR) studies were performed on a series of V2O5/TiO2 catalysts prepared by a modified sol-gel method in order to identify the vanadium species. Two species of surface vanadium were identified by Raman measurements, monomeric vanadyls and polymeric vanadates. Monomeric vanadyls are characterized by a narrow Raman band at 1030 cm–1 and polymeric vanadates by two broad bands in the region from 900 to 960 cm–1 and 770 to 850 cm–1. The Raman spectra do not exhibit characteristic peaks of crystalline V2O5. These results are in agreement with those of X-ray Diffractometry (XRD) and Fourier Transform Infrared (FT-IR) previously reported (C.B. Rodella et al., J. Sol-Gel Sci. Techn., submitted). At least three families of V4+ ions were identified by EPR investigations. The analysis of the EPR spectra suggests that isolated V4+ ions are located in sites with octahedral symmetry substituting for Ti4+ ions in the rutile structure. Magnetically interacting V4+ ions are also present as pairs or clusters giving rise to a broad and structureless EPR line. At higher concentration of V2O5, a partial oxidation of V4+ to V5+ is apparent from the EPR results. 相似文献
102.
Francesco S. Gentile Alexander Platonenko Khaled E. El-Kelany Michel Rérat Philippe D'Arco Roberto Dovesi 《Journal of computational chemistry》2020,41(17):1638-1644
The infrared (IR) and Raman spectra of eight substitutional carbon defects in silicon are computed at the quantum mechanical level by using a periodic supercell approach based on hybrid functionals, an all electron Gaussian type basis set and the CRYSTAL code. The single substitutional C s case and its combination with a vacancy (C sV and C sSiV) are considered first. The progressive saturation of the four bonds of a Si atom with C is then examined. The last set of defects consists of a chain of adjacent carbon atoms C, with i = 1–3. The simple substitutional case, C s, is the common first member of the three sets. All these defects show important, very characteristic features in their IR spectrum. One or two C related peaks dominate the spectra: at 596 cm−1 for C s (and C sSiV, the second neighbor vacancy is not shifting the C s peak), at 705 and 716 cm−1 for C sV, at 537 cm−1 for C and C (with additional peaks at 522, 655 and 689 for the latter only), at 607 and 624 cm−1, 601 and 643 cm−1, and 629 cm−1 for SiC, SiC, and SiC, respectively. Comparison with experiment allows to attribute many observed peaks to one of the C substitutional defects. Observed peaks above 720 cm−1 must be attributed to interstitial C or more complicated defects. 相似文献
103.
Poon T Turro NJ Chapman J Lakshminarasimhan P Lei X Jockusch S Franz R Washington I Adam W Bosio SG 《Organic letters》2003,5(26):4951-4953
Oxazolidinone-substituted enecarbamates represent a mechanistically rich system for the study of stereoelectronic, steric, and conformational effects on stereoselectivity and mode selectivity in (1)O(2) [2 + 2] and ene reactions. Photooxygenation of these enecarbamates with (1)O(2) leads to diastereomerically pure dioxetanes that decompose to yield an oxazolidinone carbaldehyde and one of the two enantiomers of methyldesoxybenzoin in enantiomeric excess. Stereoselectivity originates at the allylic stereocenter, a result supported by quenching studies, computational analysis, and deuterium solvent isotope effects. [reaction: see text] 相似文献
104.
Schäfer T Di Paolo RE Franco R Crespo JG 《Chemical communications (Cambridge, England)》2005,(20):2594-2596
We report on the molecular interactions between room-temperature ionic liquids (RTILs) and Nafion and PDMS membranes, proving that in contact with these polymers RTILs behave like electrolytes rather than solvents. 相似文献
105.
Ihalainen JA Croce R Morosinotto T van Stokkum IH Bassi R Dekker JP van Grondelle R 《The journal of physical chemistry. B》2005,109(44):21150-21158
Light-harvesting complex I (LHCI), which serves as a peripheral antenna for photosystem I (PSI) in green plants, consists mainly of four polypeptides, Lhca1-4. We report room temperature emission properties of individual reconstituted monomeric Lhca proteins (Lhca1, -2, -3, and -4) and dimeric Lhca1/4, performed by steady-state and time-resolved fluorescence techniques. The emission quantum yields of the samples are approximately 0.12, 0.085, 0.081, 0.041, and 0.063 for Lhca1, -2, -3, -4, and the -1/4 dimer, respectively, which is considerably lower than the value of 0.22 found for light-harvesting complex II (LHCII), the main peripheral antenna complex of photosystem II in green plants. The decay components of LHCI proteins can be divided in two categories: Lhca1 and Lhca3 have decay times of 1.1-1.6 ns and 3.3-3.6 ns, and Lhca2 and Lhca4 have decay times of 0.7-0.9 ns and 3.1-3.2 ns. These categories seem to correlate with the pigment composition of the samples. All decay times are faster than that observed previously for LHCII. When the absolute emission yields and the lifetimes of the Lhca samples are combined, the overall emission properties of the individual Lhca proteins are expressed in terms of their emitting dipole moment strength. In the samples without extreme red states, that is, Lhca1 and Lhca2, the emitting dipole moment has a value close to unity (relative to monomeric chlorophyll in acetone), which is similar to that for LHCII, whereas, in the samples with the red-most state (F-730), that is, Lhca3, -4, and the -1/4 dimer, the emitting dipole moment has a value less than unity (0.6-0.8), which can be explained by mixing the red-most (exciton) state with a dark charge-transfer state, as suggested in previous PSI red pigment studies. In addition, we find a lifetime component of approximately 50-150 ps in all red-pigment-containing samples, which cannot be due to "slow" energy transfer, but is instead assigned to an unrelaxed state of the pigment-protein, which, on this time-scale, is converted into the final emitting state. 相似文献
106.
I. Perez-Alvarez J. L. Martinez-Vidal M. Villafranca E. Gonzalez-Pradas F. Salinas 《Journal of Thermal Analysis and Calorimetry》1989,35(7):2341-2346
Solid crystalline complexes of furan-2-hydroxamic acid (FHA) and six metallic divalent cations (Ca(II), Ba(II), Co(II), Ni(II), Cu(II), and Cd(II)) were prepared. In all cases the stoichiometry was 2(FHA)1 (cation). The solids were characterized by elemental analysis, TG, DSC and IR techniques.
Zusammenfassung Es wurden feste, kristalline Komplexe von Furan-2-hydroxamsäure (FHA) und sechs verschiedenen bivalenten Metallkationen hergestellt: Ca(II), Ba(II), Co(II), Ni(II), Cu(II) und Cd(II). Die stöchiometrische Zusammensetzung betrug in allen Fällen 2(FHA)1(Kation). Die Feststoffe wurden mittels Elementaranalyse, TG-, DSC- und IR-Techniken charackterisiert.
-2- , , , , . : 21. , , .相似文献
107.
This work presents the carrying out of boiling-point distributions by simulated distillation with direct-column heating rather than oven-column heating. Column-heating rates of 300 degrees C/min are obtained yielding retention times of 73 s for n-tetratetracontane. The calibration curves of the retention time versus the boiling point, in the range of n-pentane to n-tetratetracontane, are identical to those obtained by slower oven-heating rates. The boiling-point distribution of the reference gas oil is compared with that obtained with column oven heating at rates of 15 to 40 degrees C/min. The results show boiling-point distribution values nearly the same (1-2 degrees F) as those obtained with oven column heating from the initial boiling point to 80% distilled off. Slightly higher differences are obtained (3-4 degrees F) for the 80% distillation to final boiling-point interval. Nonetheless, allowed consensus differences are never exceeded. Precision of the boiling-point distributions (expressed as standard deviations) are 0.1-0.3% for the data obtained in the direct column-heating mode. 相似文献
108.
Boundary feedback stabilizability of parabolic equations 总被引:1,自引:0,他引:1
Roberto Triggiani 《Applied Mathematics and Optimization》1980,6(1):201-220
A parabolic equation defined on a bounded domain is considered, with input acting on theboundary expressed as a specifiedfeedback of the solution. Both Dirichlet and mixed (in particular, Neumann) boundary conditions are treated. Algebraic conditions based on the finitely many unstable eigenvalues are given, ensuring the existence ofboundary vectors, for which all the solutions to theboundary feedback parabolic equation decay exponentially to zero ast+ in (essentially) the strongest possible space norm. A semigroup approach is employed.Research partially supported by Air Force Office of Scientific Research under Grant AFOSR-77-3338.A preliminary version of this paper has appeared in the Proceedings of the International Symposium on the Mathematical Theory of Networks and Systems, held at Delft University, The Netherlands, July 3–6, 1979; pp. 428–433. 相似文献
109.
110.
Badorrey R Cativiela C Díaz-de-Villegas MD Díez R Galbiati F Gálvez JA 《The Journal of organic chemistry》2005,70(24):10102-10105
[reaction: see text] Addition of trimethylsilyl cyanide to ketimines derived from (R)-2,2-dimethyl-1,3-dioxolan-4-yl methyl ketone to generate a quaternary stereocenter has been achieved with high yields and excellent diastereoselectivity. The stereoselectivity was found to be temperature and solvent dependent. The beta-hydroxy-alpha-amino nitrile of syn configuration was the major compound in kinetically controlled reactions, whereas the anti stereoisomer was obtained in excess in thermodynamically controlled reactions. Double stereodifferentiation under kinetic control conditions was successful, and the cyanation reaction occurred with complete syn diastereoselectivity using the matched pair. The versatility of the resulting amino nitrile as a synthetic intermediate was tested by performing the synthesis of orthogonally protected (R)-(2-aminomethyl)alanine. 相似文献