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81.
Combined self-consistent field and configuration-interaction calculations were carried out on the excited states of nitrosyl fluoride. Results of these calculations confirm the assignment of the electronic transition 11A″ ← X1A′ observed to occur between 3.70 and 4.77 eV, with an absorption maximum at 3.99 eV. A comparative study between the calculated vertical spectra of HNO and ONF is made. 相似文献
82.
The stress-optical coefficients and of RbCl and RbBr crystals have been measured at room temperature (26°C) over the wave length range 5750-2500 Å. 相似文献
83.
84.
85.
Kinetic studies of cholesterol oxidation catalyzed by soluble cholesterol oxidase fromBrevibacterium were conducted. The optimum temperature and pH were found to be 40–45°C and 7.0, respectively. A plot of initial reaction
rate versus cholesterol concentration is sigmoidal in shape. Analysis of the data suggests that the reaction follows a concerted
model and not a stepwise model. 相似文献
86.
X-ray and ultraviolet photoelectron spectroscopy have been employed to investigate the high temperature metal-insulator transitions
in V2O3 and (V0.99Cr0.01)2O3. The high temperature transitions are associated with more gradual changes in the 3d bands compared to the low-temperature transitions.
Communication No. 20 from Solid State & Structural Chemistry Unit. 相似文献
87.
R Bellman B Kashef R Vasudevan 《Journal of Mathematical Analysis and Applications》1973,44(1):160-174
Dynamic programming techniques were used to obtain the spline approximation for a function with prescribed values on the knot points along a line. Extending this procedure to two dimensions, the bicubic spline approximation defined over a two-dimensional region is obtained in this paper employing the methods of dynamic programming. A regular rectangular region as well as a region with irregular boundaries can be handled by this method, avoiding the difficulties of large storage and high dimensionality. 相似文献
88.
Dr. Vasudevan Dhayalan Deepika Sharma Dr. Rana Chatterjee Dr. Rambabu Dandela 《European journal of organic chemistry》2023,26(30):e202300285
This Review discusses the various methods for functionalizing pyridine and quinoline scaffolds, including direct selective metalation (DoM), halogen/metal exchange reactions, Li, Mg, and Zn insertion, and trans-metalation approaches, which are then followed by cross-coupling reactions of the Kumada or Negishi types. Selective deprotonation of aryl or pyridyl/quinolinyl derivatives can be performed using n-BuLi, LDA, and TMP-based different organolithium, -magnesium, and -zinc reagents. The functionalized pyridine and quinoline-based heterocyclic compounds were prepared by selectively deprotonating with presenting a directing functional group substituted pyridine/quinoline analogues in the presence of TMP-bases (TMP−Li, Mg, Zn reagents). Different aryl or alkyl Li, Mg, and Zn reagents with electron-donating and electron-withdrawing substituents undergo transition metal-catalyzed C(sp2)−C(sp2) and C(sp2)−C(sp3) types of cross-coupling reactions with pyridine/quinoline halides under mild conditions with the sustainable process producing complex N-heterocycles. Using moderate and sustainable reaction conditions, sensitive functional group tolerance, and inexpensive and low toxic chemicals, highly functionalization of pyridine and quinoline-based bioactive therapeutic scaffolds and natural products was accomplished. Therefore, in this article, we provide a succinct overview of the numerous synthetic strategies and practical methods used by various authors between 2010 and 2023 to functionalize pyridine and quinoline analogues using diverse Li, Mg, and Zn organometallic reagents. 相似文献
89.
Holland JP Aigbirhio FI Betts HM Bonnitcha PD Burke P Christlieb M Churchill GC Cowley AR Dilworth JR Donnelly PS Green JC Peach JM Vasudevan SR Warren JE 《Inorganic chemistry》2007,46(2):465-485
Two new types of unsymmetrical bis(thiosemicarbazone) proligands and their neutral zinc(II) and copper(II) complexes have been synthesized. These bifunctional ligands both chelate the metal ions and provide pendent amino groups that can be readily functionalized with biologically active molecules. Functionalization has been demonstrated by the synthesis of three water-soluble glucose conjugates of the new zinc(II) bis(thiosemicarbazonato) complexes, and their copper(II) analogues have been prepared in aqueous solution via transmetalation. A range of techniques including NMR, electron paramagnetic resonance, cyclic voltammetry, high-performance liquid chromatography (HPLC), UV/vis, and fluorescence emission spectroscopy have been used to characterize the complexes. Four compounds, including two zinc(II) complexes, have been characterized by X-ray crystallography. The connectivity and conformation of the glucose conjugates have been assigned by NMR spectroscopy. Time-dependent density functional theory calculations have been used to assign the electronic transitions of the copper(II) bis(thiosemicarbazonato) chromophore. Two copper-64-radiolabeled complexes, including one glucose conjugate, have been prepared and characterized using radio-HPLC, and transmetalation is shown to be a viable method for radiolabeling compounds with copper radionuclides. Preliminary cell washout studies have been performed under normoxic conditions, and the uptake and intracellular distribution have been studied using confocal fluorescence microscopy. 相似文献
90.
Vasudevan V Hanson RK Golden DM Bowman CT Davidson DF 《The journal of physical chemistry. A》2007,111(19):4062-4072
We have studied the two-channel thermal decomposition of methyl radicals in argon, involving the reactions CH3 + Ar --> CH + H2 + Ar (1a) and CH3 + Ar --> CH2 + H + Ar (1b), in shock tube experiments over the 2253-3527 K temperature range, at pressures between 0.7 and 4.2 atm. CH was monitored by continuous-wave, narrow-line-width laser absorption at 431.1311 nm. The collision-broadening coefficient for CH in argon, 2gamma(CH-Ar), was measured via repeated single-frequency experiments in the ethane pyrolysis system behind reflected shock waves. The measured 2gamma(CH-Ar) value and updated spectroscopic and molecular parameters were used to calculate the CH absorption coefficient at 431.1311 nm (23194.80 cm(-1)), which was then used to convert raw traces of fractional transmission to quantitative CH concentration time histories in the methyl decomposition experiments. The rate coefficient of reaction 1a was measured by monitoring CH radicals generated upon shock-heating highly dilute mixtures of ethane, C2H6, or methyl iodide, CH3I, in an argon bath. A detailed chemical kinetic mechanism was used to model the measured CH time histories. Within experimental uncertainty and scatter, no pressure dependence could be discerned in the rate coefficient of reaction 1a in the 0.7-4.2 atm pressure range. A least-squares, two-parameter fit of the current measurements, applicable between 2706 and 3527 K, gives k(1a) (cm(3) mol(-1) s(-1)) = 3.09 x 1015 exp[-40700/T (K)]. The rate coefficient of reaction 1b was determined by shock-heating dilute mixtures of C2H6 or CH3I and excess O2 in argon. During the course of reaction, OH radicals were monitored using the well-characterized R(1)(5) line of the OH A-X (0,0) band at 306.6871 nm (32606.52 cm(-1)). H atoms generated via reaction 1b rapidly react with O2, which is present in excess, forming OH. The OH traces are primarily sensitive to reaction 1b, reaction 9 (H + O2 --> OH + O) and reaction 10 (CH3 + O2 --> products), where the rate coefficients of reactions 9 and 10 are relatively well-established. No pressure dependence could be discerned for reaction 1b between 1.1 and 3.9 atm. A two-parameter, least-squares fit of the current data, valid over the 2253-2975 K temperature range, yields the rate expression k(1b) (cm(3) mol(-1) s(-1)) = 2.24 x 10(15) exp[-41600/T (K)]. Theoretical calculations carried out using a master equation/RRKM analysis fit the measurements reasonably well. 相似文献