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21.
The intramolecular hydrogen bond (H-bond) energies in several polyhydroxy systems are estimated using an isodesmic/homodesmic reaction approach as well as a molecular tailoring approach (MTA) [Deshmukh, M. M.; Gadre, S. R.; Bartolotti, L. J. J. Phys. Chem. A 2006, 110, 12519]. It is shown that the isodesmic/homodesmic reaction approach as advocated in the literature does not give true H-bond energy but includes the effect of strain energy due to the formation of a ring structure. Such a ring strain is duly accounted for in the MTA method. The isodesmic H-bond energies are found to be smaller than their MTA energy counterparts typically by the strain energy. The MTA is applied to decitol, a system with more than five different H-bonds for which an application of an appropriate isodesmic reaction is extremely difficult. It has been shown that the MTA method is able to predict not only the H-bond energies but also the trends in conformational energies for three different conformers of decitol studied in the present work. 相似文献
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23.
Norman Scholz Amol Jadhav Milind Shreykar Thomas Behnke Nithiya Nirmalananthan Ute Resch-Genger Nagaiyan Sekar 《Journal of fluorescence》2017,27(6):1949-1956
A comprehensive systematic study of absorption and fluorescence properties in solvents of varying viscosity and polarity of three novel and red-emitting coumarin-rhodamine hybrid derivatives with differences in the rigidity of their substituents is presented. This includes ethanol-polyethylene glycol, toluene-polyethylene glycol, and toluene-paraffin mixtures. Moreover, protonation-induced effects on the spectroscopic properties are studied. A viscosity-induced emission enhancement was observed for all coumarin-rhodamine hybrid derivatives. MCR2 bearing a julolidine donor showed the expected low sensitivity to viscosity whereas MCR3 with its freely rotatable diphenylamino substituent revealed a particularly pronounced sensitivity to this parameter. Moreover, MCR2 shows an enhancement in emission in the open, i.e., protonated form in conjunction with a largely Stokes shift fluorescence in the deep red spectral region. This enables the application of these dyes as viscosity sensors and as far red emitting pH-sensitive probes. 相似文献
24.
Kulkarni MJ Vinod VP Umasankar PK Patole MS Rao M 《Rapid communications in mass spectrometry : RCM》2006,20(18):2769-2772
Here we demonstrate for the first time the application of intact cell matrix-assisted laser desorption/ionization mass spectrometry (ICM-MS) to study the regulation of protein expression. This technique can be extended to screen the drugs that inhibit protein synthesis in various diseases. We have used Escherichia coli cells expressing a recombinant glutathione-S-transferase (GST) gene under an arabinose-inducible promoter as a model system. Using ICM-MS analysis, we have detected a 28 kDa peak corresponding to the production of recombinant GST under the arabinose-induced condition. Furthermore, recombinant GST protein was purified by a single-step affinity purification using a glutathione Sepharose 4B affinity column from arabinose-induced E. coli cells. The purified GST protein was found to be a 28 kDa protein by MALDI analysis suggesting the arabinose-induced protein is indeed GST. The regulation of protein expression was studied using glucose as an alternative metabolite. The glucose-mediated regulation of the ara-operon was followed using the ICM-MS technique. All the results obtained from ICM-MS data were validated using sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) analysis. The present technique can be extended for in vivo screening of drugs and it holds tremendous potential to discover novel drugs against specific protein expressions in different diseases. 相似文献
25.
A mixture of 9-amino-(9-deoxy)epi-dihydroquinidine and salicylic acid was able to promote the direct reaction of various cyclohexanones with dibenzoyl peroxide, thus affording the corresponding protected α-hydroxy carbonyl compounds in high yield and enantioselectivity. Interestingly the same catalytic salt was found to be active when 1-indanones derivatives were directly employed in the reaction with dibenzoyl peroxide furnishing chiral 1-oxo-2,3-dihydro-1H-inden-2-yl benzoates in high yields and enantioselectivity. Furthermore their treatment with NaBH(4) gives easy access to the corresponding enantioenriched 1,2-diols in high yields and without any loss of stereoselectivity. 相似文献
26.
Hafnocene dichloride was reduced with amalgamated magnesium in the presence of alkynes giving high yields of di-η5-cyclopentadienylhafnacyclopentadienes. Reaction with hydrochloric acid yields exclusively the corresponding (E,E)-butadiene derivatives. 相似文献
27.
Shah Hiten J. Rathod Ishwarsinh S. Shah Shailesh A. Savale Shrinivas S. Shishoo Chamanlal J. 《平面色谱法杂志一现代薄层色谱法》2003,16(1):36-44
JPC – Journal of Planar Chromatography – Modern TLC - Two fundamentally different analytical methods have been validated and used to monitor release of diclofenac and acetaminophen... 相似文献
28.
Wire-Arc Spray Modeling 总被引:5,自引:0,他引:5
A model is presented describing the details of the wire-arc spray process. The model consists of several submodels each treating a different part of the process. A compressible flow model describes the supersonic nozzle flow upstream of the wire tips. The arc is described by a 3-D arc in cross-flow model using different boundary conditions for the cathode and the anode boundary. The resulting temperature and velocity contours serve as upstream boundary for a 2-D turbulent jet model. Particle generation and acceleration is described by treating the initial droplet formation for the anode and the cathode wire separately and then using the resulting particle size and velocity distributions in a secondary break-up model. Comparison with some experimental results show acceptable agreement. This modeling approach may be used for optimization of wire-arc spray equipment. 相似文献
29.
An intermolecular Stetter reaction of aromatic aldehydes with maleimides has been developed using thiazolylidene salt derived Isa?NHC as an efficient organocatalyst. The synthesized Stetter products “3?aroylsuccinimides” are important building blocks for the synthesis of natural products and bioactive compounds. The reaction conditions are mild, and various substituents on aromatic aldehyde and maleimide nitrogen were tolerated. 相似文献
30.
Milind S. Thakare Nilesh S. Pawar Vishnu A. Adole Dipak B. Patil Vikas Patil 《印度化学会志》2022,99(10):100670
A novel strategy, involving anchoring and un-anchoring of coumarin based fluorophore, has been established for the selective detection of Au3+ species. Selective sensing of Gold (Au3+) was triggered due to alkynophilicity of gold ions to create lateral fluorescence of a latent fluorophore. The 4-methyl-2-oxo-2H-chromen-7-yl 2-(2-phenylethynyl) benzoate (CEB) probe was synthesized by reacting 7-hydroxy-4-methylcoumarin with iodo-benzoic acid. CEB probe has an absorption at 300 nm and 335 nm which decreases gradually and new absorption appeared at 406 nm due to Au3+ promoted ester hydrolysis selectively over other metal ions with great sensitivity, which accompanies a turn on fluorescence change produced by 7-hydroxy coumarin. The principle behind this sensing strategy is activation of triple bond induced uniquely by Au+3 ions leading to cascade and delivers active fluorophore. The sensing mechanism was proposed and supported by 1H NMR, MS and TD-DFT experiments. The density functional theory (DFT) and time dependent density functional theory (TD-DFT) theoretical results of the CEB-probe and Au3+ reaction is in good agreement with the experimental results. Additionally, probe could be well incorporated onto the test strips for effective detection of Au3+. 相似文献