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Clarissa O. da Silva André Gustavo H. Barbosa Emerson T. da Silva Edson Luiz L. da Silva Marco Antonio C. Nascimento 《Theoretical chemistry accounts》2004,111(2-6):231-236
In order to better understand the performance of 1,2-dimethyl-5-acetyl barbituric acid (DMB) as an amino protecting group relative to 5,5-dimethylcyclohexane-1,3-dione (DMD), ab initio calculations were performed. pKa calculations using the PCM model indicated that both molecules are more acidic in the enol form. Therefore, the protecting reaction of these molecules should involve the anions formed from the loss of a proton from the enol compounds. Contrary to what would be expected, the larger efficiency exhibited by the DMB molecule cannot be attributed to an extension of the electronic conjugation effect. In the absence of any other noticeable effect that could be responsible for the greater efficiency of the DMB molecule, we are inclined to believe that the difference could be accounted for by the presence of two independent centers of conjugation.This paper is dedicated to Jacopo Tomasi in recognition of his outstanding contribution to the field of computational chemistry in solution. The authors are honored to contribute to this volume; especially so for two of them (COS and MACN) who have the privilege of his friendship.Acknowledgements The authors would like to thank the Brazilian research agencies CNPq, CAPES and FAPERJ for the financial support. C. O. da Silva thanks the Dipartimento di Chimica e Chimica Industriale, University of Pisa, where the MCSCF calculations were performed. 相似文献
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In this work the separation of eighteen flavonoids was attempted using reduced-flow micellar elektrokinetic chromatography (RF-MEKC) electrolytes modified by selected solvents with differing properties: methanol (MeOH), acetonitrile (ACN) and tetrahydrofuran (THF). Structural aspects such as unsaturation of the C ring, number and position of OH groups, methylation and glycosylation as well as solvent effects and their impact on the electrophoretic behavior of flavonoids were addressed. By evaluating the electropherograms obtained from mixture-designed electrolytes and searching for changes in the critical pairs, a favorable separation condition was achieved using 20 mmol/L phosphate buffer at pH 2.5 containing 50 mmol/L sodium dodecyl sulfate (SDS), 15% ACN and 5% THF (one critical pair) in less than 12 min with 1.5% coefficient of variation (CV) for retention factor and 3% CV for peak area (n = 5). The applicability of the proposed separation condition was demonstrated by the inspection of flavonoids in herbal extracts of Neem. 相似文献
158.
We study the Pareto optimal equilibria payoffs of the non-cooperative game associated with the cost spanning tree problem.
We give two characterisations of these payoffs: one based on the tree they induce and another based on the strategies played
by agents. Moreover, an algorithm for computing all these payoffs is provided. 相似文献
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Remarks on a paper by J. T. Beale,T. Kato,and A. Majda 总被引:1,自引:0,他引:1
Gustavo Ponce 《Communications in Mathematical Physics》1985,98(3):349-353
We prove that the maximum norm of the deformation tensor controls the possible breakdown of smooth solutions for the 3-dimensional Euler equations. More precisely, the loss of regularity in a local smooth solution of the Euler equations implies the growth without bound of the deformation tensor as the critical time approaches; equivalently, if the deformation tensor remains bounded the existence of a smooth solution is guaranteed. 相似文献
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Tenorio-Lopez FA Valle Mondragon LD Olvera GZ Torres Narvaez JC Pastelin G 《Natural product research》2006,20(13):1176-1182
Viscum album L. aqueous extract, on the Langendorff isolated and perfused heart model, decreases coronary vascular resistance, when compared to control group (36.00 +/- 2.00 vs. 15.80 +/- 1.96 dyn s cm-5). Our data support the fact that this mechanism involves NOS-2 and NOS-3 overexpression (4.65 and 7.89 times over control, respectively), which is correlated with increases in NO (6.24 +/- 2.49 vs. 147.95 +/- 2.79 pmol) and cGMP production (43.94 +/- 2.00 vs. 74.81 +/- 1.96 pmol mg-1 of tissue), compared to control values. Such an effect is antagonized by gadolinium(III) chloride, L-NAME and ODQ. Therefore, coronary vasodilator effect elicited by V. album L. aqueous extract is mediated by the NO/sGC pathway. 相似文献