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1.
In this study, stoichiometric protonation constants of L-tyrosine, L-cysteine, L-tryptophane, L-lysine, and L-histidine, and
their methyl and ethyl esters in water and ethanol–water mixtures of 30, 50, and 70% ethanol (v/v), were determined potentiometrically
using a combined pH electrode system calibrated as the concentration of hydrogen ion. Titrations were performed at 25∘C and the ionic strength of the medium was maintained at 0.10 mol⋅L−1 using sodium chloride. Protonation constants were calculated by using the BEST computer program. The effect of solvent composition
on the protonation constants is discussed. The log10 K2 values of esters generally decreased with increasing ethanol content. However, the log10 K1 values of the esters of L-tyrosine, L-cysteine, and L-tryptophane were found to increase with increasing ethanol content
in contrast those of L-lysine and L-histidine esters. 相似文献
2.
3.
Joaquim Jaumot Montserrat Vives Raimundo Gargallo Rom Tauler 《Analytica chimica acta》2003,490(1-2):253-264
One of the difficulties frequently encountered when studying acid–base equilibria with NMR spectroscopy is the labile behaviour of the measured signal, which hinders the application of bilinear multivariate data analysis methods. In this work, a mathematical transformation is proposed for the conversion of NMR labile signals to inert signals, which make possible the application of multivariate data analysis methods, based on bilinear data models. The procedure has been applied to the analysis of NMR data corresponding to the acid–base equilibria of nucleotides dCMP and dGMP. Both hard-modelling (EQUISPEC) and soft-modelling (MCR-ALS) approaches have been applied for the analysis and resolution of transformed bilinear NMR data matrices. 相似文献
4.
Summary 1-(Dipyrrinon-9-yl)-3-(dipyrrinon-9-ylidene)-propene, ab-vinylogous verdin, was synthesized by condensation of 3-(dipyrrinon-9-yl)-propenal with a dipyrrinone unsubstituted in position 9. By condensing the latter with dimedone or squaric acid,b-vinylogous verdin pigments with restricted configurational and conformational degrees of freedom were obtained. The chemical and spectroscopic properties of these novel systems are discussed.
Zur Chemie von Pyrrolpigmenten, 94. Mitt.: 1-(Dipyrrinon-9-yl)-3-(dipyrrinon-9-yliden)-1-propen — Ein neuerb-vinyloger Verdinchromophor
Zusammenfassung 1-(Dipyrrinon-9-yl)-3-(dipyrrinon-9-yliden)-propen, einb-vinyloges Verdin, wurde durch Kondensation von 3-(Dipyrrinon-9-yl)-propenal mit einem in Position 9 unsubstituierten Dipyrrinon dargestellt. Kondensation des Letzteren mit Dimedon oder Quadratsäure lieferte vinyloge Pigmente, welche in ihren konfigurationellen und konformationellen Freiheiten eingeschränkt sind. Die chemischen und spektroskopischen Eigenschaften dieser neuen Systeme werden diskutiert.相似文献
5.
本文报道测钪新试剂均三溴氯磺酚在水溶液中的离解与质子化作用,用电位法和光度法测得了它的逐级离解常数与质子化常数,以及热力学参数,并由分布函数获得试剂主要存在形式和pH值的关系。 相似文献
6.
Lemi Türker 《Journal of Molecular Structure》2004,680(1-3):47-51
Semiempirical quantum chemical calculations at the level of AM1 (restricted Hartree–Fock) have been performed on a fullerene derivative, C54N4, theoretically obtained from C60 and its mono and diprotonated forms. All these structures are stable, but endothermic in nature. Some calculated geometrical and physicochemical properties of these have also been reported. 相似文献
7.
Summary Fringelite D was synthesized from 1,3,6,8-tetramethoxyanthracen-9-olvia two different efficient routes. The first one involved demethylation and subsequent dimerization. The other one started with dimerization to yield octamethylfringelite D and subsequent demethylation. The starting material was prepared in four steps from commercially available educts, the key step being a benzamideortho-lithiation. The spectroscopic properties of fringelite D were measured and are discussed. The dissociation, deprotonation, and protonation equilibria of fringelite D were characterized by their respectivepK values in ground and excited states and compared with those of hypericin. Homo- and heteroassociation properties of fringelite D were found to be similar to those of hypericin.
Synthese und Eigenschaften von Fringelit D (1,3,4,6,8,10,11,13-Octahydroxy-phenanthro[1,10,9,8,o,p,q,r,a]perylen-7,14-dion)
Zusammenfassung Fringelit D wurde auf zwei effizienten Routen aus 1,3,6,8-Tetramethoxyanthracen-9-ol synthetisiert. Die erste umfaßt Demethylierung und anschließende Dimerisierung. Die andere beginnt mit der Dimerisierung zu Octamethylfringelit D und endet mit einer Demethylierung. Das Ausgangsmaterial wurde in vier Stufen aus kommerziell zugänglichen Edukten dargestellt; der Schlüsselschritt ist eineortho-Lithiierung eines Benzamids. Die spektroskopischen Eigenschaften von Fringelit D wurden gemessen und werden diskutiert. Die Dissoziations-, Deprotonierungs- und Protonierungsgleichgewichte wurden durch ihrepK-Werte in Grundzustand und angeregtem Zustand charakterisiert und mit jenen des Hypericins verglichen. Die Homo- und Hetero-assoziationseigenschaften von Fringelit D sind jenen des Hypericins ähnlich.相似文献
8.
将射频等离子体技术应用于杂多蓝的制备中, 成功地制备出四电子还原的磷钼杂多蓝, 并对所制备的杂多蓝进行了结构表征及性质研究, 探讨了磷钼杂多酸在射频氢等离子体中的还原行为. 相似文献
9.
Some gauge invariant atomic orbitals-coupled-perturbed Hartree-Fock (GIAO-CPHF) calculations were performed for seven indolizine derivatives and their monoprotonated forms. Chemical shift, molecular geometry, and charge distribution data are reported for each molecule. The calculations support the results of nuclear magnetic resonance (NMR) spectroscopy measurements showing that protonation occurs preferentially at N1. The good agreement between the calculated and observed 13C and 15N chemical shifts show that such calculations can be used for chemical shift assignment purposes. Cation structures and probable sites for electrophilic reaction or second protonation are also discussed. 相似文献
10.
用标准MNDO方法优化了甘油快原子轰击正离子谱中的主要离子构型,计算了生成热、质子化能以及亚稳断裂的活化势垒,研究了质子化甘油二步脱水反应的机理,并指出脱水产物C_3H_5O~+离子存在2种不同的构型。 相似文献