全文获取类型
收费全文 | 2738篇 |
免费 | 105篇 |
国内免费 | 10篇 |
专业分类
化学 | 1765篇 |
晶体学 | 24篇 |
力学 | 58篇 |
数学 | 500篇 |
物理学 | 506篇 |
出版年
2023年 | 12篇 |
2022年 | 23篇 |
2021年 | 47篇 |
2020年 | 62篇 |
2019年 | 56篇 |
2018年 | 27篇 |
2017年 | 34篇 |
2016年 | 83篇 |
2015年 | 81篇 |
2014年 | 81篇 |
2013年 | 142篇 |
2012年 | 178篇 |
2011年 | 174篇 |
2010年 | 107篇 |
2009年 | 99篇 |
2008年 | 159篇 |
2007年 | 174篇 |
2006年 | 146篇 |
2005年 | 125篇 |
2004年 | 110篇 |
2003年 | 100篇 |
2002年 | 100篇 |
2001年 | 54篇 |
2000年 | 40篇 |
1999年 | 35篇 |
1998年 | 28篇 |
1997年 | 35篇 |
1996年 | 22篇 |
1995年 | 25篇 |
1994年 | 33篇 |
1993年 | 40篇 |
1992年 | 33篇 |
1991年 | 22篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1987年 | 14篇 |
1986年 | 11篇 |
1985年 | 24篇 |
1984年 | 16篇 |
1983年 | 24篇 |
1982年 | 21篇 |
1981年 | 20篇 |
1980年 | 21篇 |
1979年 | 11篇 |
1978年 | 17篇 |
1977年 | 21篇 |
1976年 | 15篇 |
1975年 | 19篇 |
1974年 | 17篇 |
1973年 | 11篇 |
排序方式: 共有2853条查询结果,搜索用时 31 毫秒
61.
Emil Pop Marcus E. Brewster J. J. Kaminski Nicholas Bodor 《International journal of quantum chemistry》1989,35(2):315-324
9-Amino-1,2,3,4-tetrahydroacridine (THA ), a potent cholinesterase inhibitor, was recently used in the treatment of Alzheimer's disease. On attempting to prepare a dihydropyridine ? pyridinium salt-based redox chemical delivery system (CDS ) to enhance brain delivery of THA , several of the practical synthetic challenges were examined by using a theoretical MO approach. The structures, reactivities and stability of THA , derivatives of THA and a model compound, 4-aminopyridine, a simple dibasic heterocyclic amine, were studied in the framework of the AM -1 approximation. The study included the possible protonated forms of THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine, consistent with experimental results. Electron delocalization is responsible for the remarkable stability of these molecules and for the observed lack of reactivity of the amino group, both in the basic and protonated forms. The site of N-alkylation of the 9-nicotinamide derivative of THA (an intermediate in the synthesis of THA -CDS ) is controlled by electronic, thermodynamic, and steric factors. 相似文献
62.
63.
Y. Marcus 《Journal of solution chemistry》1987,16(9):735-744
The translational entropy loss on the association of two ions to form an ion pair or 11 complex is overcompensated by a rotational entropy gain, an electrostatic entropy gain, and an entropy gain due to solvent release from translational immobilization. The first three effects can be calculated, leaving the fourth as a difference from the experimental entropy change on association. The ratio of the solvent release entropy gain to the entropy change on melting of the solvent indicates the number of solvent molecules released on the association. A similar value is obtained from data for the volume change on association.Presented as a poster at the 10th International Conference on Non-Aqueous Solvents (ICNAS) at Leuven, Belgium, August 1986, and at the 24th International Congress on Coordination Chemistry (ICCC) at Athens, Greece, August 1986. 相似文献
64.
Summary This paper describes a method for theg synthesis of flavone acetates in a sealed capillary tube. The reaction products are separated and purified on a thin-layer plate. The esters are then hydrolyzed on the plate and the parent flavones regenerated. A simple heating device is used which allows for observation of the reaction.
For part IV of this series see Mikrochim. Acta [Wien]1969, 352. 相似文献
Zusammenfassung Beschreibung der Mikrogrammsynthese von Flavonacetaten in einem verschmolzenen Kapillarröhrchen. Die Reaktionsprodukte werden auf einer Dünnschichtplatte getrennt und gereinigt. Dann verseift man die Ester auf der Platte und stellt die freien Flavone dar. Ein einfaches Heizgerät ermöglicht die Beobachtung der Reaktion.
For part IV of this series see Mikrochim. Acta [Wien]1969, 352. 相似文献
65.
A statistical treatment of data for the standard molar Gibbs free energies of transfer of monovalent ions from water to polar solvents has been made in terms of properties of the solvents and the ions. A common multiple regression equation with seven fitting constants, for almost 200 data points, has been found to describe the data in terms of four solvent properties: their electron donor and acceptor abilities, dielectric constant, and cohesive energy density, and three ionic properties: charge, size, and softness. For the ions Na+, K+, Rb+, Cs+, Tl+, (Ph)4As+, Cl?, Br? and N 3 ? the predictions of the equation are within acceptable error limits of the data, and encourage its application to solvents beyond the thirteen used for the data base. For other ions, e.g. H+, Ag+, and the larger anions, further interactions must be taken into account. 相似文献
66.
Christian Lehmann Bernd Schweizer Christian Leumann Albert Eschenmoser 《Helvetica chimica acta》1997,80(5):1421-1442
Chemistry of α-Aminonitriles. Regioselective Synthesis and Crystal Structure of Uroporphyrinogen (Type I) Octanitrile A regioselective synthesis of uroporphyrinogen-octanitrile (type I) based on the strategy of multiple use of (dimethylmethylidene)ammonium iodide for stepwise regioselective functionalization of the pyrrole nucleus is described. This uroporphyrinogen derivative is remarkably stable and beautifully crystallizes in space group P1 with one molecule per unit cell. The crystal structure of the compound shows interesting conformational characteristics which are interpreted to be caused by subtle stereoelectronic effects. The English Footnotes to Schemes 1-3 and Figs. 1-12 provide an extension of this summary. 相似文献
67.
Osmotic and activity coefficients in the aqueous quaternary system sodium chloride-potassium chloride-calcium chloride were derived from isopiestic measurements at 25°C. The isopiestic data were treated by the various procedures of Scatchard, Friedman, and Reilly, Wood, and Robinson. The results obtained showed good agreement with those obtained by pseudo-ternary transforms. Interaction parameters obtained indicated the preponderance of pairwise interactions. Excess Gibbs free energies of mixing were calculated. 相似文献
68.
Y. Marcus 《Journal of solution chemistry》1991,20(9):929-944
Taft and Kamlet's -scale of solvent hydrogen bond donation ability is reexamined with regard to its correlations with three widely used polarity scales: Dimroth and Reichardt's E
T
(30), Kosower's Z and Mayer's A
N
, as well as with the m values of the solvents when present as monomeric solutes. The correlation with E
T
serves to extend the solvent -scale according to the expression:
相似文献
69.
A microscopic polymer liquid-state theory has been developed for the structure, thermodynamics and mechanical properties of strained liquid crystalline elastomers. The theory captures the experimentally observed phenomenon of spontaneous distortion and establishes a direct correlation between it and the nematic order parameter. Strain induced softening of the elastic modulus is predicted to emerge due to coupling of the induced orientational order and anisotropic interchain excluded volume interactions. Comparison of our results with limited experiments shows good qualitative and sometimes quantitative agreement. The theory predicts that deformation in the liquid crystalline state results in an increase of the amplitude of density fluctuations (compressibility) which becomes more pronounced as chain degree of polymerization and/or segmental density are decreased. 相似文献
70.
Michael F. Cunningham Karine Tortosa Marcus Lin Barkev Keoshkerian Michael K. Georges 《Journal of polymer science. Part A, Polymer chemistry》2002,40(16):2828-2841
The rate‐accelerating effects of camphorsulfonic acid (CSA) on nitroxide‐mediated styrene miniemulsion polymerization were studied. Polymerizations were initiated with benzoyl peroxide (BPO) as an initiator and mediated with either 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO) or 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyloxy (OH‐TEMPO). Although CSA has been used to accelerate the rate in bulk nitroxide‐mediated polymerizations, it has not been well studied in emulsion/miniemulsion. With dispersed systems, the effectiveness of CSA is likely to be affected by partitioning between the aqueous and organic phases. In styrene miniemulsion experiments performed over a range of conditions, the effect of adding CSA varied from negligible to significantly increasing the final conversion and molecular weight, depending on the nitroxide:BPO ratio. At a ratio of nitroxide:BPO = 1.7, the effect of CSA addition is small, whereas the final conversion and molecular weight are dramatically enhanced by CSA addition when the nitroxide:BPO ratio is 3.6. CSA is most effective in enhancing the rate and molecular weight when the initial free‐nitroxide concentration is higher. The magnitude of the rate and molecular weight enhancement was similar for TEMPO and OH‐TEMPO despite their differences in water solubility. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2828–2841, 2002 相似文献
|