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Pilar Jiménez Maria Victoria Roux JiŘi Kulhánek Otto Exner 《Structural chemistry》1996,7(5-6):375-381
The energy of combustion of 2,5-dimethoxybenzoic acid has been determined using a static bomb calorimeter. The vapor pressures of the compound have been measured over a 18 K temperature interval by the Knudsen effusion technique. Heat capacity measurements betweenT=270 K andT=338 K were carried out by DSC. From these experimental results the standard molar enthalpies of combustion, sublimation, and formation in the crystalline and gaseous state at the temperature 298.15 K have been derived. With this compound, the series of mono- and dimethoxy-benzoic acids have been completed. Theirf H
m
o
values were expressed by an additive relationship, taking into account the number of methoxy groups and the number of all 1,2 interactions: an accuracy of 3.3 kJ·mol–1 was achieved. In an alternative approach the substituent effect of the methoxy groups was evaluated within the framework of isodesmic reactions. The effect of disubstitution was referred to mono derivatives and the excess energy—the so-called buttressing effect—was evaluated (2–24 kJ· mol–1 for individual bis derivatives). These values were explained in terms of the conformation of the methoxy group around the Car-O bond. 相似文献
34.
钢结构吊车梁在工业建筑中被广泛应用,应力集中的存在导致几何不连续位置在复杂应力下服役.借助有限元法分析吊车梁应力-应变状态,确定危险点位置,并提取应力、应变分量;以应变能密度作为损伤参量并以最大平面为临界面,基于能量准则建立临界面位置数值计算方法,结合有限元结果给出吊车梁临界面位置;考虑吊车梁在非对称载荷下服役,借助Goodman方程进行平均应力修正,并结合Q355D钢近似S-N曲线计算疲劳寿命.该方法考虑了应力集中处多轴应力对疲劳损伤的影响,可以为复杂应力下几何不连续钢构件的疲劳寿命评估提供新方法. 相似文献
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Jim Coykendall 《Proceedings of the American Mathematical Society》1996,124(6):1727-1732
The image of the norm map from to (two rings of algebraic integers) is a multiplicative monoid . We present conditions under which is a UFD if and only if has unique factorization into irreducible elements. From this we derive a bound for checking if is a UFD.
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A -symmetric spaceM is a complete connected regular Sasakian manifold, that fibers over an Hermitian symmetric spaceN, so that the geodesic involutions ofN lift to define global (involutive) automorphisms of the Sasakian structure onM. In the present paper the complete classification of -symmetric spaces is obtained. The groups of automorphisms of the Sasakian structures and the groups of isometries of the underlying Riemannian metrics are determined. As a corollary, the Sasakian space forms are also determined. 相似文献
39.
The chiral phosphine‐oxazoline ligands 3 and 4 bearing 4‐alkoxymethyl substituents on the oxazoline ring with (R)‐configuration were prepared from L‐serine methyl ester in 66% and 33% yields, respectively. Along this synthetic pathway, the β‐hydroxylamides derived from L‐serine methyl ester and 2‐halobenzoyl chlorides were expediently converted to the corresponding oxazolines by using diethylaminosulfur trifluoride as the activation agent. Potassium diphenylphosphide was the reagent of choice for replacing the bromine atom on the phenyl ring, giving the desired oxazoline‐phosphine ligands 3 and 4 . Together with [Pd(η3‐allyl)Cl]2, ligands 3 and 4 induced an enantioselective allylic substitution reaction of 1,3‐diphenyl‐2‐pro‐penyl acetate by dimethyl malonate. Although ligands 3 and 4 exhibit the (R)‐configuration, differing from the (S)‐configuration of Pfaltz‐Helmchen‐Williams phosphine‐oxazoline ligands, all these ligands led to the same enantiotopic preference in the allylic substitution reaction. To facilitate the recovery and reuse of the phosphine‐oxazoline ligand, immobilization on Merrifield resin was attempted, albeit in low loading. 相似文献
40.
Mikkelsen LM Hernáiz MJ Martín-Pastor M Skrydstrup T Jiménez-Barbero J 《Journal of the American Chemical Society》2002,124(50):14940-14951
The conformational properties of the C-glycosyl analogue of the core trisaccharide alpha-D-Man-(1 --> 3)-[alpha-D-Man-(1 --> 6)]-D-Man in solution have been carefully analyzed by a combination of NMR spectroscopy and time-averaged restrained molecular dynamics. It has been found that both the alpha-1,3- and the alpha-1,6-glycosidic linkages show a major conformational averaging. Unusual Phi ca. 60 degrees orientations for both Phi torsion angles are found. Moreover, a major conformational distinction between the natural compound and the glycomimetic affects to the behavior of the omega(16) torsion angle around the alpha-1 --> 6-linkage. Despite this increased flexibility, the C-glycosyl analogue is recognized by three mannose binding lectins, as shown by NMR (line broadening, TR-NOE, and STD) and surface plasmon resonance (SPR) methods. Moreover, a process of conformational selection takes place, so that these lectins probably bind the glycomimetic similarly to the way they recognize the natural analogue. Depending upon the architecture and extension of the binding site of the lectin, loss or gain of binding affinity with respect to the natural analogue is found. 相似文献