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101.
Li H Li Y Zhai J Cui G Liu H Xiao S Liu Y Lu F Jiang L Zhu D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(24):6031-6038
A novel, water-soluble, cationic PPV derivative poly[(2,5-bis(3-bromotrimethylammoniopropoxy)-phenylene-1,4-divinylene)-alt-1,4-(2,5-bis(2-(2-hydroxyethoxy)ethoxy))phenylene vinylene] (BH-PPV) has been synthesized by a Heck coupling reaction. Multilayered assemblies of the BH-PPV and the sodium salt of hexa(sulfobutyl)fullerenes (C(60)-HS) were fabricated successfully by an alternate deposition technique. The multilayer structures were studied by UV/Vis spectroscopy, small angle X-ray diffraction, and atomic force microscopy. The photoinduced charge transfer property of the self-assembled multilayer film was also measured by a three-electrode cell technique. A steady and rapid cathodic 5.5 microA cm(-2) photocurrent response was measured as the irradiation of the multilayer film was switched on and off. Importantly, the response of on/off cycling is prompt and reproducible. A possible mechanism for the electron-transfer process is proposed. 相似文献
102.
The semilocalized approach to chemical reactivity (J. Mol. Struct. (Theochem) 588 (2002) 99; Int. J. Quant. Chem. 94 (2003) 302) is applied to study the addition reaction of an electrophile or nucleophile to the butadiene molecule. In accordance with the classical concept of the reaction center and its neighborhood (substituent), only one of the two H2C=CH-fragments of butadiene is supposed to be under a direct attack of the reagent, whereas the remaining H2C=CH-group is assumed to play the role of the substituent and thereby to participate in the process indirectly by exerting certain electron-donating or accepting effect upon the former group and/or the reagent. The main aim of the study consists in revealing the role of the H2C=CH-substituent in the formation of the known higher reactivity of the terminal carbon atom of the attacked C=C-bond (as compared to the internal atom) irrespective of the nature of the reagent. To this end, we seek to obtain an explicit algebraic representation of the interdependence between the direction and the extent of the total influence of the H2C=CH-substituent, on the one hand, and the nature of the reagent, on the other hand. The expressions for electron density and bond order redistributions among separate fragments of contacting molecules derived previously in the form of power series are shown to yield the above-anticipated representation. On this basis, it is demonstrated that the electron-donating effect of the initially occupied (bonding) orbital of the substituent and the electron-accepting effect of its initially vacant (antibonding) orbital upon the remaining fragments of the whole reacting system may be considered independently whatever the nature of the reagent. However, a strong interdependence is established between the actual relative extents of these two components of the total effect of the H2C=CH-group and the electron-donating (accepting) properties of the reagent. Moreover, this group of atoms is shown to manifest itself as an electron-donating (accepting) substituent under influence of an electrophilic (nucleophilic) attack. Using this principal result of the paper, the actual reactivity of butadiene with respect to electrophile (nucleophile) is interpreted by invoking a model system of a substituted ethene containing a simple (one-orbital) electron-donating (accepting) substituent, and a terminal addition easily follows for both types of the reagent. 相似文献
103.
Metathesis of hex-1-ene in ionic liquids catalyzed by WCl6 was studied. The metathesis is preceded by isomerization of hex-1-ene to hex-2-ene, from which the main reaction product, viz., oct-4-ene, is derived. The WCl6-1-butyl-3-methylimidazolium tetrafluoroborate (BMIM·BF4) system efficiently catalyzes metathesis of linear olefin, the ionic liquid serving as the reaction medium by forming a stable homogeneous catalytic system with WCl6. The yields of the metathesis products increase with increasing reaction temperature. The addition of tin-containing promoters leads to a substantial increase in the reaction rate. In the WCl6-BMIM·BF4-SnBu4 system, the selectivity of the formation of oct-4-ene is significantly enhanced.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2094–2097, October, 2004. 相似文献
104.
Yarovenko V. N. Semenov S. L. Zavarzin I. V. Ignatenko A. V. Krayushkin M. M. 《Russian Chemical Bulletin》2003,52(2):451-456
The influence of catalysts, acid chlorides, and solvents on the acylation of methyl 2-methyl-4H-thieno[3,2-b]pyrrole-5-carboxylate was studied. The use of AlCl3 allows the regioselective introduction of the acyl group into position 3 to be performed, whereas the acyl group is regioselectively introduced into position 6 of thienopyrrole when SnCl4 is used. 相似文献
105.
Paul Watson Peter Willett Valerie J. Gillet Marcel L. Verdonk 《Journal of computer-aided molecular design》2001,15(9):835-857
A knowledge-based method for calculating the similarity of functional groups is described and validated. The method is based on experimental information derived from small molecule crystal structures. These data are used in the form of scatterplots that show the likelihood of a non-bonded interaction being formed between functional group A (the `central group') and functional group B (the `contact group' or `probe'). The scatterplots are converted into three-dimensional maps that show the propensity of the probe at different positions around the central group. Here we describe how to calculate the similarity of a pair of central groups based on these maps. The similarity method is validated using bioisosteric functional group pairs identified in the Bioster database and Relibase. The Bioster database is a critical compilation of thousands of bioisosteric molecule pairs, including drugs, enzyme inhibitors and agrochemicals. Relibase is an object-oriented database containing structural data about protein-ligand interactions. The distributions of the similarities of the bioisosteric functional group pairs are compared with similarities for all the possible pairs in IsoStar, and are found to be significantly different. Enrichment factors are also calculated showing the similarity method is statistically significantly better than random in predicting bioisosteric functional group pairs. 相似文献
106.
Lisa D. Harris 《Tetrahedron letters》2005,46(10):1627-1629
The enantiomeric excess observed for the exo-adduct from the Lewis acid catalysed Diels-Alder reaction between cyclopentadiene and methacrolein can be increased up to 21% by simple modification of the electronics of the aromatic ring in a series of stilbene-derived diol ligands, suggesting that the proposed face-face π-π interaction between the catalyst and the dienophile can be modulated by altering the electron density on the aromatic ring. 相似文献
107.
M. Mallouki F. Tran-Van C. Sarrazin P. Simon B. Daffos A. De C. Chevrot J. F. Fauvarque 《Journal of Solid State Electrochemistry》2007,11(3):398-406
We report on the synthesis and electrochemical characterization of nanohybrid polypyrrole (PPy) (PPy/Fe2O3) materials for electrochemical storage applications. We have shown that the incorporation of nanoparticles inside the PPy
notably increases the charge storage capability in comparison to the “pure” conducting polymer. Incorporation of large anions,
i.e., paratoluenesulfonate, allows a further improvement in the capacity. These charge storage modifications have been attributed
to the morphology of the composite in which the particle sizes and the specific surface area are modified with the incorporation
of nanoparticles. High capacity and stability have been obtained in PC/NEt4BF4 (at 20 mV/s), i.e., 47 mAh/g, with only a 3% charge loss after one thousand cyles. The kinetics of charge–discharge is also
improved by the hybrid nanocomposite morphology modifications, which increase the rate of insertion–expulsion of counter anions
in the bulk of the film. A room temperature ionic liquid such as imidazolium trifluoromethanesulfonimide seems to be a promising
electrolyte because it further increases the capacity up to 53 mAh/g with a high stability during charge–discharge processes. 相似文献
108.
Coordination reactions of copper(II) ions and their effect on non-covalent interactions in uridine (Urd) or uridine 5′-monophosphate (UMP) systems with nucleosides (Ado, Cyd, Thd) and nucleotides (AMP and CMP) in aqueous solutions have been studied. At high pH the effective coordination centers are deprotonated N(3) atoms from Urd and Thd, whereas at low pH, the N(3) atoms of pyrimidine nucleosides are blocked for coordination and the metallation sites are endocyclic
nitrogen atoms from Ado, Cyd, AMP and CMP. Moreover, at low pH, the main reaction center in nucleotide solutions is the phosphate group. The NMR study has proven the
occurrence of non-covalent ion-dipole interactions and stacking interactions in the systems considered. Introduction of a
copper ion in the majority of systems causes the disappearance of weak interactions between ligands. The structures of the
complexes in solution have been inferred from the equilibrium study: an analysis of the pH range of their occurrence with
respect to the pH range of deprotonation of particular groups in the compounds studied, using Vis, EPR and 13C as well as 31P NMR spectral analysis. 相似文献
109.
Prof. Dr. Werner Uhl 《Angewandte Chemie (International ed. in English)》1993,32(10):1386-1397
In the attempt to synthesize compounds with aluminum in a low oxidation state and an Al Al bond, by the reduction of alkylaluminum halides with alkali metals, analogous to a Wurtz coupling, in general the deposition of elemental aluminum and the formation of the corresponding trialkylaluminum compounds is observed. Thus, tetrasubstituted dialuminum compounds R2Al AlR2, apart from a few poorly characterized examples, were for a long time considered part of an unverified class of substances. Only with the sterically very highly shielded tetrakis[bis(trimethylsilyl)methyl]dialuminum did we achieve the synthesis of the first completely characterized organoelement compound with unlimited stability, which shows aluminum in the oxidation state + II and has an Al Al bond. In the meantime, corresponding compounds for the elements gallium and indium have been obtained. With the simple access to tetrasubstituted dimetal compounds, a fascinating new research area has opened for preparative chemistry, in which the particular interest will naturally lie in the reactive properties of the metal-metal bond. 相似文献
110.
D. Fennell Evans Martin Allen B. W. Ninham Abdel Fouda 《Journal of solution chemistry》1984,13(2):87-101
Critical micelle concentrations were determined by conductance measurements for decyl-, dodecyl-, tetradecyl- and hexadecyltrimethylammonium bromide in water at 25, 60, 95, 130, and 160°C. The results are discussed in terms of the equilibrium model and the nonlinear Poisson-Boltzmann model for micelle formation. The free energies of transferring a methylene group from water to the oil-like interior of the micelle are found to be –781 at 25°C, –796 at 60°C, –819 at 95°C, –815 at 130°C, and –787 at 160°C cal-mol–1. 相似文献