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991.
The reaction CH(3) + O(2) (+M) --> CH(3)O(2) (+M) was studied in the bath gases Ar and N(2) in a high-temperature/high-pressure flow cell at pressures ranging from 2 to 1000 bar and at temperatures between 300 and 700 K. Methyl radicals were generated by laser flash photolysis of azomethane or acetone. Methylperoxy radicals were monitored by UV absorption at 240 nm. The falloff curves of the rate constants are represented by the simplified expression k/k(infinity) approximately [x/(1 + x)]F(cent)(1/{1+[(log)(x)/)(N)(]2}) with x = k(0)/k(infinity) F(cent) approximately 0.33, and N approximately 1.47, where k(0) and k(infinity) denote the limiting low and high-pressure rate constants, respectively. At low temperatures, 300-400 K, and pressures >300 bar, a fairly abrupt increase of the rate constants beyond the values given by the falloff expressions was observed. This effect is attributed to a contribution from the radical complex mechanism as was also observed in other recombination reactions of larger radicals. Equal limiting low-pressure rate constants k(0) = [M]7 x 10(-31)(T/300 K)(-3.0) cm(6) molecule(-2) s(-1) were fitted for M = Ar and N(2) whereas limiting high-pressure rate constants k(infinity) = 2.2 x 10(-12)(T/300 K)(0.9) cm(3) molecule(-1) s(-1) were approached. These values are discussed in terms of unimolecular rate theory. It is concluded that a theoretical interpretation of the derived rate constants has to be postponed until better information of the potential energy surface is available. Preliminary theoretical evaluation suggests that there is an "anisotropy bottleneck" in the otherwise barrierless interaction potential between CH(3) and O(2). 相似文献
992.
Ramos JM Viana RM Téllez S CA Pereira WC Izolani AO da Silva MI 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,65(2):433-438
To elucidate tentative assignments of metal-ligand modes of thiosemicarbazide complexes, a structural study and a assignment of the normal vibrations of 2-methylthiosemicarbazide copper(II) nitrate, [Cu(2MeTSC)(2)(NO(3))(2)] have been done through the ab initio DFT: pBP86/DN** procedure, and through the normal coordinate analysis (NCA). In the vibrational calculations, the elongated CuONO(2) bonds of the nitrate groups were considered in the CS and CN tautomers of the complex. DFT calculations had revealed that the infrared spectra can be well interpreted through the CN tautomer, failing in the prediction of the -NO(2) group wavenumbers. A little difference stabilization energy for the tautomers were found: for the CN tautomer was E=-3487,36376a.u., and for the CS tautomer, E=-3473,93598a.u. The observed combination bands at 1763.0 and at 1754.0 cm(-1) are an indicative that the -NO(3)(-) groups acts as monodentate ligands. Calculations had confirmed the experimental assignment of the infrared spectrum. 相似文献
993.
Spectroscopy of auramine fluorescent probes free and bound to poly(methacrylic acid) 总被引:1,自引:0,他引:1
Auramines containing a vinyl group with strong electron-withdrawing substituent exhibit a pi-conjugated extended effect that gives a red shift in their absorption and emission bands. The new fluorochromic dyes were bound to poly(methacrylic acid) (PMA), and their photophysical dynamics in methanol and in aqueous solution were studied. These derivatives were also used as optical probes for copolymerization process. The process was monitored by the changes in electronic absorption with a concomitant fading of the free vinyl auramine absorption band in the red and an appearance of a UV band ascribed to dye bound to the polymer chain. The conformational transition of PMA with solvent and pH was clearly observed by the drastic changes in the photophysical properties of these auramine derivatives attached to the polymer chain. Time-resolved experiments revealed an unusual long-lived decay component of about 2.2-2.6 ns in aqueous solution at low pH together with two picosecond components (50 and 570 ps). Such long decay was only reported in the literature for auramine adsorbed in solid matrices. It was ascribed to the fraction of bound auramine in a region of compact coil of PMA. 相似文献
994.
995.
Alves C Fernandes C Dos Santos Neto AJ Rodrigues JC Costa Queiroz ME Lanças FM 《Journal of chromatographic science》2006,44(6):340-346
Solid-phase microextraction (SPME)-liquid chromatography (LC) is used to analyze tricyclic antidepressant drugs desipramine, imipramine, nortriptyline, amitriptyline, and clomipramine (internal standard) in plasma samples. Extraction conditions are optimized using a 2(3) factorial design plus a central point to evaluate the influence of the time, temperature, and matrix pH. A Polydimethylsiloxane-divinylbenzene (60-mum film thickness) fiber is selected after the assessment of different types of coating. The chromatographic separation is realized using a C(18) column (150 x 4.6 mm, 5-microm particles), ammonium acetate buffer (0.05 mol/L, pH 5.50)-acetonitrile (55:45 v/v) with 0.1% of triethylamine as mobile phase and UV-vis detection at 214 nm. Among the factorial design conditions evaluated, the best results are obtained at a pH 11.0, temperature of 30 degrees C, and extraction time of 45 min. The proposed method, using a lab-made SPME-LC interface, allowed the determination of tricyclic antidepressants in in plasma at therapeutic concentration levels. 相似文献
996.
In the absence of an experimentally solved structure, a homology model of a protein target can be used instead for virtual screening of drug candidates by docking and scoring. This approach poses a number of questions regarding the choice of the template to use in constructing the model, the accuracy of the screening results, and the importance of allowing for protein flexibility. The present study addresses such questions with compound screening calculations for multiple homology models of five drug targets. A central result is that docking to homology models frequently yields enrichments of known ligands as good as that obtained by docking to a crystal structure of the actual target protein. Interestingly, however, standard measures of the similarity of the template used to build the homology model to the targeted protein show little correlation with the effectiveness of the screening calculations, and docking to the template itself often is as successful as docking to the corresponding homology model. Treating key side chains as mobile produces a modest improvement in the results. The reasons for these sometimes unexpected results, and their implications for future methodologic development, are discussed. 相似文献
997.
Alanine-scanning mutagenesis of protein-protein interfacial residues is a very important process for rational drug design. In this study, we have used the improved MM-PBSA approach that combining molecular mechanics and continuum solvent permits one to calculate the free energy differences through alanine mutation. To identify the binding determinants of the complex formed between the IgG1 (immunoglobulin-binding protein G) and protein G, we have extended the experimental alanine scanning mutagenesis study to both proteins of this complex and, therefore, to all interfacial residues of this binding complex. As a result, we present new residues that can be characterized as warm spots and, therefore, are important for complex formation. We have further increased the understanding of the functionality of this improved computational alanine-scanning mutagenesis approach testing its sensitivity to a protein-protein complex with an interface made up of residues mainly polar. In this study, we also have improved the method for the detection of an important amino acid residue that frequently constitutes a hot spot--tryptophan. 相似文献
998.
Sousa Camila S. Lima Kayni C. M. S. Botelho Chirlene N. Pereira Neuma M. Fernandes Ridvan N. Silva Glaura G. Damos Flavio S. Luz Rita C. S. 《Journal of Solid State Electrochemistry》2020,24(8):1715-1726
Journal of Solid State Electrochemistry - Naringin is a flavanone that has been studied due to its important properties, such as anti-inflammatory, anti-oxidant, anti-microbial, anti-viral,... 相似文献
999.
Tiago A. Fernandes M. Fernanda N. N. Carvalho Adelino M. Galvão Nuno A. G. Bandeira Maria José Calhorda Ana M. Botelho do Rego 《Journal of polymer science. Part A, Polymer chemistry》2012,50(6):1102-1110
The first Cu(I) coordination polymer with an aromatic‐substituted camphorimine ligand [(CuCl)(μ‐Cl) (Cu(H2NC6H4NC10H14O)]n was obtained from reaction of CuCl with 3‐(4‐aminophenylimino)‐1,7,7‐trimethylbicyclo[2.2.1]heptan‐2‐one (H2NC6H4NC10H14O). The electronic and the surface properties (studied by X‐ray photoelectron spectroscopy) are consistent with two distinct coordination environments for the copper(I) atoms—tetrahedral and linear—for the polymer family [(CuCl)(μ‐Cl){Cu(YNC10H14O)}]n. DFT band calculations reveal that the highest energy bands are more localized on the copper(I) tetrahedral sites than on the copper(I) linear sites. The redox properties of [(CuCl)(μ‐Cl){Cu(YNC10H14O)}]n [Y = NMe2 ( 2b ), NH2, and H2NC6H4NC10H14O ( 2a )] studied by cyclic voltammetry show that the oxidation potentials of the two copper centers are in fact indistinguishable. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
1000.
Mitre C. Dourado Dieter Rautenbach Vinícius Fernandes dos Santos Philipp M. Schäfer Jayme L. Szwarcfiter Alexandre Toman 《Annals of Operations Research》2013,206(1):75-91
The generalization of classical results about convex sets in ? n to abstract convexity spaces, defined by sets of paths in graphs, leads to many challenging structural and algorithmic problems. Here we study the Radon number for the P 3-convexity on graphs. P 3-convexity has been proposed in connection with rumour and disease spreading processes in networks and the Radon number allows generalizations of Radon’s classical convexity result. We establish hardness results and describe efficient algorithms for trees. 相似文献