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51.
52.
Low-noise operation of a 9-GHz hybridly mode-locked laser diode is demonstrated. The integrated timing jitter was 47 fs (10 Hz to 10 MHz) and 86 fs (10 Hz to 4.5 GHz), with a pulse width of 6.7 ps. The noise performance as a function of filter bandwidth and oscillator noise is also addressed. 相似文献
53.
Svetlana V. Kirpichenko Bagrat A. Shainyan Erich Kleinpeter 《Journal of Physical Organic Chemistry》2012,25(12):1321-1327
The conformational analysis of the first representative of the Si‐alkoxy substituted six‐membered Si,N‐heterocycles, 1,3‐dimethyl‐3‐isopropoxy‐3‐silapiperidine, was performed by low‐temperature 1H and 13C NMR spectroscopy and DFT theoretical calculations. In contrast to the expectations from the conformational energies of methyl and alkoxy substituents, the Meaxi‐PrOeq conformer was found to predominate in the conformational equilibrium in the ratio Meaxi‐PrOeq : Meeqi‐PrOax of ca. 2 : 1 as from the 1H and 13C NMR study. The thermodynamic parameters obtained by the complete line shape analysis showed that the main contribution to the barrier to ring inversion originates from the entropy term of the free energy of activation. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
54.
Erich Kleinpeter Andreas Koch Bagrat A. Shainyan 《Journal of Molecular Structure》2008,863(1-3):117-122
The spatial magnetic properties (Through Space NMR Shieldings – TSNMRS) of two cyclobutadiene derivatives (2 and 5) and of a number of cyclobutadiene dianion derivatives (3, 4 and 6–8) have been calculated by the GIAO perturbation method employing the Nucleus-Independent Chemical Shift (NICS) concept of P. v. Ragué Schleyer, and visualized as Iso-Chemical-Shielding Surfaces (ICSS) of various size and direction. TSNMRS values can be successfully employed to quantify and visualize the (anti)aromaticity of the compounds studied and to discuss the influence of Li+ complexation to cyclobutadiene dianion (4a, 7 and 8) on planar 4c,6e or three-dimensional 6c,6e aromaticity. 相似文献
55.
The λ‐transition of elemental sulfur occurring at about 159°C has long been associated with the conversion of cyclic S8 rings (c‐S8) to amorphous polymer (a‐S) via a ring opening polymerization. Here we demonstrate, with the use of both density functional and Hartree‐Fock quantum mechanical calculations, the existence of an energetically accessible, locally stable, hypervalent state of S that can form branch sites in the polymer. The significance of this finding is that the λ‐transition is best described as a gelation transition. The geometry of the tetravalent S atom is trigonal bipyramidal, with a lone pair occupying one of the three equatorial sites; it lies in a local energy minimum about 31 kcal/mol above the normal divalent state, and so is accessible both thermally and photochemically. Because the branched structure is formed endothermically, Le Chatelier's principle confirms that a percolation network can form on heating the element. The reactions that form branched structures are reversible, implying that the gel is fluxional. It decomposes at higher temperatures as chain scission competes with branching. The hypervalent structure provides an essential insight into the chemistry of elemental sulfur. 相似文献
56.
Bailey BC Fan H Baum EW Huffman JC Baik MH Mindiola DJ 《Journal of the American Chemical Society》2005,127(46):16016-16017
The transient titanium alkylidyne complex (PNP)TiCtBu (PNP = N-[2-P(CHMe2)2-4-methylphenyl]2-), prepared from alpha-hydrogen abstraction of the corresponding alkylidene-alkyl species (PNP)Ti=CHtBu(CH2tBu), can readily undergo intermolecular 1,2-addition of C-H bonds of benzene and SiMe4. Synthesis and reactivity, isotopic labeling, kinetics, and theoretical studies strongly favor an alkylidyne pathway and the alpha-H abstraction step to be the rate-determining step. 相似文献
57.
Neuvonen H Neuvonen K Koch A Kleinpeter E 《The journal of physical chemistry. A》2005,109(28):6279-6289
Equilibria between the Z (tau1= 0 degrees) and E (tau1= 180 degrees) conformers of p-substituted phenyl acetates 4 and trifluoroacetates 5 (X = OMe, Me, H, Cl, CN, NO2) were studied by ab initio calculations at the HF/6-31G* and MP2/6-31G* levels of theory. The preference for the Z conformer, DeltaE(HF), was calculated to be 5.36 kcal mol(-1) and 7.50 kcal mol(-1) for phenyl acetate and phenyl trifluoroacetate (i.e., with X = H), respectively. The increasing electron-withdrawing ability of the phenyl substituent X increases the preference of the Z conformer. An excellent correlation with a negative slope was observed for both series between DeltaE of the E-Z equilibrium and the Hammett sigma constant. By using an appropriate isodesmic reaction, it was shown that electron-withdrawing substituents decrease the stability of both conformers, but the effect is higher with the E conformer. Electron-withdrawing phenyl substituents decrease the delocalization of the lone pair of the ether oxygen to the C=O antibonding orbital (nO--> pi*C=O) in both the E and Z forms and in both series studied; this effect is higher in the E conformer than in the Z conformer. The nO --> pi*C=O electron donation has a minimum value with tau1= 90 degrees and a maximum value with tau1= 0 degrees (the Z conformer), the value with tau1= 180 degrees (the E conformer) being between these two values, obviously due to steric hindrance. The effects of the phenyl substituents on the reactivity of the esters studied are discussed in terms of molecular orbital interactions. ED/EW substituents adjust the availability of the pi*C=O antibonding orbital to interact with the lone pair orbital of the attacking nucleophile and therefore affect the reactivity: EW substituents increase and ED substituents decrease it. Excellent correlations were observed between the rate coefficients of nucleophilic acyl substitutions and pi*C=O occupancies of the ester series 4 and 5. 相似文献
58.
Zellner M Winkler W Hayden H Diestinger M Eliasen M Gesslbauer B Miller I Chang M Kungl A Roth E Oehler R 《Electrophoresis》2005,26(12):2481-2489
For the preparation of proteins for proteome analysis, precipitation is frequently used to concentrate proteins and to remove interfering compounds. Various methods for protein precipitation are applied, which rely on different chemical principles. This study compares the changes in the protein composition of human blood platelet extracts after precipitation with ethanol (EtOH) or trichloroacetic acid (TCA). Both methods yielded the same amount of proteins from the platelet preparations. However, the EtOH-precipitated samples had to be dialyzed because of the considerable salt content. To characterize single platelet proteins, samples were analyzed by two-dimensional fluorescence differential gel electrophoresis. More than 90% of all the spots were equally present in the EtOH- and TCA-precipitated samples. However, both precipitation methods showed a smaller correlation with nonprecipitated samples (EtOH 74.9%, TCA 79.2%). Several proteins were either reduced or relatively enriched in the precipitated samples. The proteins varied randomly in molecular weight and isoelectric point. This study shows that protein precipitation leads to specific changes in the protein composition of proteomics samples. This depends more on the specific structure of the protein than on the precipitating agent used in the experiment. 相似文献
59.
Siethoff C Orth M Ortling A Brendel E Wagner-Redeker W 《Journal of mass spectrometry : JMS》2004,39(8):884-889
A liquid chromatographic/tandem mass spectrometric method was developed and validated for the quantitation of capecitabine and its metabolite 5-fluorouracil in human plasma. The simultaneous determination of both analytes was achieved by a column switching method using a trapping column and two analytical columns with different stationary phases. Isocratic elution was used for the separation of capecitabine on a C18 column whereas 5-fluorouracil was separated using gradient elution on an non-polar carbon phase. The calibration curves were linear for both compounds with a correlation factor (R2) > 0.9993 for 5-fluorouracil and >0.9942 for capecitabine. The assay was validated in the concentration range 5.00-1000 ng ml(-1) for both compounds. The intra-day precision was better than 10% for 5-fluorouracil and better than 11% for capecitabine whereas the inter-day precision was better than 8% for 5-fluorouracil and better than 14% for capecitabine. 相似文献
60.
Rahul S. Pawar Erich Grundel Eugene Mazzola Kevin D. White Alexander J. Krynitsky Jeanne I. Rader 《Journal of separation science》2010,33(2):200-205
Enantioseparation of the pyrrolizidine alkaloid isomers intermedine and lycopsamine, isolated from Symphytum uplandicum, is discussed. The separatory power of two immobilized carbohydrate‐based chiral HPLC columns, Chiralpak IA and IC, in different chromatographic conditions is compared. The study demonstrated the importance of solvent and column selection while developing such chiral HPLC separation methods. The baseline HPLC separation of the two alkaloid isomers in preparatory scale is reported for the first time. The optimized separations were achieved on a Chiralpak IA column with mobile phases of ACN/methanol (80:20) and methanol/methyl‐t‐butyl ether (90:10), both containing 0.1% diethylamine. 相似文献