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991.
A combination of supersonic-jet laser spectroscopy and quantum chemistry calculation was applied to 1,4-bis(phenylethynyl)benzene, BPEB, to study the role of the dark pisigma* state on electronic relaxation and the effect of ring torsion on electronic spectra. The result provides evidence for fluorescence break-off in supersonic jet at high S1(pi pi*) <-- S0 excitation energies, which can be attributed to the pi pi*-pi sigma* intersection. The threshold energy for the fluorescence break-off is much larger in BPEB (approximately 4000 cm(-1)) than in diphenylacetylene (approximately 500 cm(-1)). The high-energy barrier in BPEB accounts for the very large fluorescence quantum yield of the compound (in solution) relative to diphenylacetylene. The comparison between the experimentally derived torsional barrier and frequency with those from the computation shows overall good agreement and demonstrates that the low-energy torsional motion involves the twisting of the end ring in BPEB. The torsional barrier is almost an order of magnitude greater in the pi pi* excited state than in the ground state. The finding that the twisting of the end ring in BPEB is relatively free in the ground state, but strongly hindered in the excited state, provides rationale for the well-known temperature dependence of the spectral shape of absorption and the lack of mirror symmetry relationship between the absorption and fluorescence at elevated temperatures.  相似文献   
992.
Addition of alcohols and phenols to allyl ethers catalyzed mainly by ruthenium complexes was studied. Complexes of ruthenium generated in situ from precursors such as {[RuCl2(1,5-COD)]x} or [Ru3(CO)12] and from external ligands such as phosphines (e.g. PPh3, PBu3, BINAP) or phosphites (e.g. P(OPh)3, P(OMe)3) were found to be particularly efficient catalysts of the studied reactions. Transacetalization reaction could be practically completely eliminated by the addition of a base (particularly Na2CO3) to the catalytic systems. It was observed that the selectivity of mixed acetals formation increases with increasing value of Θ parameter of phosphines. Especially interesting results (0–5% of transacetalization) have been obtained for catalytic systems generated from {[RuCl2(1,5-COD)]x} or [Ru3(CO)12], phosphines (PPh3, BINAP, dppe, tris(2,4,6-tri-metylphenyl)phosphine, or dppf) and Na2CO3. The mechanism of mixed acetals formation has been investigated using deuterated reagents. It is postulated that the examined reaction is a nucleophilic addition of ROH to a hydrido-π-allyl complex formed during oxidative addition of allyl substrate to metal complex. As a result, a new, selective, and convenient method of the synthesis of symmetrical and, in particular, unsymmetrical (mixed) acetals has been developed. Mixed acetals CH3CH2CH(OR1)(OR2) may be obtained in the reaction of R1-O-allyl with R2OH or R1OH with R2-O-allyl, depending on the structure of R1 and R2.  相似文献   
993.
This paper takes up the systematic study of the Gottlieb groups of spheres for k≤13 by means of the classical homotopy theory methods. We fully determine the groups for k≤13 except for the 2-primary components in the cases: k=9,n=53;k=11,n=115. In particular, we show if n=2i−7 for i≥4.  相似文献   
994.
995.
We have measured the synchrotron‐induced photofragmentation of isolated 2‐deoxy‐D ‐ribose molecules (C5H10O4) at four photon energies, namely, 23.0, 15.7, 14.6, and 13.8 eV. At all photon energies above the molecule′s ionization threshold we observe the formation of a large variety of molecular cation fragments, including CH3+, OH+, H3O+, C2H3+, C2H4+, CHxO+ (x=1,2,3), C2HxO+ (x=1–5), C3HxO+ (x=3–5), C2H4O2+, C3HxO2+ (x=1,2,4–6), C4H5O2+, C4HxO3+ (x=6,7), C5H7O3+, and C5H8O3+. The formation of these fragments shows a strong propensity of the DNA sugar to dissociate upon absorption of vacuum ultraviolet photons. The yields of particular fragments at various excitation photon energies in the range between 10 and 28 eV are also measured and their appearance thresholds determined. At all photon energies, the most intense relative yield is recorded for the m/q=57 fragment (C3H5O+), whereas a general intensity decrease is observed for all other fragments— relative to the m/q=57 fragment—with decreasing excitation energy. Thus, bond cleavage depends on the photon energy deposited in the molecule. All fragments up to m/q=75 are observed at all photon energies above their respective threshold values. Most notably, several fragmentation products, for example, CH3+, H3O+, C2H4+, CH3O+, and C2H5O+, involve significant bond rearrangements and nuclear motion during the dissociation time. Multibond fragmentation of the sugar moiety in the sugar–phosphate backbone of DNA results in complex strand lesions and, most likely, in subsequent reactions of the neutral or charged fragments with the surrounding DNA molecules.  相似文献   
996.
Incoherent inelastic neutron scattering spectra for the three crystalline polymorphs (alpha- P2(1)/n, beta- P2(1), gamma- P3(1)) of glycine (C2H5NO2) at temperatures between 5 and 300 K (using the time-of-flight (ToF) spectrometer NEAT at HMI) and at pressures from ambient up to 1 GPa (using the ToF spectrometer IN6 at the ILL) were measured. Significant differences in the band positions and their relative intensities in the density of states (DoS) were observed for the three polymorphs, which can be related to the different intermolecular interactions. The mean-squared displacement, (T), dependence reveals a change in dynamic properties at about the same temperature (150 K) for all the three forms, which can be related to the reorientation of the NH3 group. Besides, a dynamic transition in beta-glycine at about 230-250 K on cooling was also observed, supporting previously obtained adiabatic calorimetry data. This behavior is similar to that already observed in amorphous solids, on approaching the glass transition temperatures, as well as in biological systems. It suggests the onset of degrees of freedom most likely related to transitions between slightly different conformational orientations. The DoS obtained as a function of pressure has confirmed the stability of the alpha-form with respect to pressure and also depicted a sign of the previously reported reversible beta-beta' glycine phase transition in between 0.6 and 0.8 GPa. Moreover, a remarkable kinetic effect in the pressure-induced phase transition in gamma-glycine was revealed. After the sample was kept at 0.8 GPa for an hour in the neutron beam, an irreversible transition into a high-pressure form (different from the beta'-form) occurred, although previously in X-Ray diffraction and Raman spectroscopy experiments a gamma- to delta-glycine phase transition was observed above 3.5 GPa only.  相似文献   
997.
Activity coefficients at infinite dilution, gammainfinity, of organic compounds in two new room-temperature ionic liquids (n-methacryloyloxyhexyl-N-methylimidazolium bromide (C10H17O2MIM)(Br) at 313.15 and 323.15 K and n-acryloyloxypropyl-N-methylimidazolium bromide(C6H11O2MIM)(Br)) were determined using inverse gas chromatography. Phase loading studies of the net retention volume per gram of packing as a function of the percent phase loading were used to estimate the influence of concurrent retention mechanisms on the accuracy of activity coefficients at infinite dilution of solutes in both ionic liquids. It was found that most of the solutes were retained largely by partition with a small contribution from adsorption and that n-alkanes were retained predominantly by interfacial adsorption on ionic liquids studied in this work. The solvation characteristics of the two ionic liquids were evaluated using the Abraham solvation parameter model.  相似文献   
998.
Microorganisms like bacteria, viruses, fungi, etc. have a major impact on human, animal, and plant life. Several decades ago it was observed that intact cells suspended in an isotonic salt solution moved toward the anode and the mobility was proportional to the density of the charge located on the cell surfaces. Since then, efforts have been made to make electrophoresis a useful tool in cell studies. Microorganisms are no exception. In the present work we applied the capillary zone electrophoresis (CZE) with dynamical modification of the capillary surface for separation of E. coli and P. vulgaris. The same method was used for identification of E. coli in infected urine (direct injection - UTIs) and also for identification of Helicobacter pylori which is a gram-negative bacillus responsible for one of the most common infections found in humans worldwide. Using spectrophotometric measurements at λ = 214 nm we proved that it is possible to measure the concentration of bacterial cells up to 5 × 108 cells/mL. Recent studies have demonstrated very practical uses for electrophoretic techniques, especially in the field of medical diagnosis. Figure The developed CZE method allows the rapid analysis and identification of pathogenic bacteria: example shown illustrates the identifcation of E. coli in a urine sample determined much more rapidly than with conventional culturing on Petri dishes Presented at the 11th International Conference on Chemistry and the Environment, 9–12 September 2007, Torun, Poland.  相似文献   
999.
An efficient method for the stereoselective construction of tertiary C−O bonds via a stereoinvertive nucleophilic substitution at the quaternary carbon stereocenter of cyclopropyl carbinol derivatives using water, alcohols and phenols as nucleophiles has been developed. This substitution reaction proceeds under mild conditions and tolerates several functional groups, providing a new access to the stereoselective formation of highly congested tertiary homoallyl alcohols and ethers.  相似文献   
1000.
A simple synthetic method to access a wide range of [Rh(acac)(CO)(NHC)] complexes is described. In situ infra-red monitoring provides insights into the mechanism of the reaction, including the identification of a key intermediate. An understanding of the reaction mechanism leads to the discovery of novel pathways to commonly used congeners.  相似文献   
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