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71.
Fiedler SL Vaskonen KJ Eloranta JM Kunttu HM 《The journal of physical chemistry. A》2005,109(20):4512-4516
Electronic spectroscopy of the C(2) molecule is investigated in Ar, Kr, and Xe matrixes in the 150-500 nm range. In the Ar matrix, the D ((1)Sigma(u)(+)) <-- ((1)Sigma(g)(+)) Mulliken band near 240 nm is the sole absorption in the UV range, whereas in the Kr matrix additional bands in the 188-209 nm range are assigned to the Kr(n)()(+)C(2)(-) <-- Kr(n)()C(2) charge-transfer absorptions. Because of the formation of a bound C(2)Xe species, the spectral observations in the Xe matrix differ dramatically from the lighter rare gases: the Mulliken band is absent and new bands appear near 300 and 423 nm. The latter is assigned to the forbidden B'((1)Sigma(g)(+)) <-- X ((1)Sigma(g)(+)) transition, but the origin of the former remains unclear. The spectral assignments are aided by electronic structure calculations at the MCSCF, CCSD(T), and BCCD(T) levels of theory and correlation consistent basis sets. A significant presence of multireference character of the C(2)Xe system was noted and a linear ground-state structure is predicted. The computational results contradict previous density functional studies on the same system. 相似文献
72.
Novel large polyazadioxime molecules 4,5,8,9-tetraaza-3,6,7,10-tetramethyl -3,5,7,9-dodecatetraene-2, 11-dione-2, 11-dioxime (H2doxN4) and 4,5,8,9,12, 13-hexaaza-3,6,7,10,11,14-hexamethyl-3, 5,7,9,11,13-hexadecahexane-2,15-dione-2, 15-dioxime (H2doxN6) were synthesized. The molecular geometries of these molecules as well as smaller dioxime molecules, H2dox and H2doxN2 were optimized by using modified intermediate neglect of differential overlap (MNDO) calculations. The optimized conformations for all the molecules under study are close to the all-E, all-s trans conformation of C2h symmetry group. However, the energy barriers of internal rotation around the N-N single bonds were found to be low. Therefore some distortions of the polyazabackbone through internal rotation the N-N bonds have been evidenced. By infrared and Raman spectroscopies in the solid state as well as in solution. From the MNDO calculations and vibrational spectroscopy, the polyaza chain molecules under study appear as a poorly conjugated system and can be represented as a sequence of single and double bond alternation. 相似文献
73.
Capillary electrophoresis coupled to mass spectrometry (CE-MS) is reported for the first time as an alternative and powerful analytical method for the characterization and monitoring of N-substituted 1-amino-1-deoxyketoses (Amadori compounds). It allows rapid separation and identification of Amadori compounds, while benefiting from the well-known advantages of MS, such as specificity and sensitivity. Amadori compounds of several amino acids, such as glycine, valine, isoleucine, methionine, proline, and phenylalanine, as well as a cysteine-derived compound, were separated and/or discriminated using CE-MS/MS under standard conditions. The technique may also be useful to study the stability and degradation kinetics of other labile charged Maillard intermediates that play an important role in food and medical science. 相似文献
74.
Guilard R Gryko DT Canard G Barbe JM Koszarna B Brandès S Tasior M 《Organic letters》2002,4(25):4491-4494
[reaction: see text] We have developed a new method that affords regioisomerically pure corroles possessing up to three different substituents at the meso positions. The corrole formation reaction involves the acid-catalyzed condensation of a dipyrromethane-dicarbinol with pyrrole followed by oxidation with DDQ. ABC-Type corroles were synthesized for the first time according to this procedure. 相似文献
75.
A kinetic method for the simultaneous determination of magnesium and calcium ions in solution is described. The method is based on the dissociation reactions of cryptand (2.2.2) complexes; a stopped-flow injection technique is used with spectrophotometric monitoring of the phthalein complexone complexes of the released metal ions. Analyses were done at a rate of 80 h?1, with injected sample volumes of 80 μl. A microcomputer system for data acquisition and control of the system is described. 相似文献
76.
We show that a simple two-dimensional vibrational model can explain most of the features observed in the first and second OH-stretching overtone region of the room temperature cis,cis-HOONO spectrum. The model uses ab initio calculated parameters and includes the OH-stretching mode coupled to the internal torsion of the OH group. 相似文献
77.
Børge Bak Niels A. Kristiansen Henrik Svanholt Arne Holm Steen Rosenkilde 《Chemical physics letters》1981,78(2):301-303
Microwave Spectra of 13CH212C80,78Se and 12CH213C80,78Se (selenoketene) are recorded. B 5-13C-1,2,3-selenadiazole all four species are formed. The 13C scrambling may take place via a three-membered ring, selenirene, but as expected its microwave spectrum was not observed. 相似文献
78.
Thermal degradation at 180° in air of PVC stabilized with an equimolar mixture of Ba and Cd stearates has been studied. The “unreacted” stearates were separated by filtering tetrahydrofuran solutions of samples. The filtration and thermal degradation were examined by means of infrared spectroscopy in the range 1400–1800 cm?1. It has been demonstrated that, during the thermal stress, CdCl2 is accumulated in the sample and that the presence of Ba stearate supports only the consumption of Cd stearate. 相似文献
79.
Ovcharenko VV Pihlaja K Stájer G 《Journal of the American Society for Mass Spectrometry》2003,14(9):1049-1056
The mass spectrometric behavior of stereo- and regioisomeric, partially saturated isoindoloquinazolines was studied by positive-ion electron ionization (EI) and fast-atom bombardment (FAB/LSIMS) mass spectrometry combined with collision-induced dissociation (CID). A highly stereospecific retro-Diels-Alder process was observed in the cyclohexene-fused isomers under the EI conditions, and a corresponding (although less specific) fragmentation was observed in their FAB spectra. In the absence of RDA fragmentations, regio- and stereoisomers of the cyclohexane-fused heterocycles could be distinguished based on their FAB/CID spectra. 相似文献
80.
B.?Stark C.?Lach B.?Farago H.?Frey C.?Schlenk B.?StühnEmail author 《Colloid and polymer science》2003,281(7):593-600
A series of carbosilane dendrimers with perfluorinated end groups has been prepared. The structure of these molecules in dilute solution is studied using small angle neutron scattering. For generations g<3 we find a non-spherical shape of the particles and a tendency for aggregation. This result is supported by the analysis of the diffusion coefficient obtained from photon correlation spectroscopy. The overall shape of the molecules is that of a core-shell particle. The generation 4 molecule is obtained as a compact sphere. Neutron spin echo spectroscopy reveals a relaxation time which is attributed to the form fluctuations of this particle. 相似文献