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21.
Janusz Grabowski 《Annals of Global Analysis and Geometry》1993,11(3):213-220
It is proved that for infinite dimensional Lie groups in the sense of the differential calculus of Frölicher and Kriegl the derivative of the exponential mappings is given by the formula d(exp)(X)Y=dexp(X)(e)
0
1
Adexp(–tX)
Y dt, where stands for the left translation ande is the neutral element.This work was supported by the Alexander von Humboldt-Stiftung. 相似文献
22.
It is shown that enantioselective solvent-generated liquid-liquid and liquid-solid Chromatographic systems with -cyclodextrin derivatives can be realized. The liquid-liquid systems are based on ternary solvent systems of limited miscibility, containing chiral additives; the chiral stationary phase is spontaneously generated on the porous microparticulate silica used as a solid support. In the solvent-generated adsorption systems a very small proportion of -cyclodextrin derivatives is added to the mobile phase. These components act as column activators, since they are strongly adsorbed on the RP solid support where they form new stereoselective adsorption sites. It is demonstrated that dynamically generated systems with -cyclodextrin derivatives as chiral agents are powerful and versatile tools for enantioseparation of different types of compounds. This technique creates not only a new type of selectivity but also leads to very stable and reproducible Chromatographic columns.Dedicated to Professor J. F. K. Huber on the occasion of his 65th birthday 相似文献
23.
In this paper we consider problems concerning the effectiveness of iterational calculations on vibrational analysis. Instead of the widespread least-squares method of force field refinement, another method is proposed based on the steepest-descent algorithm for calculation of the functional minimum of many variables. The new method does not require inverting of a large, poorly conditioned matrix or the introduction of experimental damping coefficients for improving the convergency of the calculations. Test calculations performed for several molecules exhibit a significant “elasticity” of the proposed algorithm allowing more precise reproduction of the molecular vibration frequencies than can be found in recently published works. 相似文献
24.
Prof. Dr. Stefan Smoliński Janusz Jamrozik Maria Jamrozik 《Monatshefte für Chemie / Chemical Monthly》1977,108(5):1145-1151
We have obtained four new bispirane systems in which both spiroatoms are vicinal atoms in cyclopropane or cyclobutane rings and in which the heterocyclic component has the basic structure of 1,4-dioxep-2-ene. We have shown that from two possibilities (bispiran, propellan) the general reaction leads only to a bispiran system. To the bispiran2 exhibiting the highest hyperchromism we ascribed the bispirocoplanar conformation (Fig. 1).
Mit 3 Abbildungen 相似文献
Mit 3 Abbildungen 相似文献
25.
Janusz B. Kyziol 《Journal of heterocyclic chemistry》1985,22(5):1301-1305
The synthesis of 3-nitrosocarbazole (I) by the Fischer-Hepp rearrangement of 9-nitrosocarbazole has been described. The resistance of I to oxidation provides evidence that it cannot be the intermediate in the conversion of 9-nitrosocarbazole to the C-nitro compounds. It has also been shown that I and its derivatives cannot be synthesized by the action nitrosyl chloride on carbazoles. Methylation of I yields 9-methyl-3-nitrosocarbazole, 9,9′-dimethyl-3-azocarbazole and 9,9′-dimethyl-3-azoxycarbazole as the main products. The mechanism of this disproportionation process has been proposed. The spectral data of I are given. 相似文献
26.
Reversible storage of molecular hydrogen by sorption into multilayered TiO2 nanotubes 总被引:4,自引:0,他引:4
Bavykin DV Lapkin AA Plucinski PK Friedrich JM Walsh FC 《The journal of physical chemistry. B》2005,109(41):19422-19427
The sorption of hydrogen between the layers of the multilayered wall of nanotubular TiO2 was studied in the temperature range of -195 to 200 degrees C and at pressures of 0 to 6 bar. Hydrogen can intercalate between layers in the walls of TiO2 nanotubes forming host-guest compounds TiO2 x xH2, where x < or = 1.5 and decreases at higher temperatures. The rate of hydrogen incorporation increases with temperature and the characteristic time for hydrogen sorption in TiO2 nanotubes is several hours at 100 degrees C. The rate of intercalate formation is limited by the diffusion of molecular hydrogen inside the multilayered walls of the TiO2 nanotube. 1H NMR-MAS and XRD data confirm the incorporation of hydrogen between the layers in the walls of TiO2 nanotubes. The nature and possible applications of the observed intercalates are considered. 相似文献
27.
Fastyn P Kornacki W Gierczak T Gawłowski J Niedzielski J 《Journal of chromatography. A》2005,1078(1-2):7-12
The water uptake by carbon molecular sieves (CMS) and graphitized carbons, all of which are used to determine volatile organic compounds in air, was investigated using a direct experimental approach. CMS, e.g. Carboxen 1002, Carboxen 1003 and Anasorb CMS adsorb substantial amounts of water, in the range 400 to 450 mg per gram of adsorbent. Graphitized carbons, e.g. Carbrogaph 5TD and Carbopack X show low water trapping, less than 30 mg g(-1) and Carbopack Y as little as 5 mg g(-1) or less. The water sorption capacity for graphitized carbons is strongly dependent on the relative humidity (RH). The change of RH from 95 to 90% decreases the amount of adsorbed water by more than a factor of 2. Two different water adsorption mechanisms are operative: adsorption on polar centers and micropore volume filling. For graphitized carbons and CMS at low RH, adsorption on polar centers is involved. For CMS, once the threshold value of relative humidity (RHth) is surpassed, micropore volume filling becomes predominant. RHth is 44 +/- 3 and 42 +/- 3% for Carboxen 1002 and 1003, respectively, and 32 +/- 3% for Anasorb CMS. The CMS mass in the trap was found not to affect the mass of retained water under condition of incomplete saturation of adsorbent bed with water. Thus, the restrictions commonly imposed on the CMS mass are not necessary. The dry purging technique is suggested to remove adsorbed water. Carbograph 5TD and Carbopack X require only a few hundred ml of dry air to remove adsorbed water entirely. Water can also be purged out from CMS; however, much larger volumes of dry air are needed. 相似文献
28.
We characterized valence anionic states of 1-methylcytosine using various electronic structure methods. We found that the most stable valence anion is related to neither the canonical amino-oxo nor a rare imino-oxo tautomer, in which a proton is transferred from the N4 to N3 atom. Instead, it is related to an imino-oxo tautomer, in which the C5 atom is protonated. This anion is characterized by an electron vertical detachment energy (VDE) of 2.12 eV and it is more stable than the anion based on the canonical tautomer by 1.0 kcal/mol. The latter is characterized by a VDE of 0.31 eV. Another unusual low-lying imino-oxo tautomer with a VDE of 3.60 eV has the C6 atom protonated and is 3.6 kcal/mol less stable than the anion of the canonical tautomer. All these anionic states are adiabatically unbound with respect to the canonical amino-oxo neutral, with the instability of 5.8 kcal/mol for the most stable valence anion. The mechanism of formation of anionic tautomers with carbon atoms protonated may involve intermolecular proton transfer or dissociative electron attachment to the canonical neutral tautomer followed by a barrier-free attachment of a hydrogen atom to the C5 or C6 atom. The six-member ring structure of anionic tautomers with carbon atoms protonated is unstable upon an excess electron detachment. Indeed the neutral systems collapse without a barrier to a linear or a bicyclo structure, which might be viewed as lesions to DNA or RNA. Within the PCM hydration model, the anions become adiabatically bound with respect to the corresponding neutrals, and the two most stable tautomers have a carbon atom protonated. 相似文献
29.
Dabkowska I Rak J Gutowski M Nilles JM Stokes ST Bowen KH 《The Journal of chemical physics》2004,120(13):6064-6071
The photoelectron spectrum of the uracil-alanine anionic complex (UA)(-) has been recorded with 2.540 eV photons. This spectrum reveals a broad feature with a maximum between 1.6 and 2.1 eV. The vertical electron detachment energy is too large to be attributed to an (UA)(-) anionic complex in which an intact uracil anion is solvated by alanine, or vice versa. The neutral and anionic complexes of uracil and alanine were studied at the B3LYP and second-order M?ller-Plesset level of theory with 6-31++G(*) (*) basis sets. The neutral complexes form cyclic hydrogen bonds and the three most stable neutral complexes are bound by 0.72, 0.61, and 0.57 eV. The electron hole in complexes of uracil with alanine is localized on uracil, but the formation of a complex with alanine strongly modulates the vertical ionization energy of uracil. The theoretical results indicate that the excess electron in (UA)(-) occupies a pi(*) orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of alanine to the O8 atom of uracil. As a result, the four most stable structures of the uracil-alanine anionic complex can be characterized as a neutral radical of hydrogenated uracil solvated by a deprotonated alanine. Our current results for the anionic complex of uracil with alanine are similar to our previous results for the anion of uracil with glycine, and together they indicate that the BFPT process is not very sensitive to the nature of the amino acid's hydrophobic residual group. The BFPT to the O8 atom of uracil may be relevant to the damage suffered by nucleic acid bases due to exposure to low energy electrons. 相似文献
30.
The kinetics of base hydrolysis of the trans-[Cr(NH3)2(NCS)4]– anion follows the rate law: -d[complex]/dt = k
0 + k
1[OH–] (50–70 °C, [OH–] = 0.1–1.9 M and = 2.0 M). The specific salt effect has been investigated for eight aqueous media: NaCl, NaBr, NaI, NaClO4, KCl, KBr, CsCl and CsBr. The alkali-independent path (k
0) does not show any specific effect of inert electrolyte ions, the activation parameters: H
= 113.5 ± 0.4 kJ mol–1 and S
= 24.1 ± 1.3 J mol–1 K–1 are interpreted in the frame of a dissociative interchange mechanism (I
d). For the alkali-dependent path (k
1) the specific salt effect is observed for cations of the inert electrolyte, showing an important role for ion-pair formation between the cations and reagent complex anion in the activation process. A linear correlation between lnk
1 and lnK
0 (K
0 – ion-pair formation constant) has been found for the cations studied. The dissociative, via conjugate base, mechanism (D
CB) has been proposed for the alkali-dependent path. 相似文献