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The preparation of polyhydroxylated 6-oxa-nor-tropane glycomimetics structurally related to the glycosidase inhibitor family of the calystegines is reported. The synthetic strategy involves the furanose→piperidine rearrangement of 5-deoxy-5-ureido-l-idose precursors, followed by intramolecular glycosylation involving the primary hydroxyl group. Inversion of the configuration at C-3 in the resulting 6-oxa-(+)-calystegine B2 analogue allows accessing the elusive 3-epi-6-oxa-(+)-calystegine B2 skeleton. Acid-catalyzed opening of the nor-tropane bicycle was observed, however, which could be avoided by careful neutralization of the reaction mixture. The inhibition results suggest that (+)-calystegine B2 derivatives and the corresponding C-3 epimers can be seen as glucomimetics and galactomimetics, respectively, pointing to a 1-azasugar mode of action for this family of alkaloids. 相似文献
13.
We study Willmore immersed submanifoldsf: M m →S n into then-Möbius space, withm≥2, as critical points of a conformally invariant functionalW. We compute the Euler-Lagrange equation and relate this functional with another one applied to the conformal Gauss map of immersions intoS n . We solve a Bernestein-type problem for compact Willmore hypersurfaces ofS n , namely, if ?a ∈? n+2 such that <γf, a > ≠ 0 onM, whereγ f is the hyperbolic conformal Gauss map and <, > is the Lorentz inner product of? n+2, and iff satisfies an additional condition, thenf(M) is an (n?1)-sphere. 相似文献
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Georgi E. Chernev Bisserka I. Samuneva Petar R. Djambaski Isabel M. M. Salvado Helena V. Fernandes 《Central European Journal of Chemistry》2006,4(1):81-91
In this work we present experimental results about the formation, properties and structure of sol — gel silica based biocomposite
containing Calcium alginate as an organic compound. Two different types of silicon precursors have been used in the synthesis:
tetramethylortosilicate (TMOS) and ethyltrimethoxysilane (ETMS). The samples have been prepared at room temperature. The hybrids
have been synthesized by replacing different quantitis of the inorganic precursor with alginate. The structure of the obtained
hybrid materials has been studied by XRD, IR Spectroscopy, EDS, BET and AFM. The results proved that all samples are amorphous
possessing a surface area from 70 to 290 m2/g. It has also been established by FT IR spectra that the hybrids containing TMOS display Van der Walls and Hydrogen bonding
or electrostatic interactions between the organic and inorganic components. Strong chemical bonds between the inorganic and
organic components in the samples with ETMS are present. A self-organized nanostructure has been observed by AFM. In the obtained
hybrids the nanobuilding blocks average in size at about 8–14 nm for the particles. 相似文献
17.
A method for the direct determination of volatile and non-volatile nickel and vanadium compounds in crude oil without previous treatment using direct solid sampling graphite furnace atomic absorption spectrometry is proposed. The crude oil samples were weighed directly onto solid sampling platforms using a microbalance and introduced into a transversely heated solid sampling graphite tube. In previous work of our group losses of volatile nickel and vanadium compounds have been detected, whereas other nickel and vanadium compounds were thermally stable up to 1300 and 1600 °C, respectively. In order to avoid this problem different chemical modifiers (conventional and permanent) have been investigated. With 400 μg of iridium as permanent modifier, the signal started to drop already after two atomization cycles, possibly because of an interaction of nickel (which is a catalyst poison) with iridium. Twenty micrograms of palladium applied in each determination was found to be optimum for both elements. The palladium was deposited on the platform and submitted to a drying step at 150 °C for 75 s. After that the sample was added onto the platform and submitted to the furnace program. The influence of sample mass on the linearity of the response and on potential measurement errors was also investigated using four samples with different nickel content. For the sample with the lowest nickel concentration the relationship between mass and integrated absorbance was found to be non-linear when a high sample mass was introduced. It was suspected that the modifier had not covered the entire platform surface, which resulted in analyte losses. This problem could be avoided by using 40 μL of 0.5 g L−1 Pd with 0.05% Triton X-100. Calibration curves were established with and without modifier, with aqueous standards, oil-in-water emulsions and the certified reference material NIST SRM 1634c (trace metals in residual fuel oil). The sensitivity for aqueous standards and emulsions was close to that for SRM 1634c, making possible the use of aqueous standards for calibration. The limits of detection and quantification obtained for nickel and vanadium under this condition were found to be 0.02 and 0.06 μg g−1, respectively, for both elements, based on 10 mg of sample. Nickel and vanadium were determined in the samples with (total Ni and V) and without the use of Pd (thermally stable compounds), and the concentration of volatile compounds was calculated by difference. The results were compared with those obtained by high-resolution continuum source graphite furnace atomic absorption spectrometry by emulsion technique; no significant differences were found for total Ni and V at the 95% confidence level according to a Student's t-test. 相似文献
18.
Pilar Alonso Isabel de Frutos Teresa Gutiérrez Antonio Doadrio López 《Transition Metal Chemistry》1987,12(2):133-136
Summary The synthesis and the dinuclear or mononuclear nature of several molybdenum(VI) and molybdenum(V) oxocomplexes derived from 1,3-diphenyl-1,3-propanedione (HLL) are described. These complexes were identified by i.r. and electronic spectra, magnetic susceptibility and analytical data, and are assigned the following formulae: [MoO2(LL)2], [Mo2O5(LL)2], [Mo2O4(LL)2], [MoOCl(LL)2], [MoCl2(LL)] and [MoO(OH)(LL)2)]. The low magnetic moments of the dinuclear complexes are due, in part, to intramolecular interactions. The i.r. data show that the dionate is bound by two oxygen atoms forming a chelate six-membered ring. 相似文献
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Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pKa1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pKa2 and pKa3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group. 相似文献