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121.
Boiocchi M Bonizzoni M Fabbrizzi L Foti F Licchelli M Poggi A Taglietti A Zema M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(13):3209-3216
The demetallation in acidic solution of the Cu(II) complexes with open-chain and cyclic tetramines containing a piperazine unit (2 and 3) has been investigated in terms of its kinetic aspects and compared with the behaviour of unsubstituted counterparts (tetramines 1 and 4). The presence of the piperazine fragment slows demetallation of the open-chain-ligand complex owing to the activation barrier associated with the conformational change from boat-to-half-boat; however, it does not affect the demetallation of the macrocyclic complex, which involves the spontaneous boat-to-twist conformational change. Thus, lateral reinforcement of a cyclam-like ligand does not add any further contribution to the typical inertness in demetallation of macrocyclic complexes. 相似文献
122.
Buser M Frommhold L Gustafsson M Moraldi M Champagne MH Hunt KL 《The Journal of chemical physics》2004,121(6):2617-2621
Quantum line shape calculations of the rototranslational enhancement spectra of nitrogen-methane gaseous mixtures are reported. The calculations are based on a recent theoretical dipole function for interacting N(2) and CH(4) molecules, which accounts for the long-range induction mechanisms: multipolar inductions and dispersion force-induced dipoles. Multipolar induction alone was often found to approximate the actual dipole surfaces of pairs of interacting linear molecules reasonably well. However, in the case of the N(2)-CH(4) pair, the absorption spectra calculated with such a dipole function still show a substantial intensity defect at the high frequencies (>250 cm(-1)) when compared to existing measurements at temperatures from 126 to 297 K, much as was previously reported. 相似文献
123.
Simulated Moving Bed separations of enantiomers or fine chemicals are usually carried out in the isocratic mode, i.e. by applying the same operating conditions (temperature, pressure, mobile phase composition, pH) in the whole SMB unit. However, it has been recently recognized that by properly modulating operating conditions in the SMB sections. i.e. Sections 1-4 normally, separation performance in terms of productivity and solvent consumption can be significantly improved. In this work, we study solvent gradient SMB (SG-SMB) operation, where the concentration of a modifier in the main solvent constituting the mobile phase is adjusted along the SMB unit, so as to have weaker retention of the species to be separated in the first two sections, and stronger retention in Sections 3 and 4. Overload chromatographic conditions are considered, where the adsorption behavior is characterized by a nonlinear competitive adsorption isotherm, e.g. a binary Langmuir isotherm. Design criteria to achieve complete separation are developed in the frame of the equilibrium theory of chromatography. The theoretical findings are discussed in view of typical effects of the modifier concentration on retention times and solubility of the species to be separated, and an overall assessment of the SG-SMB technology is attempted. 相似文献
124.
Aime S Calabi L Cavallotti C Gianolio E Giovenzana GB Losi P Maiocchi A Palmisano G Sisti M 《Inorganic chemistry》2004,43(24):7588-7590
An innovative MRI contrast agent based on the unprecedented and easily obtained ligand AAZTA is described. The simple and straightforward synthesis of the ligand, together with the potentiometric and relaxometric behavior of the corresponding Gd(III) chelate, is reported. The complex [Gd(AAZTA)]- shows outstanding magnetic properties connected with high thermodynamic stability in aqueous solution and a nearly complete inertness toward the influence of bidentate endogenous anions, placing this compound as one of the most promising candidates for the development of high performance MRI contrast agents. 相似文献
125.
Boiocchi M Fabbrizzi L Foti F Vazquez M 《Dalton transactions (Cambridge, England : 2003)》2004,(17):2616-2620
The spin interconversion equilibrium involving the [Ni(II)(cyclam)]2+ complex has been investigated in a variety of polar solvents, at varying temperatures. The greater the donor tendencies of the solvent, the higher the endothermicity of the high-to-low-spin conversion. In particular, a positive linear relationship exists between DeltaHdegrees and Gutmann's Donor Number (DN). In the same way, higher donor tendencies of the solvent favour the occurrence of the Ni(II)-to-Ni(III) oxidation process and negative linear relationship has been found between the E1/2(Ni(III)/Ni(II)) and DN. General behaviour is related to the intensity of the metal-solvent axial bonds in the octahedrally elongated cyclam complexes (of both Ni(II) and Ni(III)). 相似文献
126.
Sterpone F Pierleoni C Briganti G Marchit M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(11):4311-4314
Hydration of a spherical micelles of C12E6 in solution is studied by molecular dynamics simulation. The interface is found to be separated in an inner part composed of water and hydrophobic and hydrophilic moieties and an outer part with hydrophilic moiety and water only. Hydration numbers in the inner and in the outer parts are in excellent agreement with experimental data from various different methods. Temperature dehydration occurs in the inner region only and is related to the presence of water molecules directly in contact with the hydrophobic core at low temperature. 相似文献
127.
De Napoli M Nardis S Paolesse R Vicente MG Lauceri R Purrello R 《Journal of the American Chemical Society》2004,126(19):5934-5935
In aqueous solution meso-tetrakis(4-phosphonatophenyl)porphyrin shows self-aggregation processes controlled by the "sergeant-soldier rule". After partial protonation of the external phosphonic groups, it is possible (i) to further protonate the inner nitrogen atoms of the molecules or (ii) to allow, over time, the system to aggregate. Therefore, the two procedure lead to a different system evolution, producing species with different chemico-physical properties. 相似文献
128.
Callegari A Marcaccio M Paolucci D Paolucci F Tagmatarchis N Tasis D Vázquez E Prato M 《Chemical communications (Cambridge, England)》2003,(20):2576-2577
Amidoferrocenyl-functionalised single wall carbon nanotubes (Fc-SWNT) are efficient exoreceptors for the redox recognition of H2PO4-. 相似文献
129.
Ghedini M Aiello I La Deda M Grisolia A 《Chemical communications (Cambridge, England)》2003,(17):2198-2199
The newly synthesized complexes formed by cyclopalladated 2-phenylpyridine co-ordinated to 5-substituted-8-hydroxyquinolines, are at room temperature and in fluid solution, luminescent with an absolute photoluminescent quantum yield which depends on the nature of the substituent in position 5. 相似文献
130.
The autonomous composition operator is the nonlinear map whichtakes a pair of functions into its composite function. The compositionoperator often appears in problems of nonlinear analysis andto analyse such problems it is often important to know whetherthe composition operator is continuous or differentiable. Afairly large number of papers in the literature have been devotedto the study of composition operators. For fullscale references,we refer the reader to the extensive monographs of Appell andZabrejko [1] and Runst and Sickel [8]. To exemplify a typicalsituation, we consider the semilinear Dirichlet boundary valueproblem
where denotes a sufficiently regular bounded open subset ofRN, and h0 a map of R to R, and where u is the unknown of theproblem. We assume that we know that a certain function u0 belongingto a certain function space X solves (1.1). Then if we wishto know whether by perturbing h0 in a certain function space,say Y, the solutions u depend on h continuously, with differentiability,with analyticity or bifurcate, we could set G[h, u] u+h u,recast problem (1.1) into the abstract form G[h, u] (1.2) and study the solution set of equation (1.2) around the pair(h0, u0) by means of the implicit function theorem or by localbifurcation theorems in a Banach space setting. 相似文献