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101.
Jiménez JC Chavarría B López-Macià A Royo M Giralt E Albericio F 《Organic letters》2003,5(12):2115-2118
[reaction: see text] A solid-phase method for the synthesis of tentoxin has been developed. Two key steps-dehydration and N-alkylation-are carried out while the peptide is anchored to the resin. The method, which has been validated by the preparation of a library of tentoxin analogues, should be applicable to the generation of further libraries that have the tentoxin scaffold structure, as well as other structures containing N-alkylated didehydroamino acids. 相似文献
102.
Four new supramolecular compounds of Cu(II)-Ni(II) have been synthesized and characterized: [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(ClO(4))(2) (1), [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(PF(6))(2) (2), [Cu(oxpn)Ni(mu-NCS)(NCS) (tmen)](n) (3), and [Cu(Me(2)oxpn)Ni(mu-NCS)(NCS)(tmen)](n) (4), where oxpn = N,N'-bis(3-aminopropyl)oxamidate, Me(2)oxpn = N,N'-bis(3-amino-2,2'-dimethylpropyl)oxamidate, and tmen = N,N,N',N'-tetramethylethylenediamine. Their crystal structures were solved. Complexes 1 and 2 have the same tetranuclear cationic part but a different counteranion. The cationic part consists of two [Cu(Me(2)oxpn)Ni] moieties linked by SCN(-) bridged ligands and intra-tetranuclear hydrogen bonds. In the case of complex 3, a two-dimensional system was built, the thiocyanate ligand linking the dinuclear units gives a chain, and the chains are linked together by hydrogen bonds; intrachain hydrogen bonds are also present. For complex 4, the thiocyanate ligands produce intermolecular linkages between the dinuclear entities, giving a one-dimensional system; intrachain hydrogen bonds are also present. The magnetic properties of the four complexes were studied by susceptibility measurements vs temperature. DFT calculations were made to study the contribution of the SCN(-) and hydrogen bond bridges in the magnetic coupling. 相似文献
103.
A new design of a continuous flow system applied to the simultaneous determination of the concentration of zinc(II), cadmium(II), lead(II), copper(II), nickel(II), cobalt(II) and chromium(VI) in river water is described. A flow cell made in the laboratory, which has been patented, based on a 'wall-jet' configuration with a three-electrode system is described. Optimum conditions for the determination of the metal ions are reported. The detection limits and relative standard deviation values were 4.01x10(-9) M and 0.078 for Zn(II), 1.76x10(-10) M and 0.056 for Cd(II), 4.69x10(-10) M and 0.134 for Pb(II), 2.29x10(-10) M and 0.138 for Cu(II), 1.61x10(-9) M and 0.093 for Ni(II), 1.91x10(-9) M and 0.113 for Co(II), and 1.35x10(-9) M and 0.081 for Cr(VI). The procedure was applied to a sample of water from the Arlanzón river and the results were compared with inductively coupled mass plasma spectrometry (ICP-MS) as reference method. The final aim of this work is to design a flow system, which can be automated. 相似文献
104.
Torres-Valencia JM Meléndez-Rodríguez M Alvarez-García R Cerda-García-Rojas CM Joseph-Nathan P 《Magnetic resonance in chemistry : MRC》2004,42(10):898-902
A Monte Carlo random search using molecular mechanics, followed by geometry optimization of each minimum energy structure employing density functional theory (DFT) calculations at the B3LYP/6-31G* level and a Boltzmann analysis of the total energies, generated accurate molecular models which describe the conformational behavior of the antispasmodic bicyclic sesquiterpene valeranone (1). The theoretical H-C-C-H dihedral angles gave the corresponding 1H, 1H vicinal coupling constants using a generalized Karplus-type equation. In turn, the 3J(H,H) values were used as initial input data for the spectral simulation of 1, which after iteration provided an excellent correlation with the experimental 1H NMR spectrum. The calculated 3J(H,H) values closely predicted the experimental values, excepting the coupling constant between the axial hydrogen alpha to the carbonyl group and the equatorial hydrogen beta to the carbonyl group (J(2beta, 3beta)). The difference is explained in terms of the electron density distribution found in the highest occupied molecular orbital (HOMO) of 1. The simulated spectrum, together with 2D NMR experiments, allowed the total assignment of the 1H and 13C NMR spectra of 1. 相似文献
105.
Coronado E Gómez-García CJ Nuez A Romero FM Rusanov E Stoeckli-Evans H 《Inorganic chemistry》2002,41(18):4615-4617
The combination of hexacyanoferrate(III) anions, [Fe(CN)(6)](3)(-), with nickel(II) complexes derived from the chiral ligand trans-cyclohexane-1,2-diamine (trans-chxn) affords the enantiopure layered compounds [Ni(trans-(1S,2S)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (1) and [Ni(trans-(1R,2R)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (2). These chiral systems behave as ferromagnets (T(c) = 13.8 K) with a relatively high coercive field (H(c) = 0.17 T) at 2 K. They also exhibit an unusual magnetic behavior at low temperatures that has been attributed to the dynamics of the magnetic domains in the ordered phase. 相似文献
106.
An analytical potential energy surface for the gas-phase CCl4 + H --> CCl3 + ClH reaction was constructed with suitable functional forms to represent vibrational modes. This surface is completely symmetric with respect to the permutation of the four chlorine atoms and is calibrated with respect to experimental thermal rate constants available over the temperature range 297-904 K. On this surface, the thermal rate constants were calculated using variational transition-state theory with semiclassical transmission coefficients over a wider temperature range 300-2500 K, therefore obtaining kinetics information at higher temperatures than are experimentally available. This surface was also used to analyze dynamical features, such as tunneling and reaction-path curvature. In the first case, the influence of the tunneling factor is very small since a heavy chlorine atom has to pass through the barrier. In the second, it was found that vibrational excitation of the Cl-H stretching mode can be expected in the exit channel. 相似文献
107.
The ability of several water models to predict the properties of ices is discussed. The emphasis is put on the results for the densities and the coexistence curves between the different ice forms. It is concluded that none of the most commonly used rigid models is satisfactory. A new model specifically designed to cope with solid-phase properties is proposed. The parameters have been obtained by fitting the equation of state and selected points of the melting lines and of the coexistence lines involving different ice forms. The phase diagram is then calculated for the new potential. The predicted melting temperature of hexagonal ice (Ih) at 1 bar is 272.2 K. This excellent value does not imply a deterioration of the rest of the properties. In fact, the predictions for both the densities and the coexistence curves are better than for TIP4P, which previously yielded the best estimations of the ice properties. 相似文献
108.
1-Aryl-5-amino-4-(cyanoformimidoyl)imidazoles 2 were reacted with malononitrile under mild experimental conditions and led to 3-aryl-5,7-diamino-6-cyano-3H-imidazo[4,5-b]pyridines 5, when the reaction was carried out in the presence of DBU, or to 3-aryl-5-amino-6,7-dicyano-3H-imidazo[4,5-b]pyridines 3, in its absence. Both reactions evolved from the adduct formed by nucleophilic attack of the malononitrile anion to the carbon of the cyanoformimidoyl substituent. A 5-amino-1-aryl-4-(1-amino-2,2-dicyanovinyl)imidazole 4 was isolated when this reaction was carried out in the presence of DBU. The structure of compound 4 was confirmed by spectroscopic methods and by reaction with triethyl orthoformate and with acetic anhydride, leading respectively to 9-aryl-6-(cyanomethylidene)purines 11 and 12. Imidazole 2b was also reacted with ethyl acetoacetate, a carbon acid with a pK(a) comparable to that of malononitrile. Similar reaction conditions were used and the product isolated was a 6-carbamoyl-1,2-dihydropurine 10, showing that a different mechanism was operating in this case. 相似文献
109.
低聚壳聚糖及其金属配合物的抗O·-2活性研究 总被引:11,自引:0,他引:11
以NBT/VB2/蛋氨酸为O*-2产生、检测体系,对自制低聚壳聚糖及其金属配合物进行了抗O*-2活性研究,结果显示低聚壳聚糖及其金属配合物对O*-2均具有明显的清除活性.质量浓度为0.5×10-2
g/mL时,壳聚糖对O*-2的清除率达80.3%,其与氯化镧、醋酸铜、醋酸钴的配合物对O*-2的清除率分别为98.9%、84.1%、78.4%;相同条件下,高分子壳聚糖和单糖对O*-2没有明显的清除作用,清除率仅为13%、9.5%.随着样品质量浓度降低,低聚壳聚糖及其金属配合物的清除活性逐渐下降. 相似文献
110.
The effect of oxidation pretreatment temperature(500 ~ 1 000 ℃) on the catalytic activity of Kovar applied on hydrocarbon CO2reforming was examined. Catalytic performance evaluation using tetradecane at 800 ℃ with 70 μmol/s CO2revealed 700 and 1 000 ℃ as the best pre-oxidation temperature in producing CO and H2,respectively. XRD and SEM-EDX analyses showed that a separate metal oxide layer composed of iron oxide(Fe2O3and F3O4),nickel,cobalt,and possibly their respective oxides started to form when oxidation was conducted at 700 ℃ or higher.The presence of iron enhanced the stability of nickel in the structure while the compact structure of Fe3O4resulted into the formation of a thick and rigid metal oxide layer on the surface of the Kovar tube. The strong physical bond between the metal oxide layer and Kovar tube provided the catalyst good mechanical strength and consequently good catalytic activity. 相似文献