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71.
Giuseppe Guanti Luca Banfi Enrica Narisano Carlo Scolastico 《Tetrahedron letters》1984,25(41):4693-4696
threo-α-Dibenzylamino-?-hydroxyesters (2) have been synthesised with high diastereoselectivity through the NaBH4 reduction of α-dibenzylamino-β-oxoesters (4) and then tranformed into threo-α-amino-β-hydroxyacids. 相似文献
72.
73.
Zampella G Fantucci P Pecoraro VL De Gioia L 《Journal of the American Chemical Society》2005,127(3):953-960
Density functional theory has been used to investigate structural, electronic and reactivity properties of complexes related to the peroxo forms of vanadium haloperoxidases (VHPO). In particular, the reactivity of the cofactor as a function of protonation state and environment, which are two factors thought to be crucial in modulating the activity of the enzyme, has been examined. In full agreement with experimental data, results highlight the role of protonation in the activation of the peroxo-vanadium complexes and show that the oxo-transfer step involves the unprotonated axial peroxo oxygen atom, which is easily accessible to substrates in the peroxo form of the enzyme. The role of Lys353, which in the X-ray structure of the peroxide-bound form of vanadium chloroperoxidase is hydrogen bonded to the equatorial oxygen atom of the peroxo group, has been also explored. It is concluded that Lys353 can play a role similar to a H+ in the activation of the peroxo form of the cofactor. 相似文献
74.
Sandra GemmaStefania Butini Caterina FattorussoIsabella Fiorini Vito NacciKatherine Bellebaum Down McKissicAshima Saxena Giuseppe Campiani 《Tetrahedron》2003,59(1):87-93
The synthesis of two new Huperzine A analogues is reported. Both products present an amino substituted benzo-fused system in place of the pyridone ring of the natural alkaloid. The synthetic strategy to the two analogues is based on three different key palladium-catalyzed steps, namely a carbonylation reaction, an epoxide isomerization and a bicycloannulation reaction. 相似文献
75.
[reaction: see text] A new mild method for protecting alcohols as t-butyl ethers is reported. The reaction proceeds with Mg(ClO4)2 and Boc2O and shows general applicability. The deprotection of t-butyl ethers has also been revisited. Preliminary results indicate the CeCl3 x 7H2O/NaI system is a very suitable catalyst for their removal. 相似文献
76.
Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface. 相似文献
77.
Brillante A Della Valle RG Farina L Venuti E Cavazzoni C Emerson AP Syassen K 《Journal of the American Chemical Society》2005,127(9):3038-3043
We have investigated the high-pressure properties of the molecular crystal para-diiodobenzene, by combining optical absorption, reflectance, and Raman experiments with Car-Parrinello simulations. The optical absorption edge exhibits a large red shift from 4 eV at ambient conditions to about 2 eV near 30 GPa. Reflectance measurements up to 80 GPa indicate a redistribution of oscillator strength toward the near-infrared. The calculations, which describe correctly the two known molecular crystal phases at ambient pressure, predict a nonmolecular metallic phase, stable at high pressure. This high-density phase is characterized by an extended three-dimensional network, in which chemically bound iodine atoms form layers connected by hydrocarbon bridges. Experimentally, Raman spectra of samples recovered after compression show vibrational modes of elemental solid iodine. This result points to a pressure-induced molecular dissociation process which leads to the formation of domains of iodine and disordered carbon. 相似文献
78.
Giuseppe Trapani Andrea Latrofa Antonia Reho Massimo Franco Gaetano Liso 《Journal of heterocyclic chemistry》1992,29(5):1155-1159
The title compounds 3a-j together with the N-alkylacylketene S,N-acetals 12a-j were obtained by reaction of N,N'-dialkyldithiodianilines with β-ketoesters compounds. A possible reaction pathway is suggested. 相似文献
79.
Domenico Spinelli Anlonino Corrao Vincenzo Frenna Nicol
Vivona Michele Ruccia Giuseppe Cusmano 《Journal of heterocyclic chemistry》1976,13(2):357-360
The rates of the mononuclear heterocyclic rearrangement of the phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1) into 2,5-diphenyl-4-benzoylamino-1,2,3-triazole (II) have heen measured in dioxane/water (50:50, v:v) in the range of pS+ 3.8–12.2 at various temperatures and the activation parameters determined. On the basis of the results obtained, we present evidence for the occurrence of two different types of reaction: the first, base-catalyzed; the second, pS+ -independent. In the base-catalyzed range the catalysis is of the general type. 相似文献
80.
Valerio Magnasco Massimo Ottonelli Giuseppe Figari Marina Rui Camilla Costa 《Journal of Molecular Structure》1998,430(1-3):231-239
The real spherical tensor theory of long-range intermolecular coefficients developed in previous papers is applied to derive explicit formulae for the first three dispersion coefficients for like centrosymmetric linear molecules. The expansion of angle-dependent coefficients in associated Legendre polynomials allows one to identify the isotropic and anisotropic components of the dispersion interaction in terms of London dispersion constants, the treatment of higher coefficients being simplified by the coupling of the elementary (l, l′)-polarizations to resultant angular momenta LA and LB onto each molecule. The contributions from all coupling schemes are given explicitly for C6, C8, C10, and numerical results are presented for H2-H2 using two-term reduced spectra values from the Kaiserlautern group. 相似文献