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61.
In HF-SbF5, in the presence of H2O2 (source of OH+ equivalent) quinine 1a yields 10-keto derivatives 4a and 5a and cyclic ether 3 as the major product. In the same conditions 1b, 2a, and 2b give the 10-keto and 10-fluoro-3-hydroxy analogs. 相似文献
62.
Daiguebonne C Kerbellec N Guillou O Bünzli JC Gumy F Catala L Mallah T Audebrand N Gérault Y Bernot K Calvez G 《Inorganic chemistry》2008,47(9):3700-3708
Reaction in water between rare earth ions (Ln = Y, La-Tm, except Pm) and the sodium salt of terephthalic acid leads to a family of lanthanide-based coordination polymers of general formula [Ln2(C8H4O4)3(H2O)4] n with Ln = La-Tm or Y. The isostructurality of the compounds with the previously reported Tb-containing polymer is ascertained on the basis of their X-ray powder diffraction diagrams. The coordination water molecules can be reversibly removed without destroying the crystal structure for compounds involving one of the lighter lanthanide ions (La-Eu). For compounds involving one of the heavier lanthanide ions (Tb-Tm) or yttrium, a structural change occurs during the drying process. X-ray diffraction data show this new anhydrous phase corresponding to the linking of pairs of Er(III) ions through mu-carboxylate bridges. Porosity profiles calculated for the anhydrous phases of Tb(III) and Er(III) show the presence of channels with very small sections. The luminescent properties of all the compounds have been recorded and the two most luminescent polymers, namely, the europium- and the terbium-containing ones, have been studied in more detail. Tb(III)-containing compounds display large quantum yields, up to 43%. Polyvinylpyrrolidone nanoparticles doped with [Ln2(C8H4O4)3(H2O)4] n (Ln = Eu, Tb, Er) have also been synthesized and characterized. The encapsulation of the coordination polymers results in somewhat reduced luminescence intensities and lifetime, but the nanoparticles can be dispersed in water and remain unchanged in this medium for more than 20 h. 相似文献
63.
Huy Loc Nguyen James Dedier Jean-Claude Rouillon Gilles Sigaud 《Liquid crystals》2013,40(11):1637-1644
The synthesis of two series of semiperfluoroalkyloxyphenyl and perfluoroalkylphenyl β-D-glucopyranosides is described. Their mesomorphic properties are studied by DSC, polarized optical microscopy and X-ray diffraction. All mesophases are identified as smectic A with a bimolecular in-layer arrangement. 相似文献
64.
Josette Olivier-Fourcade Costana Mihaela Ionica-Bousquet Pierre-Emmanuel Lippens Jean-Claude Jumas 《Hyperfine Interactions》2012,207(1-3):33-36
Due to their high storage capacity Sn-based materials are of considerable interest as negative electrode for Li-ion batteries. However the strong volume change occurring during the alloy formation strongly limits the electrochemical performances (cycle and time life). Analysis by M?ssbauer spectroscopy using model compounds (Sn, Sn-Li and transition metal-Sn alloys) shows that the volume expansion is related to the structural change from a Sn based network to a Li based network. Two types of materials are proposed here to overcome this problem: tin dispersion in an electrochemically inactive oxide matrix with buffer role to absorb volume changes or tin alloying with an inactive transition metal to minimize the volume expansion. The use of M?ssbauer spectroscopy (in situ operando mode) allows a dynamic approach which is essential to understand the fundamental causes of ageing on cycling and to define then the key issues to be solved for material’s application. 相似文献
65.
Nuclear Overhauser effects allow us to determine all transition probabilities in a two-spin AB system, using a triple resonance apparatus we have constructed. Theoretical and experimental studies of the relaxation in the special case where the nuclei belong to a molecule interconverting slowly between two different conformations have been made, and the exchange ratio has been deduced. 相似文献
66.
A two-stage low-temperature solution polycondensation process is described for the synthesis of two kinds of block copolyamides: poly(p-biphenylene terephtalamide-co-adipamide) and poly(2,5-dimethyl trans-piperazine terephthalamide-co-adipamide). The reactivity of oligomeric end groups in various solvents is examined. This study ascertains the influence of the nature of the solvent on the extent of polycondensation. End groups seem to be more reactive in a medium in which the polyamide is soluble; this property is used for the synthesis of block copolycondensates. 相似文献
67.
Raluca Malacea Jean-Claude Daran Rinaldo Poli Eric Manoury 《Tetrahedron: Asymmetry》2013,24(9-10):612-620
Novel chiral ferrocenylthiophosphine–sulfoxide and phosphine–sulfoxide derivatives possessing planar chirality for the ferrocene moiety and central chirality at the sulfur atom have been synthesized. These ligands can be obtained as pure diastereoisomers in both racemic and enantiomerically pure forms. Complete characterization by XRD analysis has allowed the assignment of the absolute configuration in each case. Preliminary coordination studies of the phosphine–sulfoxide ligands on platinum are also reported. These show chelating complexation by the phosphorous and sulfur atoms. 相似文献
68.
Jean-Marie Coustard Jean-Claude Jacquesy 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):427-428
Abstract 1,1-bis(methylthio)-2-nitroethene gives a stable hydro-xynitrilium ion in trifluoromethanesulfonic acid. This cation can be trapped by various nucleophiles to yield a-oximinoorthothioesters. 相似文献
69.
Sandrine Bourgoin-Voillard Carlos Afonso Denis Lesage Emilie-Laure Zins Jean-Claude Tabet P. B. Armentrout 《Journal of the American Society for Mass Spectrometry》2013,24(3):365-380
The kinetic method is a widely used approach for the determination of thermochemical data such as proton affinities (PA) and gas-phase acidities (ΔH° acid ). These data are easily obtained from decompositions of noncovalent heterodimers if care is taken in the choice of the method, references used, and experimental conditions. Previously, several papers have focused on theoretical considerations concerning the nature of the references. Few investigations have been devoted to conditions required to validate the quality of the experimental results. In the present work, we are interested in rationalizing the origin of nonlinear effects that can be obtained with the kinetic method. It is shown that such deviations result from intrinsic properties of the systems investigated but can also be enhanced by artifacts resulting from experimental issues. Overall, it is shown that orthogonal distance regression (ODR) analysis of kinetic method data provides the optimum way of acquiring accurate thermodynamic information. 相似文献
70.
Yi-Hao Huang Chung-Cheng Chiang Yet-Pole I Chuen-Tzay Kuo Sheng-Hung Wu Jyh-Ping Hsu Jean-Claude Charpentier 《Journal of Thermal Analysis and Calorimetry》2013,114(3):1225-1229
This article covers the incompatible properties of nitric acid (HNO3) with formic acid (CH2O2), and more generally with various acids such as sulfuric acid (H2SO4), hydrochloric acid (HCl), and acetic acid (C2H4O2). Differential scanning calorimetry (DSC) was employed to determine the thermal hazard such as heat of decomposition (ΔH d), exothermic onset temperature (T 0), etc., in various acids. T 0 of HNO3 and CH2O2 were determined as 50 °C using DSC. Thus it has been observed that HNO3 mixed with CH2O2 should be prohibited during transportation, storage, and use. And more generally, process safety engineers and operator must take care to handle tanker and storage tank of typical acids in the transportation, storage, and manufacturing process. It is clear that there exists a need to follow and enforce in the chemical industries safety data sheets, globally harmonized system of classification and labeling of chemicals of United Nations (UN), education of safety and health, emergency response system, and process safety management. It is the aim of the present study concerning HNO3 with various acids. 相似文献