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101.
Torsten C. Schmidt Melanie Less Rainer Haas Eberhard von Lw Klaus Steinbach Gottfried Stork 《Journal of chromatography. A》1998,810(1-2):161-172
A new method for the selective determination of aromatic amines is presented, which is based on the solid-phase extraction at pH 9 and subsequent derivatization of the analytes to the corresponding iodobenzenes. These can selectively and sensitively be determined with gas chromatography and electron-capture detection. Separation of at least 30 compounds in a single chromatographic run in 30 min is possible. With this method, 56 aromatic amines were investigated, and only in six cases no derivatives were obtained. Limits of quantitation were between 0.5 and 8 μg l−1, but may still be lowered with higher sample volumes or different injection techniques. The application to water samples revealed the suitability for the investigation of ground, leachate and wastewater. 相似文献
102.
Melanie Schnell Holger Hartwig Michael Meyer Walther Caminati 《Journal of Molecular Spectroscopy》2005,229(1):1-8
The rotational spectra of the normal and 13C isotopomers of difluorodimethylsilane have been measured by molecular beam Fourier-transform microwave (FTMW) and free-jet absorption millimeter-wave (FJ-AMMW) spectroscopy. Each rotational transition is split into several component lines due to the two methyl groups internal rotations. The corresponding V3 barrier has been determined to be 5.256(3) kJ mol−1. A r0 structure of the heavy atoms skeleton has been obtained. The silicon atom lies—accidentally—on the center of mass of the molecule. 相似文献
103.
Melanie L. Lenard 《Mathematical Programming》1976,10(1):32-51
Convergence properties of restarted conjugate gradient methods are investigated for the case where the usual requirement that an exact line search be performed at each iteration is relaxed.The objective function is assumed to have continuous second derivatives and the eigenvalues of the Hessian are assumed to be bounded above and below by positive constants. It is further assumed that a Lipschitz condition on the second derivatives is satisfied at the location of the minimum.A class of descent methods is described which exhibitn-step quadratic convergence when restarted even though errors are permitted in the line search. It is then shown that two conjugate gradient methods belong to this class.Sponsored by the United States Army under Contract No. DA-31-124-ARO-D-462. 相似文献
104.
105.
It is well known that the marginal maxima of n standard normal random vectors with correlation coefficient ρ<1 are asymptotically independent. In this article, the residual dependence will be captured by asymptotic expansions and certain penultimate distributions including the case where ρ(n)↑1 at a certain rate. 相似文献
106.
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108.
Melanie Miller William E. Robinson Ana Rita Oliveira Nina Heidary Nikolay Kornienko Julien Warnan Inês A. C. Pereira Erwin Reisner 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(14):4649-4653
The integration of enzymes with synthetic materials allows efficient electrocatalysis and production of solar fuels. Here, we couple formate dehydrogenase ( FDH ) from Desulfovibrio vulgaris Hildenborough (DvH) to metal oxides for catalytic CO2 reduction and report an in‐depth study of the resulting enzyme–material interface. Protein film voltammetry (PFV) demonstrates the stable binding of FDH on metal‐oxide electrodes and reveals the reversible and selective reduction of CO2 to formate. Quartz crystal microbalance (QCM) and attenuated total reflection infrared (ATR‐IR) spectroscopy confirm a high binding affinity for FDH to the TiO2 surface. Adsorption of FDH on dye‐sensitized TiO2 allows for visible‐light‐driven CO2 reduction to formate in the absence of a soluble redox mediator with a turnover frequency (TOF) of 11±1 s?1. The strong coupling of the enzyme to the semiconductor gives rise to a new benchmark in the selective photoreduction of aqueous CO2 to formate. 相似文献
109.
Courtney C. Roberts Nicole M. Camasso Eric G. Bowes Melanie S. Sanford 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(27):9202-9206
Described is a systematic comparison of factors impacting the relative rates and selectivities of C(sp3)?C and C(sp3)?O bond‐forming reactions at high‐valent Ni as a function of oxidation state. Two Ni complexes are compared: a cationic octahedral NiIV complex ligated by tris(pyrazolyl)borate and a cationic octahedral NiIII complex ligated by tris(pyrazolyl)methane. Key features of reactivity/selectivity are revealed: 1) C(sp3)?C(sp2) bond‐forming reductive elimination occurs from both centers, but the NiIII complex reacts up to 300‐fold faster than the NiIV, depending on the reaction conditions. The relative reactivity is proposed to derive from ligand dissociation kinetics, which vary as a function of oxidation state and the presence/absence of visible light. 2) Upon the addition of acetate (AcO?), the NiIV complex exclusively undergoes C(sp3)?OAc bond formation, while the NiIII analogue forms the C(sp3)?C(sp2) coupled product selectively. This difference is rationalized based on the electrophilicity of the respective M?C(sp3) bonds, and thus their relative reactivity towards outer‐sphere SN2‐type bond‐forming reactions. 相似文献
110.
Di Liu Alvaro D. Sponza Dandan Yang Melanie Chiu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(45):16356-16362
Deterministic methods for tuning polymer dispersity are rare, especially for nonradical polymerizations. Reported here is the first example of photomodulating dispersity in controlled cationic polymerizations of vinyl ethers using carboxy‐functionalized dithienylethene initiators. Reversible photoisomerization of these initiators induces changes in their acidities by up to an order of magnitude. Using the more acidic, ring‐closed isomers as initiators results in polymers with lower dispersities. The degree of light‐induced pKa change in the initiators correlates with the degree of dispersity change in polymers derived from the isomeric initiators. The polymerizations are controlled, and dynamic photoswitching of dispersity during the polymerization reaction was demonstrated. This work provides a framework for photomodulating dispersity in other controlled polymerizations and developing one‐pot block copolymerization reactions in which the dispersities of component blocks can be controlled using light. 相似文献