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排序方式: 共有406条查询结果,搜索用时 687 毫秒
81.
S. H. Eberhardt F. Marone M. Stampanoni F. N. Büchi T. J. Schmidt 《Journal of synchrotron radiation》2014,21(6):1319-1326
Synchrotron‐based X‐ray tomographic microscopy is investigated for imaging the local distribution and concentration of phosphoric acid in high‐temperature polymer electrolyte fuel cells. Phosphoric acid fills the pores of the macro‐ and microporous fuel cell components. Its concentration in the fuel cell varies over a wide range (40–100 wt% H3PO4). This renders the quantification and concentration determination challenging. The problem is solved by using propagation‐based phase contrast imaging and a referencing method. Fuel cell components with known acid concentrations were used to correlate greyscale values and acid concentrations. Thus calibration curves were established for the gas diffusion layer, catalyst layer and membrane in a non‐operating fuel cell. The non‐destructive imaging methodology was verified by comparing image‐based values for acid content and concentration in the gas diffusion layer with those from chemical analysis. 相似文献
82.
83.
A Nörder SA Warren E Herdtweck SM Huber T Bach 《Journal of the American Chemical Society》2012,134(32):13524-13531
The diastereoselectivity of the Rh-catalyzed C-H amination was examined with 18 chiral open-chain substrates, which bear a benzylic methylene group in the α-position to a stereogenic center (-CHMeX), and with four chiral cyclic tetralins, in which the stereogenic center was positioned at carbon atom C2. The C-H amination was performed using trichloroethoxysulfonyl-substituted amine (H(2)NTces) as the nitrogen source, a diacyloxyiodobenzene as the oxidant, and bis[rhodium(α,α,α',α'-tetramethyl-1,3-benzenedipropionate)] [Rh(2)(esp)(2)] as the catalyst. For acyclic substrates a high syn diastereoselectivity (dr > 95/5) was found if the substituent X was Br, PO(OEt)(2), SO(2)Ph, or OOCCF(3) (eight examples). Moderate to good syn selectivities (dr = 80/20 to 91/9) were found for X = NO(2), OAc, COOMe, and CN (eight examples). Only two substrates gave a low diastereoselectivity. Kinetic isotope effect (KIE) experiments revealed that there is no secondary KIE when replacing -CHMeCOOMe by -CDMeCOOMe, but there is a significant primary KIE at the benzylic methylene position (4.8 ± 0.7). Deuteration experiments provided evidence that the reaction proceeds stereospecifically with retention of configuration. A preferred conformation is proposed, which explains the outcome of the reaction. In this conformation the X substituent is antiperiplanar to the C-H bond, which is diastereoselectively attacked, and steric strain between the remaining substituents at the stereogenic and the prostereogenic center is minimized. DFT calculations support this model. They suggest, however, that the reaction is not concerted but occurs via hydrogen atom abstraction and subsequent radical rebound. Further support for an antiperiplanar attack relative to a given substituent X = Br, COOMe, or CN was obtained with the respective 2-substituted tetralins. Attack at C1 provides almost exclusively the trans-amination product. If the size of the X substituent increases [Br < CN < COOMe < PO(OEt)(2)], attack at the carbon atom C4 prevails, delivering the respective trans-amination products at this position. 相似文献
84.
85.
Ahmed K. Hijazi Hui Y. Yeong Yanmei Zhang Eberhardt Herdtweck Oskar Nuyken Fritz E. Kühn 《Macromolecular rapid communications》2007,28(5):670-675
CuII compounds coordinated octahedrally with nitriles and associated with bulky, non‐coordinating counter ions can be applied in the polymerization of isobutene at 30 °C. High yields and a high content of terminal double bonds are reached in the resulting highly reactive polyisobutylenes, while the molecular masses are moderate. Two of the coordinating nitriles are more weakly coordinated than the other four, as can be concluded from an exemplary X‐ray structure and from vibrational spectra, thus providing easily accessible sites for substrate coordination.
86.
Summary: Reversible addition fragmentation chain transfer (RAFT) polymerization of pentafluorophenyl methacrylate (PFMA) was carried out in the presence of cumyldithiobenzoate and 4‐cyano‐4‐((thiobenzoyl)sulfanyl)pentanoic acid, respectively. These chain transfer agents with 2,2′‐azoisobutyronitrile (AIBN) as initiator yielded the active ester polymer poly(PFMA) with up to 17 000 g · mol−1 and low polydispersity index ( < 1.2). Kinetic analysis using 19F NMR spectroscopy and gel permeation chromatography (GPC) measurements showed controlled polymerization behavior for both chain transfer agents. Successful preparation of linear diblock copolymers consisting of an active ester block and methyl methacrylate, N‐acryloylmorpholine, or N,N‐diethylacrylamide, respectively, could be demonstrated. These polymers could easily react with amines in a polymer analogous reaction to form multifunctional polymers.
87.
88.
G. Lhersonneau B. Pfeiffer J. Alstad P. Dendooven K. Eberhardt S. Hankonen I. Klöckl K.-L. Kratz A. Nähler R. Malmbeck J.P. Omtvedt H. Penttilä S. Schoedder G. Skarnemark N. Trautmann J. Äystö 《The European Physical Journal A - Hadrons and Nuclei》1998,1(3):285-297
The decay of 111Ru obtained from fast on-line chemical and mass separation has been investigated by β-γ-t and γ-γ coincidence techniques. Earlier spin and parity assignments of 111Rh levels based on extrapolations of level systematics are confirmed. In particular, the K=1/2 intruder band is supported
by the hindrance of E2 transitions between deformed and spherical states and enhancement of intraband E2 transitions. The
excitation energies of intruder band members in Rh isotopes show a minimum at 109Rh64, with two neutrons less than 111Rh at the N=66 midshell. This trend, which differs from the one in the higher-Z neighbouring elements Ag and Cd with minima
at N=66, follows the evolution of deformation observed in the lower-Z elements Ru and Mo.
Received: 25 June 1997 / Revised version: 10 September 1997 相似文献
89.
T. Böske W. Clemens D. Schmitz J. Kojnok M. Schäfer V. Cros G. Y. Guo W. Eberhardt 《Applied Physics A: Materials Science & Processing》1995,61(2):119-122
The coupling of Cr to Fe in stacked Cr/Fe/Cr trilayers is studied by circular magnetic X-ray dichroism using fluorescence yield to monitor the absorption. From the dichroic spectra, we determine the thickness dependent average magnetic coupling of Cr to Fe for Cr layer thicknesses of 1, 2 and 3 ML. We compare our results to new calculated spectra. Additionally, all Cr spectra show significant contributions due to photon scattering processes at theL
2, 3 absorption edges depending on the degree of circular polarization. 相似文献
90.