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1.
A. Hoffknecht O. Uwira A. Frank S. Schennach W. Spies M. Wagner S. Schippers A. Müller R. Becker M. Kleinod N. Angert P.H. Mokler 《Hyperfine Interactions》1998,114(1-4):257-261
The origin of the widely observed enhancement of rates for electron-ion recombination at very low energies is still unknown.
We investigated the recombination of Au25+ with free electrons in a merged-beams experiment at the UNILAC accelerator of the GSI in Darmstadt. At E
rel= 0 eV we found an enormous enhancement factor of 365 compared to the theory of radiative recombination. An increase of the
electron density by a factor of 10 had not much influence on the measured rate coefficient.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
2.
Spies MA Woodward JJ Watnik MR Toney MD 《Journal of the American Chemical Society》2004,126(24):7464-7475
Free energy profiles for alanine racemase from Bacillus stearothermophilus have been determined at pH 6.9 and 8.9 from global analysis of racemization progress curves. This required a careful statistical design due to the problems in finding the global minimum in mean square for a system with eight adjustable parameters (i.e., the eight rate constants that describe the stepwise chemical mechanism). The free energy profiles obtained through these procedures are supported by independent experimental evidence: (1). steady-state kinetic constants, (2). solvent viscosity dependence, (3). spectral analysis of reaction intermediates, (4). equilibrium overshoots for progress curves measured in D(2)O, and (5). the magnitudes of calculated intrinsic kinetic isotope effects. The free energy profiles for the enzyme are compared to those of the uncatalyzed and the PLP catalyzed reactions. At pH 6.9, PLP lowers the free energy of activation for deprotonation by 8.4 kcal/mol, while the inclusion of apoenzyme along with PLP additionally lowers it by 11 kcal/mol. 相似文献
3.
Schmidt R Blaich T Elze TW Emling H Freiesleben H Grimm K Henning W Holzmann R Keller JG Klingler H Kulessa R Kratz JV Lambrecht D Lange JS Leifels Y Lubkiewicz E Moore EF Wajda E Prokopowicz W Schütter C Spies H Stelzer K Stroth J Walus W Wollersheim HJ Zinser M Zude E 《Physical review letters》1993,70(12):1767-1770
4.
S. Schennach A. Müller O. Uwira J. Haselbauer W. Spies A. Frank M. Wagner R. Becker M. Kleinod E. Jennewein N. Angert P. H. Mokler N. R. Badnell M. S. Pindzola 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1994,30(4):291-306
Dielectronic recombination (DR) of Ar15+(1s 22s) ions was studied in a single-pass merged-beams experiment at the UNILAC (universal linear accelerator) of GSI. Absolute recombination rates and cross sections were measured for electron-ion center-of-mass energies from 0 to 580 eV. A number of Rydberg states formed by DR with 2s → 2p (Δn=0) and 2s → 3? (Δn=1) core excitations and even individual terms in the 1s 23?3?′ configuration could be resolved. Theoretical calculations of DR cross sections are in good overall agreement with the data. In the calculations for Δn=0 transitions, effects of electric fields have to be included to reproduce the magnitude of the measured DR rates at the limit of the 2 p 1/2? and 2 p 3/2? Rydberg series. Discrepancies between theory and experiment are observed at the series limits of the (1s 23?n?′) Rydberg series. 相似文献
5.
This work is part of an effort to develop chelating agents for stable binding and easy conjugation of Re-188 to biologically interesting structures. Starting from the well-known in vivo stability of [(188)ReO(DMSA)(2)](-), we want to exploit this coordination system for the design of (188)ReO(V) chelates, which are stable toward reoxidation to perrhenate and toward ligand exchange under all conditions of radiopharmaceutical development. Therefore, a new type of tetradentate ligand has been synthesized by bridging two molecules of N,N'-diisobutyl-2,3-dimercaptosuccinamide with N-(3-aminopropyl)propane-1,3-diamine. The resulting stereoisomeric tetrathiolato S(4) ligand of composition ((i)()Bu)(2)N(O)C-C(SH)-C(SH)-C(O)NH-(CH(2))(3)-NH-(CH(2))(3)-NHC(O)-C(SH)-C(SH)-C(O)N((i)Bu)(2) forms anionic five-coordinate oxorhenium(V) complexes by a ligand-exchange reaction of NBu(4)[ReOCl(4)] in methanol. In the absence of a base, the compounds were isolated as "betaine", [ReO(S(4))], with the protonated nitrogen of the bridge serving as an internal "counterion". Two representatives have been fully characterized in both the solid and solution states and found to adopt the expected square-pyramidal coordination geometry. The equatorial plane is formed by four thiolate sulfur atoms, whereas the oxygen occupies the apical position. The orientation of the metal oxo group is exo in relation to the carbamido groups in both isomers. Both complexes are stereoisomeric regarding the junction of the triamine chain. 相似文献
6.
7.
Cindy Strehl Timo Gaber Manuela Jakstadt Martin Hahne Paula Hoff Cornelia M. Spies Alexander Scheffold Gerd-Rüdiger Burmester Frank Buttgereit 《Journal of fluorescence》2013,23(3):509-518
Flow cytometry has become a widely-used and powerful tool for the characterization of cells according to their expression of specific proteins. However, sensitivity of this method is still limited since conventionally labeled antibodies can be conjugated with at maximum 1–10 dye molecules. This fact resulted in the need to develop new techniques in order to identify molecules which are expressed in very low but functionally relevant amounts. In the past, we have successfully used a liposome-based high-sensitivity immunofluorescence technique to measure the expression of low abundant membrane bound glucocorticoid receptors (mGR) on different cell types. The use of this technique allows the detection of as few as 50–100 antigen molecules per cell which is due to a 100-fold to 1000-fold increase in fluorescence signal intensity compared with conventional methods. The higher sensitivity is achieved since thousands of dye molecules can be enclosed in liposomes. Another modern high-sensitivity immunofluorescence staining method is the purchasable Fluorescence Amplification by Sequential Employment of Reagents (FASER) procedure. Here, we aimed at comparing sensitivity and specificity of these two techniques for the detection of the mGR. Our data demonstrate the FASER technique to be more sensitive and also more specific for the detection of mGR as compared to the liposome technique. However, both methods have advantages and disadvantages which are discussed in detail. 相似文献
8.
Felix Burkhardt Carl G. Schirmeister Christian Wesemann Massimo Nutini Stefano Pieralli Erik H. Licht Marc Metzger Frederik Wenz Rolf Mülhaupt Benedikt C. Spies 《Molecules (Basel, Switzerland)》2020,25(24)
A polyolefin with certified biocompatibility according to USP class VI was used by our group as feedstock for filament-based 3D printing to meet the highest medical standards in order to print personal protective equipment for our university hospital during the ongoing pandemic. Besides the chemical resistance and durability, as well as the ability to withstand steam sterilization, this polypropylene (PP) copolymer is characterized by its high purity, as achieved by highly efficient and selective catalytic polymerization. As the PP copolymer is suited to be printed with all common printers in fused filament fabrication (FFF), it offers an eco-friendly cost–benefit ratio, even for large-scale production. In addition, a digital workflow was established focusing on common desktop FFF printers in the medical sector. It comprises the simulation-based optimization of personalized print objects, considering the inherent material properties such as warping tendency, through to validation of the process chain by 3D scanning, sterilization, and biocompatibility analysis of the printed part. This combination of digital data processing and 3D printing with a sustainable and medically certified material showed great promise in establishing decentralized additive manufacturing in everyday hospital life to meet peaks in demand, supply bottlenecks, and enhanced personalized patient treatment. 相似文献
9.
A. Zablotskaya I. Segal A. Kemme S. Germane J. Popelis E. Lukevics R. Berger H. Spies 《Chemistry of Heterocyclic Compounds》2002,38(4):477-489
With the aim of studying the structure-physicochemical properties-biological activity relation, we have synthesized a series of organosilicon neutral oxorhenium(V) complexes with mixed ligands and we have determined their lipophilicity. X-ray diffraction has been used to establish the molecular structure of (3-triphenylsiloxypropanethiolato)(3-thiapentane-1,5-dithiolato)oxorhenium(V), (2-trimethylsiloxy- and 2-hydroxyethanethiolato)[3-(N-methyl)azapentane-1,5-dithiolato]oxorhenium(V). We have studied the neurotropic properties and acute toxicity of the synthesized complexes in vivo and their dependence on the nature of the monodentate and tridentate ligands. We have established that all the studied compounds have pronounced sedative action (they prolong the life of mice under hypoxia conditions, they are phenamine antagonists, they exhibit anticonvulsive action and prevent retrograde amnesia). 相似文献
10.
Amrutha Prabodh Yichuan Wang Stephan Sinn Paolo Albertini Christian Spies Eduard Spuling Liu-Pan Yang Wei Jiang Stefan Brse Frank Biedermann 《Chemical science》2021,12(27):9420
Fluorescence-detected circular dichroism (FDCD) spectroscopy is applied for the first time to supramolecular host–guest and host–protein systems and compared to the more known electronic circular dichroism (ECD). We find that FDCD can be an excellent choice for common supramolecular applications, e.g. for the detection and chirality sensing of chiral organic analytes, as well as for reaction monitoring. Our comprehensive investigations demonstrate that FDCD can be conducted in favorable circumstances at much lower concentrations than ECD measurements, even in chromophoric and auto-emissive biofluids such as blood serum, overcoming the sensitivity limitation of absorbance-based chiroptical spectroscopy. Besides, the combined use of FDCD and ECD can provide additional valuable information about the system, e.g. the chemical identity of an analyte or hidden aggregation phenomena. We believe that simultaneous FDCD- and ECD-based chiroptical characterization of emissive supramolecular systems will be of general benefit for characterizing fluorescent, chiral supramolecular systems due to the higher information content obtained by their combined use.Fluorescence-detected circular dichroism (FDCD) spectroscopy is applied for the first time to supramolecular host–guest and host–protein systems and compared to the more known electronic circular dichroism (ECD). 相似文献