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61.
Alexander K. Mengele Dominik Weixler Avinash Chettri Maite Maurer Fabian Lukas Huber Prof. Gerd M. Seibold Prof. Benjamin Dietzek Prof. Bernhard J. Eikmanns Prof. Sven Rau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):16840-16845
A series of three Ru(II) polypyridine complexes was investigated for the selective photocatalytic oxidation of NAD(P)H to NAD(P)+ in water. A combination of (time-resolved) spectroscopic studies and photocatalysis experiments revealed that ligand design can be used to control the mechanism of the photooxidation: For prototypical Ru(II) complexes a 1O2 pathway was found. Rudppz ([(tbbpy)2Ru(dppz)]Cl2, tbbpy=4,4'-di-tert-butyl-2,2'-bipyridine, dppz=dipyrido[3,2-a:2′,3′-c]phenazine), instead, initiated the cofactor oxidation by electron transfer from NAD(P)H enabled by supramolecular binding between substrate and catalyst. Expulsion of the photoproduct NAD(P)+ from the supramolecular binding site in Rudppz allowed very efficient turnover. Therefore, Rudppz permits repetitive selective assembly and oxidative conversion of reduced naturally occurring nicotinamides by recognizing the redox state of the cofactor under formation of H2O2 as additional product. This photocatalytic process can fuel discontinuous photobiocatalysis. 相似文献
62.
Grégoire Sieg Quentin Pessemesse Sascha Reith Stefan Yelin Prof. Dr. Christian Limberg Prof. Dr. Dominik Munz Dr. C. Gunnar Werncke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(67):16760-16767
Carbonyl and iminyl based radical anions are reactive intermediates in a variety of transformations in organic synthesis. Herein, the isolation of ketyl, and more importantly unprecedented ketiminyl and aldiminyl radical anions coordinated to cobalt and iron complexes is presented. Insights into the electronic structure of these unusual metal bound radical anions is provided by X-Ray diffraction analysis, NMR, IR, UV/Vis and Mössbauer spectroscopy, solid and solution state magnetometry, as well as a by a detailed computational analysis. The metal bound radical anions are very reactive and facilitate the activation of intra- and intermolecular C−H bonds. 相似文献
63.
For some saline environments (e.g. deeply percolating groundwater, interstitial water in marine sediments, water sample collected after several steps of fractionation) the volume of water sample available is limited. A technique is presented which enables simultaneous determination of major and trace elements after preconcentration of only 60 mL sample on chelating resins. Chelex-100 and Chelamine were used for the preconcentration of trace elements (Cd, Cu, Pb, Zn, Sc) and rare earth elements (La, Ce, Nd, Yb) from saline water before their measurement by inductively coupled plasma mass spectrometry. Retention of the major elements (Na, Ca, Mg) by the Chelamine resin was lower than by Chelex; this enabled their direct measurement in the solution after passage through the resin column. For trace metal recoveries both resins yield the same mass balance. Only Chelex resin enabled the quantitative recovery of rare earth elements. The major elements, trace metals and rare earth elements cannot be measured after passage through one resin only. The protocol proposes the initial use of Chelamine for measurement of trace and major elements and then passage the same sample through the Chelex resin for determination of the rare earth elements. The detection limit ranged from 1 to 12 pg mL(-1). At concentrations of 1 ng mL(-1) of trace metals and REE spiked in coastal water the precision for 10 replicates was in the range of 0.3-3.4% (RSD). The accuracy of the method was demonstrated by analyzing two standard reference waters, SLRS-3 and CASS-3. 相似文献
64.
Dominik Schumacher Dr. Jonas Helma Anselm F. L. Schneider Prof. Dr. Heinrich Leonhardt Prof. Dr. Christian P. R. Hackenberger 《Angewandte Chemie (International ed. in English)》2018,57(9):2314-2333
Nanobodies can be seen as next‐generation tools for the recognition and modulation of antigens that are inaccessible to conventional antibodies. Due to their compact structure and high stability, nanobodies see frequent usage in basic research, and their chemical functionalization opens the way towards promising diagnostic and therapeutic applications. In this Review, central aspects of nanobody functionalization are presented, together with selected applications. While early conjugation strategies relied on the random modification of natural amino acids, more recent studies have focused on the site‐specific attachment of functional moieties. Such techniques include chemoenzymatic approaches, expressed protein ligation, and amber suppression in combination with bioorthogonal modification strategies. Recent applications range from sophisticated imaging and mass spectrometry to the delivery of nanobodies into living cells for the visualization and manipulation of intracellular antigens. 相似文献
65.
Raúl Pérez-Ruiz Robert Fichtler Yrene Diaz Miara Matthieu Nicoul Dominik Schaniel Helfried Neumann Matthias Beller Dirk Blunk Axel G. Griesbeck Axel Jacobi von Wangelin 《Journal of fluorescence》2010,20(3):657-664
The photophysical properties of a series of structurally related 4-aminophthalimides and the corresponding 5-aminophthalic
hydrazides (luminols) are reported. Absorption, steady-state, and time-resolved fluorescence spectra of luminols exhibited
substitution, solvent, and pH dependence. Singlet lifetimes have been determined by time-resolved laser flash spectroscopy.
UV spectra in gas phase and DMSO solution were calculated by TD-DFT which revealed the existence of two low-energy excited
singlet states with strong pH-sensitivity. 相似文献
66.
67.
The highly enantiomerically enriched silyllithium compound lithiomethylphenyl(1-piperidinylmethyl)silane (4) reacts stereospecifically with chlorosilanes, but over a period of several hours slow racemization in solution at room temperature occurs, which can be suppressed by a transmetalation reaction with MgBr2(thf)4. 相似文献
68.
69.
Schreiner E Nicolini C Ludolph B Ravindra R Otte N Kohlmeyer A Rousseau R Winter R Marx D 《Physical review letters》2004,92(14):148101
The temperature-dependent behavior of a solvated oligopeptide, GVG(VPGVG), is investigated. Spectroscopic measurements, thermodynamic measurements, and molecular dynamics simulations find that this elastinlike octapeptide behaves as a two-state system that undergoes an "inverse temperature" folding transition and reentrant unfolding close to the boiling point of water. A molecular picture of these processes is presented, emphasizing changes in the dynamics of hydrogen bonding at the protein/water interface and peptide backbone librational entropy. 相似文献
70.