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941.
Dr. Mathieu Lesieur Dr. Claudio Battilocchio Dr. Ricardo Labes Dr. Jérôme Jacq Dr. Christophe Genicot Prof. Steven V. Ley Dr. Patrick Pasau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(5):1203-1207
A fast, scalable, and safer Csp3−H oxidation of activated and un-activated aliphatic chains can be enabled by methyl(trifluoromethyl)dioxirane (TFDO). The continuous flow platform allows the in situ generation of TFDO gas and its rapid reactivity toward tertiary and benzylic Csp3−H bonds. The process exhibits a broad scope and good functional group compatibility (28 examples, 8–99 %). The scalability of this methodology is demonstrated on 2.5 g scale oxidation of adamantane. 相似文献
942.
Mark Augath Patrick Heiler Stefan Kirsch Lothar R. Schad 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2009,200(1):134-136
The maintenance of a gradient of potassium and sodium ions across the cell membranes is essential for the physiological function of the mammal organism. The measurement of the spatial distribution of pathologically changing ion concentrations of 23Na and 39K with magnetic resonance imaging offers a promising approach in clinical diagnostics to measure tissue viability. Existing studies were focused mainly on 23Na imaging as well as spectroscopy with only one post-mortem study for 39K imaging. In this paper a triple resonant RF coil setup for the rat head at 9.4 T is presented for imaging of both nuclei (23Na and 39K) and the acquisition of anatomical proton images in the same experiment without moving the subject or the RF coil. In vivo MR images of 39K and 23Na in the rat brain were acquired as well as anatomical proton images in the same scanning session. 相似文献
943.
Szegő polynomials are orthogonal with respect to an inner product on the unit circle. Numerical methods for weighted least-squares
approximation by trigonometric polynomials conveniently can be derived and expressed with the aid of Szegő polynomials. This
paper discusses the conditioning of several mappings involving Szegő polynomials and, thereby, sheds light on the sensitivity
of some approximation problems involving trigonometric polynomials.
This Research supported in part by NSF grant DMS-0107858. 相似文献
944.
945.
Costa J Balogh E Turcry V Tripier R Le Baccon M Chuburu F Handel H Helm L Tóth E Merbach AE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(26):6841-6851
We have synthesized ditopic ligands L(1), L(2), and L(3) that contain two DO3A(3-) metal-chelating units with a xylene core as a noncoordinating linker (DO3A(3-) = 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate; L(1) = 1,4-bis{[4,7,10-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecane-1-yl]methyl}benzene; L(2) = 1,3-bis{[4,7,10-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecane-1-yl]methyl}benzene; L(3) = 3,5-bis{[4,7,10-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecane-1-yl]methyl}benzoic acid). Aqueous solutions of the dinuclear Gd(III) complexes formed with the three ligands have been investigated in a variable-temperature, multiple-field (17)O NMR and (1)H relaxivity study. The (17)O longitudinal relaxation rates measured for the [Gd(2)L(1-3)(H2O)(2)] complexes show strong field dependence (2.35-9.4 T), which unambiguously proves the presence of slowly tumbling entities in solution. The proton relaxivities of the complexes, which are unexpectedly high for their molecular weight, and in particular the relaxivity peaks observed at 40-50 MHz also constitute experimental evidences of slow rotational motion. This was explained in terms of self-aggregation related to hydrophobic interactions, pi stacking between the aromatic linkers, or possible hydrogen bonding between the chelates. The longitudinal (17)O relaxation rates of the [Gd(2)L(1-3)(H2O)(2)] complexes have been analysed with the Lipari-Szabo approach, leading to local rotational correlation times tau(1)(298) of 150-250 ps and global rotational correlation times tau(g)(298) of 1.6-3.4 ns (c(Gd): 20-50 mM), where tau(1)(298) is attributed to local motions of the Gd segments, while tau(g)(298) describes the overall motion of the aggregates. The aggregates can be partially disrupted by phosphate addition; however, at high concentrations phosphate interferes in the first coordination sphere by replacing the coordinated water. In contrast to the parent [Gd(DO3A)(H2O)(1.9)], which presents a hydration equilibrium between mono- and dihydrated species, a hydration number of q = 1 was established for the [Ln(2)L(1-3)(H2O)(2)] chelates by (17)O chemical shift measurements on Ln = Gd and UV/Vis spectrophotometry for Ln = Eu. The exchange rate of the coordinated water is higher for [Gd(2)L(1-3)(H2O)(2)] complexes k(ex)(298) = 7.5-12.0 x 10(6) s(-1)) than for [Gd(DOTA)(H2O)](-). The proton relaxivity of the [Gd(2)L(1-3)(H2O)(2)] complexes strongly decreases with increasing pH. This is related to the deprotonation of the inner-sphere water, which has also been characterized by pH potentiometry. The protonation constants determined for this process are logK(OH) = 9.50 and 10.37 for [Gd(2)L(1)(H2O)(2)] and [Gd(2)L(3)(H2O)(2)], respectively. 相似文献
946.
947.
Lothar Jaenicke 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》1990,102(5):594-595
948.
Lothar Matter 《Journal of separation science》1992,15(8):514-516
It is possible to determine the animal of origin of dairy products and raw and cooked meats by high resolution capillary GC of fatty acid methyl esters. This is demonstrated by several examples. 相似文献
949.
Crosslinked highly carboxylated acrylic latices with narrow particle size distributions were prepared by emulsion polymerization and characterized carefully by different AUC techniques (particle size distributions and particle density measurements). The acid form of those latices was neutralized with metal oxides like MgO, CaO, ZnO, or PbO in order to obtain the corresponding salt form of the latices which again were characterized carefully. The kinetics of the ion exchange between latex particles were studied by mixing, for example, the acid and the salt form of the latices monitoring the density distribution of the latex particles by density gradient ultracentrifugation. With all latices the hydrogen-metal ion exchange tends to be a complete one provided this process is given a sufficiently long exchange time. Theoretical models are provided which yield a qualitative explanation of the experimental data. 相似文献
950.