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1.
Dr. Carla Carrera Dr. Eleonora Cavallari Dr. Giuseppe Digilio Dr. Oksana Bondar Prof. Silvio Aime Dr. Francesca Reineri 《Chemphyschem》2021,22(11):1042-1048
An efficient synthesis of vinyl-[1-13C]pyruvate has been reported, from which 13C hyperpolarized (HP) ethyl-[1-13C]pyruvate has been obtained by means of ParaHydrogen Induced Polarization (PHIP). Due to the intrinsic lability of pyruvate, which leads quickly to degradation of the reaction mixture even under mild reaction conditions, the vinyl-ester has been synthesized through the intermediacy of a more stable ketal derivative. 13C and 1H hyperpolarizations of ethyl-[1-13C]pyruvate, hydrogenated using ParaHydrogen, have been compared to those observed on the more widely used allyl-derivative. It has been demonstrated that the spin order transfer from ParaHydrogen protons to 13C, is more efficient on the ethyl than on the allyl-esterdue to the larger J-couplings involved. The main requirements needed for the biological application of this HP product have been met, i. e. an aqueous solution of the product at high concentration (40 mM) with a good 13C polarization level (4.8 %) has been obtained. The in vitro metabolic transformation of the HP ethyl-[1-13C]pyruvate, catalyzed by an esterase, has been observed. This substrate appears to be a good candidate for in vivo metabolic investigations using PHIP hyperpolarized probes. 相似文献
2.
Oksana Yakimova 《Acta Appl Math》2004,81(1):339-345
In this paper, we give a partial classification of commutative spaces of Heisenberg type. Several classification results were known previously. In order to avoid complicated technical details, we restrict ourselves to saturated commutative spaces. Our results are presented in Table II. 相似文献
3.
Teresa Borowia Marek Mączyński Marek Pietraszkiewicz Oksana Pietraszkiewicz 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(1-2):131-138
The crystal structure of the molecular complex of C-undecylcalix[4]resorcinarene with dioxane has been determined by X-ray analysis. The asymmetric unit contains one host and four guest molecules. The calix[4]resorcinarene moiety adopts a bowl conformation with C4v
symmetry. Four undecyl chains are axially oriented. Calix molecules are packed in a bowl-to-bowl fashion with alternating hydrophilic and hydrophobic layers. One of the hydrophilic dioxane molecules is located at the rim of the calix moiety and is hydrogen bonded to the other one. There is no interaction to attract, or direct the dioxane molecule into the interior of the cavity. There is an exo complex formed. The dioxane molecules – located in the hydrophobic part – are highly disordered. 相似文献
4.
Vijayasarathi Nagarajan Barbara Müller Oksana Storcheva Klaus Köhler Andreas Pöppl 《Research on Chemical Intermediates》2007,33(8):705-724
Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)2) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin
echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data
of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental
and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)2 and chloroform interacts via hydrogen bonding to oxygens of the acac ligands. 相似文献
5.
O. I. Yakimova A. M. Eremenko A. A. Chuiko 《Reaction Kinetics and Catalysis Letters》1993,50(1-2):199-201
A photochemical model reaction between anthracene and N,N-diethylaniline on aerosil has been studied. It is found that the nature of the surface is responsible for the mechanism of intermolecular interaction (dynamic or static one). 相似文献
6.
Teresa Borowiak Maciej Kubicki Grzegorz Dutkiewicz Marek Pietraszkiewicz Oksana Pietraszkiewicz 《Journal of inclusion phenomena and macrocyclic chemistry》2005,51(3-4):181-189
Two newly identified supramolecular structures arise from self-assembly of the macrocyclic 1,5,9,18,22,26- hexaaza[11.11]-p-cyclophane salts with o-nitrophenol (C28H50N6)4+·4(C6H4NO2O)− (1) and with HCl (C28H52N6)6+·6Cl-·4H2O (2). In both cases two-dimensional supramolecular sheets are formed. 相似文献
7.
Svitlana R. Petrusenko Wolfgang Linert Viktoria V. Dyakonenko Oksana V. Nesterova Oleg V. Shishkin 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(7):m281-m283
The title salt, [Zn(C2N2H8)3]2[CdI4]I2, conventionally abbreviated [Zn(en)3]2[CdI4]I2, where en is ethylenediamine, contains discrete [Zn(en)3]2+ cations and [CdI4]2− anions with distorted octahedral and nearly tetrahedral geometries, respectively, as well as uncoordinated I− ions. The cation and the free I− anion lie on twofold rotation axes and the [CdI4]2− anion lies on a axis in the space group I2d. The structure exhibits numerous weak inter‐ionic hydrogen bonds of two types, viz. N—H⋯I−(free ion) and N—H⋯I([CdI4]2−), which support the resulting three‐dimensional framework. 相似文献
8.
Boris A. Trofimov Lidiya N. Parshina Anatolii P. Tantsyrev Oksana V. Vysotskaya Nina K. Gusarova 《Tetrahedron》2007,63(47):11661-11665
Vinyl ethers, promising chiral carbohydrate synthons, have been synthesized by the addition of glucose acetals (1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, methyl 4,6-O-benzylidene-α-d-glucopyranoside, 1,2-O-cyclohexylidene-α-d-glucofuranose, methyl α-d-glucopyranoside) to acetylene under atmospheric and elevated pressures in an autoclave in the presence of superbase catalytic systems (KOH-DMSO, t-BuOK-DMSO). The complete vinylation of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose and methyl α-d-glucopyranoside has been realized under elevated pressure of acetylene in the system KOH-THF as well. 相似文献
9.
Das C Berezovska O Diehl TS Genet C Buldyrev I Tsai JY Hyman BT Wolfe MS 《Journal of the American Chemical Society》2003,125(39):11794-11795
gamma-Secretase cleaves the transmembrane domain of the amyloid precursor protein, a process implicated in the pathogenesis of Alzheimer's disease, and this enzyme is a founding member of an emerging class of intramembrane proteases. Modeling and mutagenesis suggest a helical conformation for the substrate transmembrane domain upon initial interaction with the protease. Moreover, biochemical evidence supports the presence of an initial docking site for substrate on gamma-secretase that is distinct from the active site, a property predicted to be generally true of intramembrane proteases. Here we show that short peptides designed to adopt a helical conformation in solution are inhibitors of gamma-secretase in both cells and enzyme preparations. Helical peptides with all d-amino acids are the most potent inhibitors and represent potential therapeutic leads. Subtle modifications that disrupt helicity also substantially reduce potency, suggesting that this conformation is critical for effective inhibition. Fluorescence lifetime imaging in intact cells demonstrates that helical peptides disrupt binding between substrate and protease, whereas an active site-directed inhibitor does not. These findings are consistent with helical peptides interacting with the initial substrate docking site of gamma-secretase, suggesting a general strategy for the development of potent and specific inhibitors of intramembrane proteases. 相似文献
10.
B. E. Ivanov L. A. Valitova T. G. Bykova N. V. Yakimova 《Russian Chemical Bulletin》1978,27(7):1416-1418
Conclusions The reaction of 2,2-bis(4-hydroxy-3-N,N-diethylaminomethylphenyl)propane with triethyl phosphite gave 2,2-bis(4-ethoxy-3-diethylphosphonomethylphenyl)propane via the intermediate formation of a compound with a pentacovalent phosphorus atom. In the presence of acetic acid the reaction leads to 2,2-bis(4-hydroxy-3-diethylphosphonomethylphenyl)propane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1621–1624, July, 1978. 相似文献