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21.
Metalloprotein tethered CdSe nanoparticles have been generated to provide selective and reagentless maltose biosensing. As opposed to cell or protein detection by semiconducting nanoparticle bioconjugates, a modular method for small-molecule detection using semiconducting nanoparticle bioconjugates has been difficult. Here we report a method for reagentless protein-based semiconducting nanoparticle biosensors. This method uses Ru(II) complex-CdSe nanoparticle interactions and the maltose-induced conformation changes of maltose binding protein to alter the CdSe nanoparticle fluorescence emission intensity. In this proof-of-principle system, the maltose-induced protein conformation changes alter the Ru(II) complex-CdSe nanoparticle interaction, which increases the CdSe emission intensity. Altered CdSe emission intensity effects are best described as electron transfer from the Ru(II) complex to the CdSe excited state forming the nonfluorescent CdSe anion. Four surface-cysteine, Ru(II) complex-attached maltose-binding proteins have been studied for maltose dependent alteration of CdSe emission intensities. With 3.0-3.5 nm diameter CdSe nanoparticles, all ruthenated maltose-binding proteins display similar maltose-dependent increases (1.4-fold) in CdSe emission intensity and maltose binding affinities (KA = 3 x 106 M-1). For these four systems, the only difference was the sample-to-sample variation in maltose-dependent responses. Thus, very few surface cysteine mutations need to be examined to find a successful biosensor, as opposed to analogous systems using organic fluorophores. This strategy generates a unimolecular, or reagentless, semiconducting nanoparticle biosensor for maltose, which could be applied to other proteins with ligand-dependent conformation changes. 相似文献
22.
Volumetric heat capacities of the six binary mixtures formed from cyclopentane, cyclohexane, cycloheptane and cyclooctane were determined at 298.15 K in a Picker flow microcalorimeter. Excess heat capacities obtained from the results are compred with the temperature variation of excess enthalpies from the literature. 相似文献
23.
Brian A. Naughton Benson Sibanda Jory P. Weintraub Julia San Román Vafa Kamali 《Applied biochemistry and biotechnology》1995,54(1-3):65-91
A method of coculturing adult rat hepatic parenchymal cells (PC) and stromal cells in a three-dimensional framework of nylon
filtration screens or biodegradable polymer meshes was developed in our laboratory. Rat liver stroma, which includes vascular
and bile duct endothelial cells, fat-storing cells, fibroblasts, and Kupffer cells, were isolated by gradient centrifugation
afterin situ liver perfusion and expanded in monolayer culture prior to seeding onto nylon screens or bioresorbable polyglycolic acid
(PGA) polymers oriented into a felt-like construct. A second inoculum of freshly isolated PC was applied after the stromal
cells became established. Histological analyses revealed that PC proliferation occurred until all available space for expansion
within the template was exhausted. These cells retained their rounded morphology, and after 4–5 wk 7–9 “layers” of PC filled
the 140-μm deep template. Dioxin-inducible cytochrome P450 activity was detected for up to 58 d in culture, and albumin, fibrinogen,
transferrin, and soluble fibronectin were detected in the medium by enzyme-linked immunosorbent assay (ELISA) for 48 d in
vitro. Immunohistochemical analysis of sections through the cultures confirmed the presence of these proteins as well as cytokeratin
at the cellular level; the extracellular matrix stained for both collagen type III and laminin. Long-term PC proliferation
and function were enhanced by the presence of stromal cells as well as by a meshwork template whose geometry allows the interaction
of PC with stroma and matrix on several different planes. To permit transplantation, co-cultures of hepatic PC and stromal
cells were established on PGA felt constructs instead of nylon screens. After 24 d in vitro, these constructs were grafted
into sites in the mesentery, omentum, and sub-cutaneous tissues of adult Long-Evans rats. The growth of hepatocytes after
30 din situ was evident by histological analysis; grafts of co-cultures regenerated a liver-like architecture consisting of sinusoids
and putative biliary structures. In addition, PC at these extrahepatic graft sites were positive for albumin, transferrin,
and fibrinogen synthesis by immunohistochemistry. Graft survival was enhanced when recipients were subjected to 40% hepatectomy.
Hepatic PC:stromal cell cocultures may prove useful in the restoration of liver function either by direct transplantation
using PGA or similar templates, or as extracorporeal devices, using nylon screens. 相似文献
24.
Lee SW Lee K Seomoon D Kim S Kim H Kim H Shim E Lee M Lee S Kim M Lee PH 《The Journal of organic chemistry》2004,69(14):4852-4855
Tetraorganoindates, which were prepared easily from the reaction of 1 equiv of InCl(3) with 4 equiv of organometallics, could be employed as effective nucleophilic cross-coupling partners in Pd-catalyzed carbonylative cross-coupling reactions with a variety of organic electrophiles. The present method gave unsymmetrical ketones and 1,4-diacylbenzenes in good yields with highly efficient transfer of almost all the organic groups attached to the indium under a carbon monoxide atmosphere in THF at 60 degrees C. 相似文献
25.
A formally exact Kirkwood-Buff virial formula for the surface tension of a supersaturated interface is derived. A modified Gibbs ensemble method is given that allows the creation of interacting supersaturated phases of equal chemical potential, and which enables the Kirkwood-Buff formula to be applied. The methods are tested by Monte Carlo simulation of a supersaturated Lennard-Jones fluid with a planar liquid-vapor interface. The Kirkwood-Buff results for the supersaturated surface tension are found to be in reasonable agreement with new results obtained here using the recently developed, formally exact, ghost interface method, [M. P. Moody and P. Attard, J. Chem. Phys., 2002, 117, 6705]. The surface tension is obtained as a function of supersaturation at four temperatures, and it is found to decrease with increasing supersaturation, and to vanish at the vapor spinodal. The relevance of the present results to the nucleation of droplets in a supersaturated vapor is discussed. 相似文献
26.
MacLean EJ Harris KD Kariuki BM Kitchin SJ Tykwinski RR Swainson IP Dunitz JD 《Journal of the American Chemical Society》2003,125(47):14449-14451
The transformation of ammonium cyanate into urea, first studied over 170 years ago by W?hler and Liebig, has an important place in the history of chemistry. To understand the nature of this solid state reaction, knowledge of the crystal structure of ammonium cyanate is a prerequisite. Employing neutron powder diffraction, we demonstrate conclusively that, in the structure of ammonium cyanate, the NH(4)(+) cation forms N-H...N hydrogen bonds to four cyanate N atoms at alternate corners of a distorted cube, rather than our previously proposed alternative arrangement with N-H...O hydrogen bonds to cyanate O atoms at the other four corners. 相似文献
27.
28.
Lee K Kim H Miura T Kiyota K Kusama H Kim S Iwasawa N Lee PH 《Journal of the American Chemical Society》2003,125(32):9682-9688
3-tert-Butyldimethylsilyloxyalk-2-enylsulfonium salts, generated in situ from the reaction of alpha,beta-enones with dimethyl sulfide in the presence of TBSOTf, underwent a novel nucleophilic substitution with allylindiums to give silyl enol ethers of delta,epsilon-alkenyl ketones in good yields, which correspond to formal Michael addition products. In a similar manner, 1,4-propargylation of propargylindiums onto the sulfonium salts produced the corresponding silyl enol ethers of delta,epsilon-alkynyl ketones in good yields. Organoindium reagents derived from gamma-substituted propargyl bromide and indium afforded the corresponding silyl enol ethers of beta-allenyl ketones in good yields. The reaction proceeds via an addition-substitution mechanism involving the formation of allylic sulfonium salts. The presence of the intermediate sulfonium salt was confirmed by observation of the low-temperature (1)H NMR spectra. 相似文献
29.
Lee PH Kim S Lee K Seomoon D Kim H Lee S Kim M Han M Noh K Livinghouse T 《Organic letters》2004,6(26):4825-4828
[reaction: see text] The cyclization of 1-bromo-2,7- and 1-bromo-2,8-enynes mediated by indium in DMF produced five- and six-membered cyclic compounds. Although KI was a necessary additive in the cyclization of terminal 1-bromo-2,7-enynes to give the desired products at 25 degrees C, reactions of terminal 1-bromo-2,8-enynes and internal 1-bromo-2,7-enynes with indium proceeded at 100 degrees C in DMF without KI. After cyclizations, subsequent cross-coupling reaction and iodolysis increase the usefulness of this reaction. 相似文献
30.