全文获取类型
收费全文 | 4754篇 |
免费 | 257篇 |
国内免费 | 16篇 |
专业分类
化学 | 3844篇 |
晶体学 | 20篇 |
力学 | 77篇 |
数学 | 475篇 |
物理学 | 611篇 |
出版年
2023年 | 54篇 |
2022年 | 147篇 |
2021年 | 191篇 |
2020年 | 146篇 |
2019年 | 137篇 |
2018年 | 76篇 |
2017年 | 75篇 |
2016年 | 197篇 |
2015年 | 195篇 |
2014年 | 188篇 |
2013年 | 266篇 |
2012年 | 378篇 |
2011年 | 423篇 |
2010年 | 237篇 |
2009年 | 205篇 |
2008年 | 316篇 |
2007年 | 301篇 |
2006年 | 284篇 |
2005年 | 211篇 |
2004年 | 206篇 |
2003年 | 162篇 |
2002年 | 138篇 |
2001年 | 34篇 |
2000年 | 36篇 |
1999年 | 35篇 |
1998年 | 21篇 |
1997年 | 23篇 |
1996年 | 28篇 |
1995年 | 26篇 |
1994年 | 25篇 |
1993年 | 9篇 |
1992年 | 6篇 |
1991年 | 9篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 7篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 25篇 |
1984年 | 19篇 |
1983年 | 20篇 |
1982年 | 22篇 |
1981年 | 23篇 |
1980年 | 11篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1977年 | 13篇 |
1976年 | 7篇 |
1975年 | 7篇 |
1974年 | 9篇 |
排序方式: 共有5027条查询结果,搜索用时 15 毫秒
41.
G. Solano S. A. Katz J. Holzbecher A. Chatt 《Journal of Radioanalytical and Nuclear Chemistry》1994,179(1):173-176
Reference materials for the speciation and quantification of chromium in contaminated soils were prepared by impregnating diatomaceous earth with BaCrO4 and Cr2O3. The chronium concentrations of these materials were confirmed to be 200 mg/kg both by atomic absorption spectrometry and by instrumental neutron activation analysis, but monthly assays over two calendar quarters of the reference material impregnated with BaCrO4 revealed the hexavalent chromium was not stable in this matrix. 相似文献
42.
Ireland RE Gleason JL Gegnas LD Highsmith TK 《The Journal of organic chemistry》1996,61(20):6856-6872
A total synthesis of FK-506 (1) is presented. The synthesis features a highly convergent approach utilizing a block coupling strategy. Top and bottom half sections of the molecule are coupled by addition of a vinyl cuprate with a spiroenone. The alpha-allyl aldol functionality is revealed by a reductive opening of the spiroenone system. The labile alpha,beta-diketoamide hemiketal portion of the molecule is prepared by a late stage generation and oxidation of a masked enediol. Top and bottom half segments are themselves derived by coupling of smaller subunits, resulting in a very convergent route. 相似文献
43.
Soltero-Higgin M Carlson EE Phillips JH Kiessling LL 《Journal of the American Chemical Society》2004,126(34):10532-10533
The flavoenzyme uridine 5'-diphosphate (UDP)-galactopyranose mutase (UGM) plays a key role in the cell wall biosynthesis of many pathogens, including Mycobacterium tuberculosis. Using a synthetic fluorescent ligand, we screened 16 000 compounds in a fluorescence polarization assay. Effective inhibitors of UGM were identified. 相似文献
44.
Gas chromatographic (GC) optimization studies are conducted for the 10 methylenedioxyphenethylamine regioisomeric substances related to the drug of abuse 3,4-methylenedioxymethamphetamine (MDMA, Ecstasy). These 10 compounds, having the same molecular weight and equivalent major mass spectral fragments, are not completely resolved using typical GC-mass spectrometry screening methods for illicit drugs. MDMA coelutes with at least one nondrug regioisomer under standard drug screening conditions. Separation of the 10 regioisomers is studied using stationary phases of varying polarities. Resolution optimization shows that very slow program rates give the best separation for the nonpolar stationary phases, requiring analysis times of as much as 85 min. Narrow-bore columns containing the same nonpolar stationary phases improve the analysis time to approximately 29 min. The polar stationary phase DB-35MS allows high-temperature programming rates, yielding complete resolution of all 10 compounds in less than 7 min. Temperature program optimization studies on the DB-35MS phase allow the separation time to be reduced to approximately 4.5 min. 相似文献
45.
Rosenthal SJ Tomlinson I Adkins EM Schroeter S Adams S Swafford L McBride J Wang Y DeFelice LJ Blakely RD 《Journal of the American Chemical Society》2002,124(17):4586-4594
To explore the potential for use of ligand-conjugated nanocrystals to target cell surface receptors, ion channels, and transporters, we explored the ability of serotonin-labeled CdSe nanocrystals (SNACs) to interact with antidepressant-sensitive, human and Drosophila serotonin transporters (hSERT, dSERT) expressed in HeLa and HEK-293 cells. Unlike unconjugated nanocrystals, SNACs were found to dose-dependently inhibit transport of radiolabeled serotonin by hSERT and dSERT, with an estimated half-maximal activity (EC(50)) of 33 (dSERT) and 99 microM (hSERT). When serotonin was conjugated to the nanocrystal through a linker arm (LSNACs), the EC(50) for hSERT was determined to be 115 microM. Electrophysiology measurements indicated that LSNACs did not elicit currents from the serotonin-3 (5HT(3)) receptor but did produce currents when exposed to the transporter, which are similar to those elicited by antagonists. Moreover, fluorescent LSNACs were found to label SERT-transfected cells but did not label either nontransfected cells or transfected cells coincubated with the high-affinity SERT antagonist paroxetine. These findings support further consideration of ligand-conjugated nanocrystals as versatile probes of membrane proteins in living cells. 相似文献
46.
Claudio Baggiani Gianfranco Giraudi Cristina Giovannoli Cinzia Tozzi Laura Anfossi 《Analytica chimica acta》2004,504(1):43-52
The current opinion about molecular imprinted polymers (MIPs) is that their molecular recognition properties are due to the presence of nanocavities formed during a polymerization process developed in the presence of a template molecule. According to this principle, the shape of these nanocavities is complementary to that of the template and non-covalent interactions are established between the binding site and a single template molecule. Nevertheless, there are some experimental indications that the real molecular recognition mechanism involves clusters of template molecules being packed into the binding site. Recently, it has been proposed that template molecules covalently linked to the binding site can act as nucleation points, enhancing the formation of these molecular clusters.We have tested this hypothesis by studying the adsorption isotherms of polymers prepared by imprinting them with 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). Three different polymers were considered: P0, prepared without the template, P1, whose template was represented by 2,4,5-T molecules, and P2, whose template was 1/3 constituted by the polymerisable 2-(2,4,5-trichlorophenoxyacetoxy)-ethylmethacrylate (2,4,5-TEMA) and 2/3 by 2,4,5-T. The polymers were prepared by thermoinduced polymerization of template mixtures, 4-vinylpyridine and ethylene dimethacrylate. The crushed polymers were packed into HPLC columns and frontal chromatographic runs were performed by eluting the columns with a mobile phase containing variable amounts of 2,4,5-T.The experimental adsorption isotherms were fitted by using several isotherm models, and the Freundlich-Langmuir model was found to give the best fitting in terms of F-test. All the models considered showed a significant difference between the affinity constant values measured for the polymer P1 and P2, with a higher value for the polymer P2 (for Freundlich-Langmuir model: polymer P1, k=(2.00±0.43)×104 M−1; polymer P2, k=(1.93±0.0535)×105 M−1; ratio P2/P1, 9.65±2.09). Such experimental results support the hypothesis that a polymer prepared with a limited amount of template covalently attached to the binding site shows an increased affinity for the template itself. 相似文献
47.
Laura S. Zamorano Francisco Gavilanes Ivan Yu. Sakharov Robert B. van Huystee Valery L. Shnyrov 《Thermochimica Acta》2004,417(1):67-73
Detailed differential scanning calorimetry (DSC), steady-state tryptophan fluorescence and far-UV circular dichroism (CD) studies, together with enzymatic assays, were carried out to monitor the thermal stability of anionic peanut peroxidase (aPrx) at pH 3.0. The spectral parameters were seen to be good complements to the highly sensitive but integral method of DSC. Thus, changes in far-UV CD corresponded to changes in the overall secondary structure of the enzyme, while changes in intrinsic tryptophan fluorescence emission corresponded to changes in the tertiary structure of the enzyme. The results, supported with data concerning changes in enzymatic activity with temperature, show that thermally induced transitions for aPrx are irreversible and strongly dependent upon the scan rate, suggesting that denaturation is under kinetic control. It is shown that the process of aPrx denaturation can be interpreted with sufficient accuracy in terms of the simple kinetic scheme, , where k is a first-order kinetic constant that changes with temperature, as given by the Arrhenius equation; N is the native state, and D is the denatured state. On the basis of this model, the parameters of the Arrhenius equation were calculated. 相似文献
48.
René Rojas 《Journal of organometallic chemistry》2004,689(13):2268-2272
Reaction of CrCl3 with LiCpSiMe3 in THF leads to the formation of a solvated intermediate, [(η5-Me3SiCp)CrCl2(THF)], which in turn reacts with diphenyl-2-pyridylphosphine to yield the complex [(C6H5)2PC5H4NH][(η5-Me3SiCp)CrCl3] (1) in 66% yield. As a secondary product was isolated the neutral complex [(η5-Me3SiCp)CrCl2{(C6H5)2PC5H4N}] (2) in 5% yield. The structure of complex 1 has been determined by single crystal X-ray diffraction. In the anion the metal centre shows a pseudo-octahedral geometry with the centroid of the trimethylsilylcyclopentadienyl ligand occupying the centre of three octahedral sites, and three chloride atoms completing the co-ordination sphere. Complex 1 in the presence of MAO leads to the formation of an active catalyst for the polymerization of ethylene. 相似文献
49.
Six isotypic R6ZTe2 phases have been synthesized in Ta at elevated temperatures and characterized by single crystal X-ray refinements for R=Y, Z=Rh, Pd, Ag, Y and for R=Lu, Z=Cu, Ag. All crystallize in the Sc6PdTe2-type structure, Pnma, Z=4, a∼21.5 Å, b∼4.1 Å, c∼11.4 Å. The results can be viewed as the replacement of Te3 atoms in the parent isotypic Sc2Te (or in the hypothetical Y2Te or Lu2Te analogues) by the above the Z, the Y example giving the new binary phase Y7Te2. The shorter (and stronger) metal-metal bonds concentrate in the region of metal (Z, Y) substitution, as revealed by larger integrated crystal orbital Hamilton population (ICOHP) values derived from linear muffin-tin-orbital (LMTO) calculations. Partial densities-of-states data for Y7Te2 reflect a similar behavior. Individual R-R bond distances are seen to deviate appreciably from the more fundamental overlap population measures for each. 相似文献
50.
Dip-pen nanolithography in tapping mode 总被引:1,自引:0,他引:1
Dip-pen nanolithography (DPN) is becoming a popular nano-patterning technique for depositing materials onto a substrate using the probe of an atomic force microscope (AFM). Here, we demonstrate the deposition of a short synthetic peptide by DPN using the Tapping Mode of AFM rather than the commonly used contact mode. DPN in Tapping Mode requires drive amplitude modifications for deposition, yet allows for gentle imaging of the deposited material and enables deposition on soft surfaces. 相似文献