全文获取类型
收费全文 | 2814篇 |
免费 | 143篇 |
国内免费 | 7篇 |
专业分类
化学 | 2395篇 |
晶体学 | 6篇 |
力学 | 37篇 |
数学 | 255篇 |
物理学 | 271篇 |
出版年
2023年 | 20篇 |
2022年 | 123篇 |
2021年 | 138篇 |
2020年 | 69篇 |
2019年 | 73篇 |
2018年 | 63篇 |
2017年 | 45篇 |
2016年 | 128篇 |
2015年 | 92篇 |
2014年 | 123篇 |
2013年 | 163篇 |
2012年 | 182篇 |
2011年 | 228篇 |
2010年 | 133篇 |
2009年 | 127篇 |
2008年 | 194篇 |
2007年 | 177篇 |
2006年 | 163篇 |
2005年 | 148篇 |
2004年 | 111篇 |
2003年 | 96篇 |
2002年 | 76篇 |
2001年 | 27篇 |
2000年 | 21篇 |
1999年 | 24篇 |
1998年 | 21篇 |
1997年 | 14篇 |
1996年 | 25篇 |
1995年 | 16篇 |
1994年 | 9篇 |
1993年 | 9篇 |
1992年 | 12篇 |
1991年 | 9篇 |
1990年 | 9篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 8篇 |
1985年 | 16篇 |
1984年 | 5篇 |
1983年 | 16篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1972年 | 2篇 |
1933年 | 2篇 |
排序方式: 共有2964条查询结果,搜索用时 15 毫秒
21.
Marta Filizola Maria Carteni-Farina Juan J. Perez 《Journal of computer-aided molecular design》1999,13(4):397-407
3D models of the opioid receptors , and were constructed using BUNDLE, an in-house program to build de novo models of G-protein coupled receptors at the atomic level. Once the three opioid receptors were constructed and before any energy refinement, models were assessed for their compatibility with the results available from point-site mutations carried out on these receptors. In a subsequent step, three selective antagonists to each of three receptors (naltrindole, naltrexone and nor-binaltorphamine) were docked onto each of the three receptors and subsequently energy minimized. The nine resulting complexes were checked for their ability to explain known results of structure-activity studies. Once the models were validated, analysis of the distances between different residues of the receptors and the ligands were computed. This analysis permitted us to identify key residues tentatively involved in direct interaction with the ligand. 相似文献
22.
Serrano MC Portolés MT Vallet-Regí M Izquierdo I Galletti L Comas JV Pagani R 《Macromolecular bioscience》2005,5(5):415-423
Tissue engineering offers the potential of providing vessels that can be used to replace diseased and damaged native blood vessels. The endothelization of a synthetic vascular graft minimizes the failures associated with blood clotting and platelet activation. The aim of this study was to culture vascular-derived endothelial and smooth muscle cells on both untreated and NaOH-treated poly(epsilon-caprolactone) (PCL) films, a biocompatible and bio-resorbable polymer, and to evaluate the behavior of both cell types as a preliminary study for vascular graft development. PCL films were prepared by hot pressing; characterized by DSC, IR, SEM, and scanning force microscopy; and treated with NaOH to increase the surface hydrophilicity before cell culture. Endothelial and smooth muscle cells, isolated from pig cava vein, were characterized by immunofluorescence and confocal microscopy studies of endothelial nitric oxide synthase and alpha-smooth muscle actin. Good adhesion, growth, viability and morphology of both the endothelial and smooth muscle cells on PCL films were obtained, but a light stimulation of mitochondrial activity was observed during short culture times. NaOH treatment improved the adhesion and enhanced the proliferation in both cell types. This verified the possible use of this modified polymer as a support in the preparation of a synthetic vascular graft. [Diagram: see text] SEM micrograph of smooth muscle cells cultured on NaOH-treated PCL film. (Original magnification: 1000x). 相似文献
23.
High mobility of dithiophene-tetrathiafulvalene single-crystal organic field effect transistors 总被引:1,自引:0,他引:1
Mas-Torrent M Durkut M Hadley P Ribas X Rovira C 《Journal of the American Chemical Society》2004,126(4):984-985
Single-crystal field effect transistors of the organic semiconductor dithiophene-tetrathiafulvalene (DT-TTF) were prepared by drop casting. Long, thin crystals connected two microfabricated gold electrodes, and a silicon substrate was used as a back gate. The highest hole mobility observed was 1.4 cm2/Vs, which is the highest reported for an organic semiconductor not based on pentacene. A high ON/OFF ratio of at least 7 x 105 was obtained for this device. 相似文献
24.
J. Giménez-Izquierdo J. Guiteras A. Izquierdo M. D. Prat 《Fresenius' Journal of Analytical Chemistry》1991,341(10):638-640
Summary The absorption spectrum of the nitrate radical (NO3) in aqueous solution and the kinetic of the reactions with Cl– and OH– have been determined using laser-spectrometric techniques. The maximum absorption was found at 635 nm with a decadic absorption coefficient of =(530±110) l/mol·cm. At 298 K rate constants of k1=(1.0±0.2)·107 l/mol·s for the reaction with chloride and of k2=(8.2±0.9)·107 l/mol·s for the reaction with hydroxide were obtained. 相似文献
25.
Isocytosine (ICH) exists in solution as two major tautomers, the keto form with N1 carrying a proton (1a) and the keto form with N3 being protonated (1b). In water, 1a and 1b exist in equilibrium with almost equal amounts of both forms present. Reactions with a series of Pd(II) and Pt(II) am(m)ine species such as (dien)Pd(II), (dien)Pt(II), and trans-(NH(3))(2)Pt(II) reveal, however, a distinct preference of these metals for the N3 site, as determined by (1)H NMR spectroscopy. Individual species have been identified by the pD dependence of the ICH resonances. pK(a) values (calculated for H(2)O) for deprotonation of the individual tautomers complexes are 6.5 and 6.4 for the N3 linkage isomers of dienPd(II) and dienPt(II), respectively, as well as 6.2 and 6.0 for the N1 linkage isomers. The dimetalated species [(dienM)(2)(IC-N1,N3)](3+) (M = Pd(II) or Pt(II)) are insensitive over a wide range of pD. The crystal structure analysis of [(dien)Pd(ICH-N3)](NO(3))(2) is reported. Ab initio calculations have been performed for tautomer compounds of composition [(NH(3))(3)Pt(ICH)](2+), cis- and trans-[(NH(3))(2)PtCl(ICH)](+), as well as trans-[(NH(3))(2)Pt(ICH)(2)](2+). Without exception, N3 linkage isomers are more stable, in agreement with experimental findings. As to the reasons for this binding preference, an NBO (natural bond orbital) analysis for [(NH(3))(3)Pt(ICH-N3)](2+)strongly suggests that intramolecular hydrogen bonding between trans-positioned NH(3) ligands and the two exocyclic groups of the ICH is of prime importance. The calculations furthermore show a marked pyramidalization of the NH(2) group of ICH in the complex once the heterocyclic ligand forms a dihedral angle <90 degrees with the Pt coordination plane. 相似文献
26.
Haralampus-Grynaviski N Ransom C Ye T Rôzanowska M Wrona M Sarna T Simon JD 《Journal of the American Chemical Society》2002,124(13):3461-3468
Urocanic acid, UCA, is characterized by two electronic transitions in the UV-B (280-320 nm) which comprise its broad absorption spectrum and give rise to wavelength-dependent isomerization quantum yields. The absorption spectrum of UCA extends into the UV-A (320-400 nm). Given the UV-A component of sunlight is significantly greater than the UV-B component it is hypothesized even weak UV-A photochemistry of UCA could be important for in vivo responses to UV radiation. Degenerate pump-probe experiments performed on t-UCA at several wavelengths in the UV-A reveal an excited-state absorption that undergoes a rapid, approximately 1 ps decay. Photoacoustic experiments performed on both the cis and trans isomers reveal the formation of a long-lived intermediate following UV-A excitation. The efficiency and action spectra for this latter photoactive process are presented and are similar for both isomers of UCA. Cholesterol hydroperoxide assays designed to investigate the nature of the UV-A photoreactivity of t-UCA confirm the production of reactive oxygen species. The bimolecular rate constant for the quenching of singlet oxygen by t-UCA is determined to be 3.5 x 10(6) M(-1) s(-1). Taking into consideration recent theoretical calculations and jet expansion studies of the electronic structure of gas-phase t-UCA, a model is proposed to explain the isomerization and photoreactivity of t-UCA in solution over the UV-A region. 相似文献
27.
This work focuses on the optimization of the rheological behavior of suspensions considering different solvent compositions. The effects of methyl ethyl ketone (MEK)/ethanol (E) solvent mixtures on reaction sialon suspensions were investigated by measuring sedimentation behavior, adsorption of dispersant, and flow behavior. It was shown that both the flow behavior and the sedimentation behavior strongly depended on selection of solvent composition. Using 3 wt% KD1 as dispersant, well-dispersed colloidal suspensions could be obtained in MEK-rich solvents. The suspensions with 60 vol% MEK/40 vol% E as solvent could be fitted to the Bingham model with very low yield stress, while suspensions with pure MEK or ethanol-rich mixtures as solvent showed pseudo plastic behavior with relatively high yield stress values. A model was proposed to explain the different flow behaviors of suspensions considering the different configurations of dispersant at particles' surfaces. 相似文献
28.
Marta M.?Conceio V. J.?Fernandes Jr. F. S. M.?Sinfrnio J. C. O.?Santos M. C. D.?Silva V. M.?Fonseca A. G.?Souza 《Journal of Thermal Analysis and Calorimetry》2005,79(2):263-266
Summary Sulfonylureas are widely used for the treatment of non-insulin dependent diabetes mellitus. Glibenclamide belongs to the group of substituted arylsulfonylureas. Many representative of this group shows polymorphism. The purpose of this work was to investigate the thermal behaviour and compatibility between glibenclamide and some excipients using thermoanalytical techniques (TG-DTG/DSC). The thermal and isothermal kinetics data showed incompatibility between glibenclamide and magnesium stearate. 相似文献
29.
The α-mercaptobenzeneacetic acid has been synthesized and screened for its properties as an analytical reagent. The acid dissociation constants have been determined potentiometrically in 0.1 M KNO3 and 0.5 M KNO3 ethanol-water 20% (v/v) solutions at 25 ± 0.1 °C. 相似文献
30.
Since its inception five decades ago, imprinted sol-gel materials went practically unnoticed, until in the 1970s the conceptual introduction of molecular imprinting in synthetic polymers triggered a new interest in this field. The recent growth in interest in organic–inorganic hybrid materials prepared by sol-gel chemistry and the development of a variety of new strategies for imprinting polymeric matrices have led to a growing activity in what became known as molecularly imprinted sol-gel materials. This paper intends to give an overview of recent progress in molecular imprinting in sol-gel matrices, the potential analytical applications of these tailor-made materials and their limitations, with the aim of drawing attention to useful information and to enhancing interest in this practically unexplored but promising field. 相似文献