全文获取类型
收费全文 | 1740篇 |
免费 | 35篇 |
国内免费 | 15篇 |
专业分类
化学 | 950篇 |
晶体学 | 9篇 |
力学 | 56篇 |
数学 | 264篇 |
物理学 | 511篇 |
出版年
2021年 | 23篇 |
2020年 | 12篇 |
2019年 | 10篇 |
2018年 | 18篇 |
2017年 | 15篇 |
2016年 | 20篇 |
2015年 | 25篇 |
2014年 | 34篇 |
2013年 | 92篇 |
2012年 | 46篇 |
2011年 | 89篇 |
2010年 | 38篇 |
2009年 | 44篇 |
2008年 | 77篇 |
2007年 | 82篇 |
2006年 | 61篇 |
2005年 | 69篇 |
2004年 | 63篇 |
2003年 | 55篇 |
2002年 | 58篇 |
2001年 | 44篇 |
2000年 | 41篇 |
1999年 | 26篇 |
1998年 | 16篇 |
1997年 | 25篇 |
1996年 | 38篇 |
1995年 | 32篇 |
1994年 | 22篇 |
1993年 | 29篇 |
1992年 | 37篇 |
1991年 | 25篇 |
1990年 | 18篇 |
1989年 | 16篇 |
1988年 | 27篇 |
1987年 | 17篇 |
1986年 | 15篇 |
1985年 | 30篇 |
1984年 | 23篇 |
1983年 | 18篇 |
1982年 | 21篇 |
1981年 | 20篇 |
1980年 | 33篇 |
1979年 | 26篇 |
1978年 | 22篇 |
1977年 | 19篇 |
1976年 | 24篇 |
1975年 | 23篇 |
1974年 | 17篇 |
1973年 | 27篇 |
1972年 | 13篇 |
排序方式: 共有1790条查询结果,搜索用时 15 毫秒
51.
52.
The first-order thermodynamic perturbation theory of Wertheim (TPT1) is extended to treat ring aggregates, formed by inter- and intramolecular association. The expression for the residual association contribution to the Helmholtz free energy for ring aggregates, incorporating the appropriate terms in Wertheim's fundamental graph sum of the TPT1 density expansion, is derived to calculate the distribution of the molecular bonding states. This requires the introduction of two new parameters to characterise each possible ring type: the ring size τ, which is equal to one in the case of intramolecular association, and a parameter W that captures the likelihood of two ring-forming sites bonding. The resulting framework can be incorporated in equations of state that account for the residual association contribution to the free energy, such as the statistical associating fluid theory (SAFT) family, or the cubic plus association (CPA) equation of state. This extends the applicability of these equations of state to mixtures with an arbitrary number of association sites capable of hydrogen bonding to form intramolecular and intermolecular rings. The formalism is implemented within SAFT-VR Mie to calculate the fluid-phase equilibria of model chain-like molecules containing two associating sites A and B, allowing for the formation of open-chain aggregates and intramolecular bonds. The effect of adding a second component that competes for the association sites that mediate intramolecular association in the chain is also examined. Accounting for intramolecular bonding is shown to have a significant impact on the phase equilibria of such systems. 相似文献
53.
Matthew B.D. Mitchell David Jackson Peter F. James 《Journal of Sol-Gel Science and Technology》1998,13(1-3):359-364
Mg2SiO4 gels were prepared from alkoxide precursors, and the formation of the forsterite crystal phase was studied after heat treatments up to 1200°C. Prehydrolyzed TEOS in solution with 2-methoxyethanol was mixed with Mg(OEt)2, and the solution was hydrolyzed using excess water. The resultant gels were dried at 100°C to form xerogels which were subsequently powdered. These powders were characterized using thermal analysis (DTA and TGA), surface area analysis (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM).DTA and XRD indicated that forsterite crystallized at 770°C, and by 1000°C the powders were predominantly crystalline. BET gave powder surface areas between 400 and 550 m2 g–1. TEM revealed angular particles with sizes between 0.2 and 2 m. The low temperature of crystallization of forsterite indicates a high degree of intimate mixing between the precursor alkoxides, although XRD indicated some degree of inhomogeneity. 相似文献
54.
Nomkoko TE Jackson GE Nakani BS Louw WK Zeevaart JR 《Dalton transactions (Cambridge, England : 2003)》2004,(5):741-749
The thermodynamic equilibria of copper(II), zinc(II), calcium(II) and gadolinium(III) with 3,3,9,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime (L1) have been studied at 25 degrees C and an ionic strength of 0.15 mol dm(-3). Copper and gadolinium form stable complexes with the ligand while the corresponding zinc species are more than 9 log units less stable. No complexes between calcium and the ligand were detected. The low binding strength of L1 towards zinc is attributed to the square-planar coordination geometry forced on the metal ion by the ligand as revealed by molecular mechanics calculations and molecular dynamics simulations. Speciation calculations, using a computer model of blood plasma, indicate that, despite the high concentration of zinc(II) and calcium(II) in vivo, L1 is able to increase the low-molecular-mass fraction of copper in plasma. Octanol/water partition coefficient of [CuL1H(-1)] indicates that although this species is largely hydrophilic, approximately 6% of the complex goes into the octanol phase and hence may promote dermal absorption of copper by the same amount. The dermal penetration rate is calculated to be 4.0 x 10(-4) mm h(-1). The [CuL1H(-1)] complex, which predominates at pH 7.4, is a poor mimic of native copper-zinc superoxide dismutase. Biodistribution experiments using the 64Cu-labelled [CuL1H(-1)] complex indicate an initial high uptake of this species in the liver followed by redistribution into muscle. Only a small amount is excreted through the urine. 相似文献
55.
19F NMR is a powerful tool for monitoring protein conformational changes and interactions; however, the inability to site-specifically introduce fluorine labels into proteins of biological interest severely limits its applicability. Using methods for genetically directing incorporation of unnatural amino acids, we have inserted trifluoromethyl-l-phenylalanine (tfm-Phe) into proteins in vivo at TAG nonsense codons with high translational efficiency and fidelity. The binding of substrates, inhibitors, and cofactors, as well as reactions in enzymes, were studied by selective introduction of tfm-Phe and subsequent monitoring of the 19F NMR chemical shifts. Subtle protein conformational changes were detected near the active site and at long distances (25 Angstrom). 19F signal sensitivity and resolution was also sufficient to differentiate protein environments in vivo. Since there has been interest in using 19F-labeled proteins in solid-state membrane protein studies, folding studies, and in vivo studies, this general method for genetically incorporating a 19F-label into proteins of any size in Escherichia coli should have broad application beyond that of monitoring protein conformational changes. 相似文献
56.
An aqueous aluminum liftoff process suitable for fabrication of hybrid patterns of protein and supported lipid membrane on silica surfaces is described. Patterned aluminum thin films, which can be produced by conventional optical or electron beam lithography, are employed as sacrificial protecting layers to define the geometry of the protein-lipid patterns. The aluminum is lifted off in a mildly basic aqueous solution, which preserves the integrity of bound protein layers. The newly exposed substrate can then be filled with supported membrane by exposure to an aqueous vesicle suspension. The final substrate consists of patterned protein and lipid membranes with spatial resolution determined by aluminum patterns, down to 200 nm line widths in this case. Inorganic surfaces were characterized by atomic force microscopy and X-ray photoelectron spectroscopy while supported bilayers and protein patterns were characterized by epifluorescence microscopy. 相似文献
57.
Core cross-linked star polymers possessing responsiveness to pH and temperature stimuli have been prepared, and we demonstrate how changes to pH and temperature can be used to trigger the release and uptake of a hydrophobic dye. 相似文献
58.
Fluorescence quantum yields and lifetimes of coumarin dyes are sharply reduced in polar solvents if amine substituent groups are free to rotate. The polar solvent effect is interpreted in terms of relaxation of excited dye from an initial planar conformation to a twisted zwitterionic state. 相似文献
59.
60.
All seven possible geometric isomers (four mer and three facial) for the [Co(dien)(ibn)Cl](2+) system have been synthesized (dien = diethylenetriamine, ibn = 1,2-diamino-2-methylpropane). Their structures in dimethyl sulfoxide solution have been uniquely determined by two-dimensional NMR spectroscopy (DQCOSY and NOESY). 相似文献