全文获取类型
收费全文 | 2200篇 |
免费 | 126篇 |
国内免费 | 10篇 |
专业分类
化学 | 1520篇 |
晶体学 | 4篇 |
力学 | 58篇 |
数学 | 418篇 |
物理学 | 336篇 |
出版年
2023年 | 24篇 |
2022年 | 27篇 |
2021年 | 74篇 |
2020年 | 57篇 |
2019年 | 56篇 |
2018年 | 52篇 |
2017年 | 43篇 |
2016年 | 111篇 |
2015年 | 91篇 |
2014年 | 93篇 |
2013年 | 135篇 |
2012年 | 182篇 |
2011年 | 222篇 |
2010年 | 90篇 |
2009年 | 93篇 |
2008年 | 151篇 |
2007年 | 144篇 |
2006年 | 147篇 |
2005年 | 121篇 |
2004年 | 93篇 |
2003年 | 79篇 |
2002年 | 67篇 |
2001年 | 23篇 |
2000年 | 17篇 |
1999年 | 18篇 |
1998年 | 11篇 |
1997年 | 8篇 |
1996年 | 13篇 |
1995年 | 2篇 |
1994年 | 12篇 |
1993年 | 14篇 |
1992年 | 12篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有2336条查询结果,搜索用时 109 毫秒
31.
Oscillatory properties of a weak convergent sequence of functions bounded inL
p
, 1 ≤p ≤ ∞, may be summarized by the parametrized measure it generates. When such a measure is generated by the gradients of a sequence
of functions bounded inH
1,p
, it must have special properties. The purpose of this paper is to characterize such parametrized measures as the ones that
obey Jensen’s inequality for all quasiconvex functions with the appropriate growth at infinity. We have found subtle differences
between the casesp < ∞ andp = ∞. A consequence is that any measure determined by biting convergence is in fact generated by a sequence convergent in
a stronger sense. We also give a few applications.
Research groupTransitions and Defects in Ordered Materials, funded by the NSF, the AFOSR, and the ARO. The work of the second author is also supported by DGICYT (Spain) through “Programa
de Perfeccionamiento y Movilidad del Personal Investigador” and through Grant PB90-0245. 相似文献
32.
An introduction to population approaches for optimization and hierarchical objective functions: A discussion on the role of tabu search 总被引:3,自引:0,他引:3
Pablo Moscato 《Annals of Operations Research》1993,41(2):85-121
Population approaches suitable for global combinatorial optimization are discussed in this paper. They are composed of a number of distinguishable individuals called "agents", each one using a particular optimization strategy. Periods of independent search follow phases on which the population is restarted from new configurations. Due to its intrinsic parallelism and the asynchronicity of the method, it is particularly suitable for parallel computers. Results on two test problems are presented in this paper. The individual search optimization strategies for each agent have been chosen having the basic characteristics of tabu search. This has been done in order to avoid mixing the hypothesized properties of these population approaches with those of more elaborate tabu search strategies, but remarking on its main characteristics. A set of four test problem "landscapes" is discussed and their use to improve and benchmark the results by using tabu search as the individual optimization strategy within a population heuristic is suggested and explored. The application of tabu search to new problem areas, like molecular biology, is also investigated. 相似文献
33.
den Brok MW Nuijen B Miranda E Floriano P Munt S Manzanares I Beijnen JH 《Journal of chromatography. A》2003,1020(2):251-258
ES-285 x HCl [(2S,3R)-2-amino-3-octadecanol hydrochloride] is a novel investigational anticancer agent, which has shown in vitro and in vivo cytotoxic activity against various tumor cell lines with selectivity for certain solid tumors. The pharmaceutical development of ES-285 x HCl warranted the availability of an assay for the quantification and purity determination of ES-285 x HCl active pharmaceutical ingredient (API) and its pharmaceutical dosage form. A liquid chromatographic method (LC) comprising of derivatisation of ES-285 x HCl with phenylisothiocyanate and UV-detection was developed. The method was found to be linear, precise and accurate. The assay also proved selectivity as determined by analysing ES-285 x HCl in combination with 15 analogues and in combination with hydroxypropyl-beta-cyclodextrin, the excipient used in the lyophilised pharmaceutical dosage form. Stress testing showed that the degradation products were separated from the parent compound, confirming its stability indicating capacity. The method was found robust as determined with design of experiments (DoE), which made it possible to predict system suitability responses in worst case experimental conditions and to define criteria for system suitability testing. 相似文献
34.
Different transformations of chiral epoxy esters 1 afford two different amino gamma-butyrolactones 2 and 6, and amino gamma-butenolides 8, by different nucleophilic opening-closing processes. [reaction: see text] 相似文献
35.
Mary E. R. McHale Ann-Sofi M. Kauppila Joyce R. Powell Pablo Otero Jr. Melani Jayasekera William E. Acree Jr. 《Journal of solution chemistry》1996,25(3):295-302
Experimental solubilities are reported for benzil dissolved in six binary mixtures containing dibutyl ether with hexane, heptane, octane, cyclohexane, methylcyclohexane, and 2,2,4-trimethylpentane at 25°C. Results of these measurements are compared to the predictions of equations developed previously for solubility in systems of nonspecific interactions. The most successful equation in terms of goodness of fit involved a volume fraction average of the excess Gibbs energies relative to the Flory-Huggins model, and predicted the experimental solubilities in the six systems studied to within an overall average absolute deviation of 3.4% and with a maximum deviation of 6.0%. 相似文献
36.
A computational study of hydration, solution structure, and dynamics in dilute carbohydrate solutions 总被引:1,自引:0,他引:1
We report results from a molecular simulation study of the structure and dynamics of water near single carbohydrate molecules (glucose, trehalose, and sucrose) at 0 and 30 degrees C. The presence of a carbohydrate molecule has a number of significant effects on the microscopic water structure and dynamics. All three carbohydrates disrupt the tetrahedral arrangement of proximal water molecules and restrict their translational and rotational mobility. These destructuring effects and slow dynamics are the result of steric constraints imposed by the carbohydrate molecule and of the ability of a carbohydrate to form stable H bonds with water, respectively. The carbohydrates induce a pronounced decoupling between translational and rotational motions of proximal water molecules. 相似文献
37.
de Oliveira MC Scarpellini M Neves A Terenzi H Bortoluzzi AJ Szpoganics B Greatti A Mangrich AS de Souza EM Fernandez PM Soares MR 《Inorganic chemistry》2005,44(4):921-929
The crystal structures and redox and UV-vis/EPR spectroscopic properties of two new mononuclear copper(II) complexes, [Cu(HL1)Cl2] (1) and [Cu(L1)Cl] (2), prepared through the reaction between copper(II) chloride and the ligand 2-[(bis(pyridylmethyl)amino)methyl]-4-methyl-6-formylphenol (HL1) under distinct base conditions, are reported along with solution studies. Also, we demonstrate that these CuII complexes are able to cleave unactivated peptide bonds from bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active Cu(II) complexes described to date, since their cleavage activity is detected in minutes and evidence is here presented for a hydrolytic mechanism mediating protein cleavage by these complexes. 相似文献
38.
Vicente J González-Herrero P Pérez-Cadenas M Jones PG Bautista D 《Inorganic chemistry》2005,44(20):7200-7213
Platinum(II) complexes with (fluoren-9-ylidene)methanedithiolato and its 2,7-di-tert-butyl- and 2,7-dimethoxy-substituted analogues were obtained by reacting different chloroplatinum(II) precursors with the piperidinium dithioates (pipH)[(2,7-R2C12H6)CHCS2] [R = H (1a), t-Bu (1b), or OMe (1c)] in the presence of piperidine. The anionic complexes Q2[Pt{S(2)C=C(C12H6R(2)-2,7)}2] [R = H, (Pr(4)N)(2)2a; R = t-Bu, (Pr4N)(2)2b, (Et4N)(2)2b; R = OMe, (Pr4N)(2)2c] were prepared from PtCl(2), piperidine, the corresponding QCl salt, and 1a-c in molar ratio 1:2:2:2. In the absence of QCl, the complexes (pipH)(2)2b and [Pt(pip)(4)]2b were isolated depending on the PtCl(2):pip molar ratio. The neutral complexes [Pt{S2C=C(C12H6R(2)-2,7)L(2)] [L = PPh(3), R = H (3a), t-Bu (3b), OMe (3c); L = PEt(3), R = H (4a), t-Bu (4b), OMe (4c); L(2) = dbbpy, R = H (5a), t-Bu (5b), OMe (5c) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridyl)] were similarly prepared from the corresponding precursors [PtCl2L2] and 1a-c in the presence of piperidine. Oxidation of Q(2)2b with [FeCp2]PF6 afforded the mixed Pt(II)-Pt(IV) complex Q2[Pt2{S2C=C[C12H6(t-Bu)(2)-2,7]}4] (Q(2)6, Q = Et4N+, Pr4N+). The protonation of (Pr4N)(2)2b with 2 equiv of triflic acid gave the neutral dithioato complex [Pt2{S2CCH[C12H6(t-Bu)(2)-2,7]}4] (7). The same reaction in 1:1 molar ratio gave the mixed dithiolato/dithioato complex Pr4N[Pt{S2C=C[C12H6(t-Bu)(2)-2,7]}{S2CCH[C12H6(t-Bu)(2)-2,7]}] (Pr(4)N8) while the corresponding DMANH+ salt was obtained by treating 7 with 2 equiv of 1,8-bis(dimethylamino)naphthalene (DMAN). The crystal structures of 3b and 5c.CH2Cl2 have been solved by X-ray crystallography. All the platinum complexes are photoluminescent at 77 K in CH2Cl2 or KBr matrix, except for Q(2)6. Compounds 5a-c and Q8 show room-temperature luminescence in fluid solution. The electronic absorption and emission spectra of the dithiolato complexes reveal charge-transfer absorption and emission energies which are significantly lower than those of analogous platinum complexes with previously described 1,1-ethylenedithiolato ligands and in most cases compare well to those of 1,2-dithiolene complexes. 相似文献
39.
Pablo Albores Zulema D. Chaia Luis Baraldo Eduardo E. Castellano Oscar E. Piro 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m235-m236
The octahedral title compound, [Ru(C2H5O)(NO)(NO2)2(C6H16N2)], crystallizes in the rhombohedral space group P31 with an ethoxy ligand axially coordinated trans to the nitrosyl ligand. The RuII ion is equatorially coordinated by a tetramethylethylenediamine group acting as a bidentate ligand, and to two nitro moieties whose planes are tilted with respect to the mean equatorial plane. Each nitrogen ligand bonded to the metallic centre has a different hybridization state. 相似文献
40.
Salgado-Petinal C Lamas JP Garcia-Jares C Llompart M Cela R 《Analytical and bioanalytical chemistry》2005,382(6):1351-1359
In this paper a solid-phase microextraction–gas chromatography–mass spectrometry (SPME–GC–MS) method is proposed for a rapid analysis of some frequently prescribed selective serotonin re-uptake inhibitors (SSRI)—venlafaxine, fluvoxamine, mirtazapine, fluoxetine, citalopram, and sertraline—in urine samples. The SPME-based method enables simultaneous determination of the target SSRI after simple in-situ derivatization of some of the target compounds. Calibration curves in water and in urine were validated and statistically compared. This revealed the absence of matrix effect and, in consequence, the possibility of quantifying SSRI in urine samples by external water calibration. Intra-day and inter-day precision was satisfactory for all the target compounds (relative standard deviation, RSD, <14%) and the detection limits achieved were <0.4 ng mL–1 urine. The time required for the SPME step and for GC analysis (30 min each) enables high throughput. The method was applied to real urine samples from different patients being treated with some of these pharmaceuticals. Some SSRI metabolites were also detected and tentatively identified. 相似文献