全文获取类型
收费全文 | 1015篇 |
免费 | 75篇 |
国内免费 | 3篇 |
专业分类
化学 | 863篇 |
晶体学 | 7篇 |
力学 | 12篇 |
数学 | 100篇 |
物理学 | 111篇 |
出版年
2023年 | 9篇 |
2022年 | 13篇 |
2021年 | 21篇 |
2020年 | 22篇 |
2019年 | 13篇 |
2018年 | 17篇 |
2017年 | 11篇 |
2016年 | 42篇 |
2015年 | 35篇 |
2014年 | 41篇 |
2013年 | 41篇 |
2012年 | 76篇 |
2011年 | 89篇 |
2010年 | 41篇 |
2009年 | 51篇 |
2008年 | 83篇 |
2007年 | 79篇 |
2006年 | 93篇 |
2005年 | 78篇 |
2004年 | 54篇 |
2003年 | 33篇 |
2002年 | 33篇 |
2001年 | 18篇 |
2000年 | 15篇 |
1999年 | 8篇 |
1998年 | 13篇 |
1997年 | 11篇 |
1996年 | 7篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 1篇 |
1984年 | 3篇 |
1982年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有1093条查询结果,搜索用时 100 毫秒
11.
Blanco M Coello J Iturriaga H Maspoch S Pou N 《Fresenius' Journal of Analytical Chemistry》2000,368(5):534-539
A near infrared diffuse reflectance spectroscopy (NIRS) procedure for the quantitative control analysis of the active compound (otilonium bromide) in a pharmaceutical preparation in three steps of the production process (blended product, cores and coated tablets) and a methodology for its validation are proposed. The analytical procedure is composed by two consecutive steps. First, the sample is identified by comparing its spectrum with a second derivative spectral library. If the sample is positively identified, the active compound is quantified by using a previously established partial least squares (PLS) calibration model. The procedure was validated by studying repeatability, intermediate precision, accuracy and linearity. To this end, an adaptation of ICH (International Conference on Harmonisation) validation methodology to an NIR multivariate calibration procedure is proposed. The relative standard error of prediction (RSEP) was < or = 1% and the suitability of the procedure for control analysis was confirmed by the results obtained analysing new production samples produced over a three-month period. 相似文献
12.
New spin-state-selective (S3) NMR pulse sequences exclusively applying cross-polarization schemes to achieve optimum homonuclear and heteronuclear 1H-X coherence transfer are reported for the simple and accurate measurement of the magnitude and sign of heteronuclear coupling constants for samples at natural abundance. The proposed spin-edited HCP-TOCSY experiments are based on clean heteronuclear S3 excitation, generated by simultaneous co-addition of two independent in-phase and anti-phase components created during the mixing heteronuclear J-cross-polarization (HCP) step, which is finally transferred to other protons by a conventional homonuclear TOCSY mechanism. Selective 1D and non-selective 2D approaches for the easy determination of long-range proton-carbon and proton-nitrogen coupling constants on any protonated and non-protonated heteronuclei are presented and discussed for several organic molecules. 相似文献
13.
Elena Laukhina Vladislava Tkacheva Salavat Khasanov Leokadia Zorina Jordi Gómez-Segura Angel Pérez del Pino Jaume Veciana Vladimir Laukhin Concepció Rovira 《Chemphyschem》2006,7(4):920-923
Temperature has great impact on the structure and size of the linked crystallites of the conducting topmost layer formed at the surface of a polycarbonate film via the reaction BEDT-TTF+IBr [BEDT-TTF=bis(ethylenedithio)tetrathiafulvalene]. We show that fine temperature control permits formation of a semiconducting topmost layer of alpha'-(BEDT-TTF)(2)(I(x)Br(1-x))(3) crystallites with either micro- or nanometre size, a result that opens a route to miniaturized conducting plastic materials. 相似文献
14.
Pizarro N Llebaria A Cano S Joglar J Farré M Segura J de la Torre R 《Rapid communications in mass spectrometry : RCM》2003,17(4):330-336
3,4-Methylenedioxymethamphetamine (MDMA, ecstasy) is consumed as the racemate but some metabolic steps are enantioselective. In addition, chiral properties are preserved during MDMA biotransformation. A quantitative analytical methodology using gas chromatography/mass spectrometry (GC/MS) to determine enantioselective disposition in the body of MDMA and its main metabolites including 3,4-methylenedioxyamphetamine (MDA), 4-hydroxy-3-methoxymethamphetamine (HMMA), and 4-hydroxy-3-methoxyamphetamine (HMA) was developed. Plasma and urine samples were collected from a male volunteer. The analysis of MDMA, MDA, and 4-hydroxy-3-methoxy metabolites by GC/MS required a two-step derivatization procedure. The first step consisted of derivatization of the amine with enantiomerically pure Mosher's reagent ((R)-MTPCl). Triethylamine was used as a base to neutralize hydrochloric acid formed during the reaction allowing quantitative derivatization, which resulted in a substantial improvement in the sensitivity of the method compared with other previously described techniques. Further treatment with ammonium hydroxide was required since both amine and hydroxyl groups underwent derivatization in the reaction. Ammonium hydroxide breaks bonds formed with hydroxyl groups without affecting amine derivatives. The second derivatization step using hexamethyldisilazane was needed for metabolites containing phenol residues. This derivatization method permitted the stereochemically specific study of MDMA and its main monohydroxylated metabolites by GC/MS. A detailed study of the chemical reactions involved in the derivatization steps was indispensable to develop a straightforward, sensitive, and reproducible method for the analysis of the parent drug compound and its metabolites. 相似文献
15.
A method for the identification of double bond locations in polyunsaturated long chain alkenones adapted to nanogram amounts
as currently analyzed by gas chromatography coupled to mass spectrometry (GC-MS) has been developed. The method is based on
interpretation of the electron impact mass spectra of the imino derivatives of the carbonyl groups using either cyclopentyl
or phenyl substitutents. Other complementary derivatization methods such as elaidization and hydrogenation have also been
used for structural characterization of these compounds. This application has led to the identification of a novel homologous
series of di-, tri-, and tetraunsaturated ketones with carbon number chain lengths between 37 and 40 in coastal hypersaline
sediments. The novel series identified shows a distribution in which the double bond position between different homologs is
established by reference to the distance from the carbonyl group whereas the previously known alkenones were constituted by
unsaturated homologs with double bonds located at defined distances of the terminal methyl. This difference points out to
a dissimilar, but still unknown, biogenic precursor of these novel alkenones. 相似文献
16.
In this paper we propose a method for carrying out variational transition state theory calculations without first obtaining
a converged minimum-energy path (MEP). We illustrate the method in two ways, first of all by employing an unconverged MEP
and secondly by using a dynamically optimized distinguished reaction path. Preliminary tests of the algorithm for the reactions
OH+H2→H2O+H and C2H5→C2H4+H are very encouraging.
Received: 22 January 1997 / Accepted: 11 March 1997 相似文献
17.
M. Blanco J. Coello H. Iturriaga S. Maspoch E. Bertrán 《Fresenius' Journal of Analytical Chemistry》1991,340(7):410-414
Summary A procedure for the simultaneous spectrophotometric determination of organic additives and the quantitation of Ni(II) in Zn-Ni electrolytic baths is described. Organic additives were determined by resolving the mixed spectrum over the wavelength range 278–330 nm by applying a least-squares fitting computational program to the standard spectrum of each component. Spectra were recorded on a hydroalcoholic medium (15% methanol) containing 0.1 mol/l NH4Cl. The Ni(II) concentration was determined by applying the program to the first-derivative spectrum over the wavelength range 660–820 nm. 相似文献
18.
Ignés-Mullol J Claret J Albalat R Crusats J Reigada R Romero MT Sagués F 《Langmuir : the ACS journal of surfaces and colloids》2005,21(7):2948-2955
Preparation of Langmuir monolayers of a mixture of trans- and cis-isomers of an azobenzene derivative, 4-[4-[(4-octylphenyl)azo]phenoxy]butanoic acid, results in the segregation of birefringent trans-isomer domains embedded in an isotropic medium of cis-isomers. Brewster angle microscopy observations allow us to identify different textures inside the domains depending on surface pressure, temperature, and domain size. The evolution of the monolayer in the dark, from initial droplets formed after spreading to a stable stripe texture, is described. The dynamics of domain coalescence and some morphological transitions induced by temperature and surface pressure changes are also discussed. A simple theoretical model is included to supplement some of these experimental observations. 相似文献
19.
Martí M Barsukov LI Fonollosa J Parra JL Sukhanov SV Coderch L 《Langmuir : the ACS journal of surfaces and colloids》2004,20(8):3068-3073
Despite the promising application of liposomes in wool dyeing, little is known about the mechanism of liposome interactions with the wool fiber and dyestuffs. The kinetics of wool dyeing by two dyes, Acid Green 27 (hydrophobic) and Acid Green 25 (hydrophilic), were compared in three experimental protocols: (1) without liposomes, (2) in the presence of phosphatidylcholine (PC) liposomes, and (3) with wool previously treated with PC liposomes. Physicochemical interactions of liposomes with wool fibers were studied under experimental dyeing conditions with particular interest in the liposome affinity to the fiber surface and changes in the lipid composition of the wool fibers. The results obtained indicate that the presence of liposomes favors the retention of these two dyes in the dyeing bath, this effect being more pronounced in case of the hydrophobic dye. Furthermore, the liposome treatment is accompanied by substantial absorption of PC by wool fibers with simultaneous partial solubilization of their polar lipids (more evident at higher temperatures). This may result in structural modification of the cell membrane complex of wool fibers, which could account for a high level of the dye exhaustion observed at the end of the liposome dyeing process. 相似文献
20.
The reaction of several α-amino acids and peptides (containing Gly, L-Ala, L-Leu, L- or DL-Phe, and/or L- or D-Val) with air-diluted nitrogen oxides has been studied to roughly mimic the N-nitrosation of peptide bonds that the contaminated urban air might produce in pulmonary tissues. Most N-protected α-amino acids give practically quantitative yields of N-nitroso derivatives. N-Protected dipeptides afford either dinitrosated peptides, mixtures of di- and mononitrosated compounds, selectively mononitrosated products, or no reaction at all, depending mainly on steric effects. The same trends are observed for some higher peptides. The (po1y)nitrosated Peptides, which retain the chirality of the starting materials, have been characterized by 1H and 13C NMR spectroscopy and are cleaved by pyrrolidine and amino esters under mild conditions to give (new) amides or peptides plus diazo derivatives. 相似文献