全文获取类型
收费全文 | 10077篇 |
免费 | 177篇 |
国内免费 | 39篇 |
专业分类
化学 | 5750篇 |
晶体学 | 85篇 |
力学 | 355篇 |
数学 | 1648篇 |
物理学 | 2455篇 |
出版年
2021年 | 111篇 |
2020年 | 123篇 |
2019年 | 127篇 |
2018年 | 118篇 |
2017年 | 102篇 |
2016年 | 179篇 |
2015年 | 159篇 |
2014年 | 165篇 |
2013年 | 571篇 |
2012年 | 355篇 |
2011年 | 441篇 |
2010年 | 321篇 |
2009年 | 274篇 |
2008年 | 400篇 |
2007年 | 359篇 |
2006年 | 348篇 |
2005年 | 318篇 |
2004年 | 336篇 |
2003年 | 273篇 |
2002年 | 273篇 |
2001年 | 189篇 |
2000年 | 180篇 |
1999年 | 144篇 |
1998年 | 114篇 |
1997年 | 132篇 |
1996年 | 164篇 |
1995年 | 120篇 |
1994年 | 123篇 |
1993年 | 153篇 |
1992年 | 156篇 |
1991年 | 158篇 |
1990年 | 118篇 |
1989年 | 119篇 |
1988年 | 131篇 |
1987年 | 180篇 |
1986年 | 148篇 |
1985年 | 196篇 |
1984年 | 185篇 |
1983年 | 144篇 |
1982年 | 166篇 |
1981年 | 176篇 |
1980年 | 172篇 |
1979年 | 170篇 |
1978年 | 164篇 |
1977年 | 163篇 |
1976年 | 141篇 |
1975年 | 158篇 |
1974年 | 126篇 |
1973年 | 123篇 |
1972年 | 75篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
211.
Lenaerts J Van Vaeck L Gijbels R Van Luppen J 《Rapid communications in mass spectrometry : RCM》2004,18(3):257-264
Organic carbocyanine dye coatings have been analyzed by time-of-flight static secondary ion mass spectrometry (TOF-S-SIMS) using three types of primary ions: Ga(+) operating at 25 keV, and Xe(+) and SF(5) (+) both operating at 9 keV. Secondary ion yields obtained with these three primary ions have been compared for coatings with different layer thickness, varying from (sub)-monolayer to multilayers, on different substrates (Si, Ag and AgBr cubic microcrystals). For (sub)-monolayers deposited on Ag, Xe(+) and SF(5) (+) primary ions generate similar precursor ion intensities, but with Ga(+) slightly lower precursor ion intensities were obtained. Thick coatings on Ag as well as mono- and multilayers on Si produce the highest precursor and fragment ion intensities with the polyatomic primary ion. The yield difference between SF(5) (+) and Xe(+) can reach a factor of 6. In comparison with Ga(+), yield enhancements by up to a factor of 180 are observed with SF(5) (+). For the mass spectrometric analysis of dye layers on AgBr microcrystals, SF(5) (+) again proves to be the primary ion of choice. 相似文献
212.
Selection of reversed-phase liquid chromatographic columns with diverse selectivity towards the potential separation of impurities in drugs 总被引:1,自引:0,他引:1
Van Gyseghem E Jimidar M Sneyers R Redlich D Verhoeven E Massart DL Vander Heyden Y 《Journal of chromatography. A》2004,1042(1-2):69-80
To select appropriate stationary phases from the continuously expanding supply of potentially suitable HPLC columns, the properties of 28 frequently applied stationary phases were determined by measuring several chromatographic parameters. From these results, based on chromatographic expertise, eight stationary phases with different properties and selectivities were selected. The aim of this study is to apply chemometric tools to evaluate the initially selected set of columns, i.e. a more systematic approach for making such a selection is examined. Starting from the information obtained on the 28 stationary phases, the re-evaluation was performed independently based on the chemometric techniques Pareto-optimality, principal component analysis (PCA), and Derringer's desirability functions. The aim was to select a set of efficient columns exhibiting large selectivity differences. The chemometrically selected stationary phases were divided in groups based on hydrophobicity, a critical retention-determining property in reversed-phase chromatography. This allowed to further reducing the selection to three columns. It is demonstrated that the selection by the chemometric approaches in general is fairly comparable with the initial selection. 相似文献
213.
J.C.M. De Wit W.H. Van Riemsdijk M.M. Nederlof D.G. Kinniburgh L.K. Koopal 《Analytica chimica acta》1990
Humic substances are characterized by a variable electric potential and by a variety of binding sites leading to chemical heterogeneity. Binding of ions to these substances is influenced by both factors. A methodology based on acid—base titrations at several salt levels is presented that allows for the assessment of an appropriate electrostatic double-layer model and the intrinsic proton affinity distribution. The double-layer model is used for the conversion of pH to pHS for each data point, where HS is the proton concentration in the diffuse layer near the binding site. It is shown that with an appropriate double-layer model the proton binding curves at different salt levels converge into one “master curve” when plotted as a function of pHS. The intrinsic proton affinity distribution can then be derived from the “master curve” using the LOGA method. A rigorous analysis of metal binding to humic substances is complex and in practice is not feasible. Under two different (simplifying) assumptions, namely fully coupled and uncoupled binding, it is shown how intrinsic metal ion affinity distributions can be obtained. Model calculations show that apparent metal ion affinity distributions do not resemble the intrinsic metal ion affinity distribution. 相似文献
214.
215.
Cooper TJ Talaty ER Van Stipdonk MJ 《Journal of the American Society for Mass Spectrometry》2005,16(8):1305-1310
We report a new fragmentation pathway for the CID of (b3 - 1 + Cat)+ product ions derived from the model peptide AXAG, where X = beta-alanine, gamma-aminobutyric acid, epsilon-amino-n-caproic acid, or 4-aminomethylbenzoic acid. By changing the amino acid to the C-terminal side of the amino acid X, and incorporating 15N and 13C labeled residues at the same position, we conclude that the dissociation pathway most likely leads to a metal cationized nitrile. With respect to the various amino acids at position X, the putative nitrile product becomes more prominent, relative to the conventional (a3 - 1 + Cat)+ species, in the order beta-alanine < gamma-aminobutyric acid < epsilon-aminocaproic acid < 4-aminomethylbenzoic acid. The pathway is not observed for peptides with alpha-amino acids at position X. The product ion is observed most prominently during the CID of Li+ and Na+ cationized peptides, only to a small extent for Ag+ cationized peptides, and not at all from protonated analogues. 相似文献
216.
The Commission Decision of August 12, 2002 on the performance of analytical methods and the interpretation of results was applied to the HPLC method for the analysis of parabens, 2-phenoxyethanol and 1-phenoxypropan-2-ol in cosmetic products. This method is published in the seventh Directive 96/45/EC of the European Commission. Non-compliant concentrations, taking into account the data distribution (CC) and the probability of false negative values (CC) were determined. The repeatability and reproducibility amount to <4% and <7%, respectively. These values were obtained with blanc samples that were fortified in the laboratory. Calibration linearity was confirmed by absence of lack of fit for all seven preservatives. Matrix effects on the determinations of the preservatives in body milk or shampoo are negligible. 相似文献
217.
Bose G Nguyen VT Ullah E Lahiri S Görls H Langer P 《The Journal of organic chemistry》2004,69(26):9128-9134
The Lewis acid mediated domino "[3+3]-cyclization-homo-Michael" reaction of 1,3-bissilyl enol ethers with 1,1-diacylcyclopropanes allows an efficient one-pot synthesis of functionalized salicylates containing a halogenated side chain. A great variety of substitution patterns could be realized by variation of the starting materials and of the Lewis acid. The mechanism of the domino process was studied. 相似文献
218.
Cocquyt J Olsson U Olofsson G Van der Meeren P 《Langmuir : the ACS journal of surfaces and colloids》2004,20(10):3906-3912
Dilute dispersions of the synthetic bilayer forming double-chained cationic lipid dioctadecyldimethylammonium bromide (DODAB) were investigated. In dispersions sonicated above the chain melting temperature Tm (approximately 45 degrees C) it was found by H NMR that about 50% of the surfactant chains remained fluid when the samples were cooled to room temperature, which is 20 degrees C below Tm. In contrast, there was no sign of a fluid fraction in unsonicated samples at room temperature. The addition of the anionic surfactant sodium dodecyl sulfate (SDS) to DODAB dispersions at room temperature resulted in the formation of an essentially stoichiometric DODA-DS complex with frozen chains, as seen by titration calorimetry and H NMR experiments. For sonicated samples, turbidity experiments demonstrated that, after a fast complexation reaction, the system remains colloidally stable unless the SDS-to-DODAB mixing ratio is too close to unity. H NMR experiments also showed that in the unreacted DODAB the fraction of fluid chains remained close to 50%, indicating either that SDS reacts equally fast with fluid and frozen DODAB or that there is a relaxation of the fluid fraction after the complexation. The melting enthalpy and the melting temperature of the alkyl chains rise gradually as the mixing ratio increases. We observed with cryo-TEM that the fraction of large unilamellar vesicles was significantly larger after addition of SDS. This indicates vesicle fusion. Based on both wide- and small-angle X-ray scattering patterns, the structure of the equimolar SDS-DODAB complex at 25 degress C was proposed to be lamellar. 相似文献
219.
The direct reaction field (DRF ) method, developed to incorporate the effects of a (large) semiclassical environment into the Hamiltonian of a quantum mechanical system, is briefly reviewed. It is shown that the DRF method behaves—at least—like a supermolecule SCF calculation. With the water dimer as an example, the similarity with the SCF procedure is demonstrated, and an application to the interaction between the active site of papain and the remaining 3000 or so atoms of this protein shows the inadequacy of dielectric constant models and the necessity of including atomic polarizabilities in model force fields. 相似文献
220.
Various rice samples /seed, brand layer, husk/ from Vietnam were analyzed for Se, Hg, Cr, Ni, Sc, Rb, Fe, Zn and Co by neutron activation analysis. The concentration values found /seed/ were the following: Se 0.04–0.07 ppm, Hg 0.02–0.07 ppm, Cr 2.13–8.65 ppm, Ni 1.56–4.95 ppm, Sc 0.02–0.06 ppm, Rb 0.84–2.71 ppm, Fe 26.31–96.07 ppm, Zn 10.65–27.39 ppm and Co 0.02–0.15 ppm. The values were reported in ppm /dry weight/. Statistical analysis /t-test, t=0.05/ showed that the content of elements varies between sorts of rice; the content of Rb, Fe, Ni, Cr of rice husk was significantly higher than in rice seed and brand layer. 相似文献