全文获取类型
收费全文 | 855篇 |
免费 | 26篇 |
国内免费 | 11篇 |
专业分类
化学 | 601篇 |
晶体学 | 3篇 |
力学 | 19篇 |
数学 | 149篇 |
物理学 | 120篇 |
出版年
2023年 | 4篇 |
2022年 | 28篇 |
2021年 | 25篇 |
2020年 | 19篇 |
2019年 | 26篇 |
2018年 | 12篇 |
2017年 | 21篇 |
2016年 | 29篇 |
2015年 | 16篇 |
2014年 | 31篇 |
2013年 | 65篇 |
2012年 | 47篇 |
2011年 | 71篇 |
2010年 | 45篇 |
2009年 | 32篇 |
2008年 | 53篇 |
2007年 | 50篇 |
2006年 | 49篇 |
2005年 | 36篇 |
2004年 | 32篇 |
2003年 | 35篇 |
2002年 | 28篇 |
2001年 | 13篇 |
2000年 | 15篇 |
1999年 | 18篇 |
1998年 | 9篇 |
1997年 | 8篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 9篇 |
1993年 | 3篇 |
1992年 | 9篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1984年 | 1篇 |
1982年 | 6篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 2篇 |
1970年 | 1篇 |
1966年 | 2篇 |
1965年 | 1篇 |
1937年 | 2篇 |
1931年 | 1篇 |
排序方式: 共有892条查询结果,搜索用时 15 毫秒
71.
The aim of this work was to study the possibility of simultaneous voltammetric determination of some disinfectants used as components in cosmetic products. The examined compounds were: triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol), chloramine-T (N-chloro-p-toluenesulfonamide sodium salt), 4-chloro-3-methylphenol and 2-mercaptobenzothiazole. Measurements were performed using glassy carbon electrode immersed in Britton-Robinson buffers which acted as supporting electrolytes. The dependence of oxidation and reduction potentials on pH was examined using cyclic voltammetry. Britton-Robinson buffer of pH 9.9 was chosen for further studies to ensure the best separation of compounds. The resultant oxidation potentials indicate the possibility to simultaneously determine some of the disinfectants.. Oxidation reactions of mixtures containing two compounds (4-chloro-3-methylphenol and chloramine-T, 2-mercaptobenzothiazole and 4-chloro-3-methylphenol, 2-mercaptobenzothiazole and triclosan) were recorded as differential pulse voltammograms. 相似文献
72.
Myjavcová R Marhol P Křen V Simánek V Ulrichová J Palíková I Papoušková B Lemr K Bednář P 《Journal of chromatography. A》2010,1217(51):7932-7941
Anthocyanins from the fruit Lonicera caerulea L. var. kamtschatica (blueberry honeysuckle, Caprifoliaceae) were studied via (semi)preparative chromatographic fractionation followed by MS and μLC/MS analysis. The extraction procedure was optimized with respect to analytical purposes as well as its potential use for the preparation of nutraceuticals. The highest yield of anthocyanins was obtained using acidified methanol as the extraction medium. A comparable total anthocyanin content was obtained using a mixture of methanol and acetone. However, when Lonicera anthocyanins were in contact with acetone, a condensation reaction occurred to a large extent and related 5-methylpyranoanthocyanins were found. The effect of other extraction media, including ethanol as a "green" solvent, is also discussed. The potential of two fractionation procedures for extract purification differing in their chromatographic selectivity and scale was studied (i.e. using a Sephadex LH-20 gel column and a reversed phase). Fractions obtained by both procedures were used for a detailed analysis. MS and μLC/MS(2) methods were used for monitoring anthocyanin and 5-methylpyranoderivatives content as well as identifying less common and more complex dyes (dimer of cyanidin-3-hexoside, cyanidin-ethyl-catechin-hexosides, etc.). These more complex dyes are most likely formed during fruit treatment. 相似文献
73.
Irena Pankratov Sara Elhanany Sharona Henig Shunit Zaritsky Ivan Ostapenko Ilya Kuselman 《Accreditation and quality assurance》2010,15(8):459-466
A proficiency testing (PT) scheme was developed for a limited number of analytical laboratories participating in the analysis
of natural water in Israel. Three fit-for-intended-use reference materials (RMs) were prepared for a pilot PT from natural
water: RM-blank and two in-house reference materials (IHRMs) with seven analytes fortified to achieve different levels of
analyte concentrations. The measurands for the PT participants were the traceable spike values certified in the IHRMs, i.e.,
added mass concentrations of the analytes. The RM-blank and IHRMs were found to be homogeneous and stable over 11 days, the
time necessary for the experimental part of the PT. The RMs were distributed to the PT participants as unknown test items
similar to routine samples. The test results were evaluated using their deviations from the IHRM-certified values. Eight Israeli
laboratories took part in the interlaboratory comparison. Individual laboratory performance and metrological compatibility
of the PT results of the participants, as a local group of laboratories, were evaluated for every analyte. 相似文献
74.
We study the temperature dependence of the radiative deactivation of triplet states of Pdand Pt-porphin molecules in n-alkane matrices in the temperature range 4.2–210 K. The nature of the thermally activated “hot” lines that are observed in
phosphorescence spectra of Pdand Pt-porphin is discussed in detail. We show that, because of the degeneracy lifting of the
triplet state T
1, 2 in the crystal field of n-alkane matrices, lines of the transitions T1 → S
0 and T
2 → S
0 are spectrally spaced and, in all cases, the T
2 state is the first state that is activated with increasing temperature. We analyze the dependences of the T
2-T
1 splitting on the chelated metal ion and the type of the matrix. The possibility of measuring cryogenic temperatures with
molecular thermometers that use the thermochromic properties of Pdand Pt-porphin in n-alkane matrices is discussed. 相似文献
75.
The influence of alcohol additives on etch rate anisotropy of Si(hkl) planes has been studied. The etching processes were carried out in 3 and 5 M KOH aqueous solutions saturated and non-saturated
with alcohols. Isopropanol, 1-propanol and tert-butanol were examined. It has been showed that the etching process cannot be controlled only by the surface tension of the
solution. Saturation of the etching solution with alcohols modifies etch rate anisotropy, lowering the ratio of the etch rate
of (110) and vicinal planes to the etch rate of (100) plane. The morphology of Si(hkl) planes etched in 3 M KOH solution saturated with tert-butyl alcohol has been studied in detail. Smooth (331) and (221) planes
have been achieved in this solution. The (100) plane turned out to be densely covered by hillocks, opposite to the (100) plane
etched in weak-alkaline solution saturated with isopropanol. To explain this phenomenon, the mechanism of hillocks formation
on Si(100) surface has been proposed. 相似文献
76.
The influence of fluorination of microcrystalline γ-alumina on the acidity of Lewis sites was studied by quantum chemical cluster model approach. B3LYP and HF/6-31++G(d,p) levels of theory were employed, considering the standard and counterpoise-corrected potential energy surfaces (PESs). Explicit inclusion of dynamical electron correlation effects along with the elimination of the basis set superposition effects in geometry optimization and harmonic vibrational analysis were found to be crucial to reproduce the experimental trends in the shifts of the pyridine ν19b and ν8a modes upon fluorination. The acidity of surface-exposed Al-sites was found to increase upon fluorination, which is manifested as a ~ 10% increase of the interaction energies, and also in the characteristics of the electronic density and density Laplacian at the intermolecular bond critical point. Bader analysis of the electronic density has shown that pyridine adsorption on pure and fluorinated γ-alumina can be classified as non-covalent interaction. 相似文献
77.
Irena Akhrem Dzhul’etta Avetisyan Lyudmila Afanas’eva Nikolai Kagramanov Pavel Petrovskii Alexander Orlinkov 《Tetrahedron letters》2010,51(6):907-911
A novel ‘alkane-like’ methodology for the direct and very simple one-pot functionalization of amides and an ester of 1-adamantanecarboxylic acid provides access to new and synthetically challenging 1,3-dicarbonyl-containing adamantanoid compounds with the same or different functional groups. 相似文献
78.
Janusz Zachara Izabela D. Madura Andrzej Zimniak Irena Oszczapowicz Iwona Chrobak 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(11):o625-o627
The structural analysis of deacetylcephalothin [systematic name: (6R,7R)‐3‐hydroxymethyl‐8‐oxo‐7‐(2‐thiophen‐2‐ylacetylamino)‐5‐thia‐1‐azabicyclo[4.2.0]oct‐2‐ene‐2‐carboxylic acid], C14H14N2O5S2, shows that the geometry of the central bicyclic moiety is close to the geometry exhibited by other biologically active cephalosporin antibiotics. The molecules are arranged in a helical chain running parallel to the 21 axis via a strong O—H⋯O hydrogen bond. The main helices are zipped together via N—H⋯O interactions, forming infinite layers. The supramolecular architecture is stabilized by O—H⋯S and C—H⋯O hydrogen bonds. 相似文献
79.
We prove that Gotzmann's Persistence Theorem holds over every Clements–Lindström ring. We also construct the infinite minimal free resolution of a square-free Borel ideal over such a ring. 相似文献
80.
Irena Lasiecka 《Applied Mathematics and Optimization》1990,21(1):167-189
We consider the question of strong stability of solutions to plate equations with nonlinear dissipation in the boundary conditions. Two cases are discussed: (1) dissipation occurring through the nonlinear forces applied on the boundary and (2) dissipation acting through the nonlinear moments. Asymptotic stability results are presented for both cases. In the first case the results are established under the natural geometric conditions imposed on the domain, while in the second case certain restrictions on the curvature on the active portion of the boundary are required.Research partially supported by NSF Grant DMS-8301668 and by AFOSR Grant AFOSR-84-0365. 相似文献