全文获取类型
收费全文 | 9058篇 |
免费 | 361篇 |
国内免费 | 20篇 |
专业分类
化学 | 6152篇 |
晶体学 | 68篇 |
力学 | 342篇 |
数学 | 1373篇 |
物理学 | 1504篇 |
出版年
2023年 | 51篇 |
2022年 | 67篇 |
2021年 | 122篇 |
2020年 | 159篇 |
2019年 | 161篇 |
2018年 | 183篇 |
2017年 | 147篇 |
2016年 | 310篇 |
2015年 | 247篇 |
2014年 | 276篇 |
2013年 | 576篇 |
2012年 | 580篇 |
2011年 | 656篇 |
2010年 | 349篇 |
2009年 | 333篇 |
2008年 | 578篇 |
2007年 | 609篇 |
2006年 | 545篇 |
2005年 | 530篇 |
2004年 | 405篇 |
2003年 | 372篇 |
2002年 | 292篇 |
2001年 | 146篇 |
2000年 | 133篇 |
1999年 | 121篇 |
1998年 | 92篇 |
1997年 | 71篇 |
1996年 | 114篇 |
1995年 | 97篇 |
1994年 | 85篇 |
1993年 | 75篇 |
1992年 | 66篇 |
1991年 | 48篇 |
1990年 | 48篇 |
1989年 | 46篇 |
1988年 | 29篇 |
1987年 | 32篇 |
1985年 | 61篇 |
1984年 | 44篇 |
1983年 | 32篇 |
1982年 | 53篇 |
1981年 | 44篇 |
1980年 | 55篇 |
1979年 | 41篇 |
1978年 | 42篇 |
1977年 | 37篇 |
1976年 | 47篇 |
1975年 | 47篇 |
1974年 | 30篇 |
1973年 | 29篇 |
排序方式: 共有9439条查询结果,搜索用时 78 毫秒
961.
The determination of six phthalate acid esters was achieved in artificial saliva using gas chromatography-mass spectrometry following activated carbon enrichment of samples. Central composite experimental design was applied to optimize method parameters, such as pH, adsorption time and amount of activated carbon. The best compromise of analytical conditions for the simultaneous determination of analytes from spiked artificial saliva were found to be: pH (3), adsorption time (30 min), activated carbon amount (1.8 g L−1) and elution solvent (chloroform). These conditions were applied to study the migration of phthalate acid esters from different children's toys into saliva. A horizontal agitation method was applied to extract the analytes from plastic toys into saliva for 2 h at 37 °C. The detection limits of the method were in the range of 1.3-5.1 μg L−1, while the relative standard deviation (%) values for the analysis of 100 μg L−1 of the analytes were below 3.0% (n = 5). Di-2-ethylhexyl phthalate was the main analyte found in these samples. 相似文献
962.
The validation of a microbiological assay applying the cylinder-plate method to determine the quinolone gemifloxacin mesylate (GFM) content is described. Using a strain of Staphylococcus epidermidis ATCC 12228 as the test organism, the GFM content in tablets at concentrations ranging from 0.5 to 4.5 μg mL−1 could be determined. A standard curve was obtained by plotting three values derived from the diameters of the growth inhibition zone. A prospective validation showed that the method developed is linear (r = 0.9966), precise (repeatability and intermediate precision), accurate (100.63%), specific and robust. GFM solutions (from the drug product) exposed to direct UVA radiation (352 nm), alkaline hydrolysis, acid hydrolysis, thermal stress, hydrogen peroxide causing oxidation, and a synthetic impurity were used to evaluate the specificity of the bioassay. The bioassay and the previously validated high performance liquid chromatographic (HPLC) method were compared using Student's t test, which indicated that there was no statistically significant difference between these two validated methods. These studies demonstrate the validity of the proposed bioassay, which allows reliable quantification of GFM in tablets and can be used as a useful alternative methodology for GFM analysis in stability studies and routine quality control. The GFM reference standard (RS), photodegraded GFM RS, and synthetic impurity samples were also studied in order to determine the preliminary in vitro cytotoxicity to peripheral blood mononuclear cells. The results indicated that the GFM RS and photodegraded GFM RS were potentially more cytotoxic than the synthetic impurity under the conditions of analysis applied. 相似文献
963.
Tremoy G Vimeux F Cattani O Mayaki S Souley I Favreau G 《Rapid communications in mass spectrometry : RCM》2011,25(23):3469-3480
The new infrared laser spectroscopic techniques enable us to measure the isotopic composition (δ(18)O and δ(2)H) of atmospheric water vapor. With the objective of monitoring the isotopic composition of tropical water vapor (West Africa, South America), and to discuss deuterium excess variability (d=δ(2)H - 8δ(18)O) with an accuracy similar to measurements arising from isotope-ratio mass spectrometry (IRMS), we have conducted a number of tests and calibrations using a wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) technique. We focus in this paper on four main aspects regarding (1) the tubing material, (2) the humidity calibration of the instrument, (3) the water vapor concentration effects on δ, and (4) the isotopic calibration of the instrument. First, we show that Synflex tubing strongly affects δ(2)H measurements and thus leads to unusable d values. Second, we show that the mixing ratio as measured by WS-CRDS has to be calibrated versus atmospheric mixing ratio measurements and we also suggest possible non-linear effects over the whole mixing ratio range (~2 to 20 g/kg). Third, we show that significant non-linear effects are induced by water vapor concentration variations on δ measurements, especially for mixing ratios lower than ~5 g/kg. This effect induces a 5 to 10‰ error in deuterium excess and is instrument-dependent. Finally, we show that an isotopic calibration (comparison between measured and true values of isotopic water standards) is needed to avoid errors on deuterium excess that can attain ~10‰. 相似文献
964.
Auneau F Michel C Delbecq F Pinel C Sautet P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(50):14288-14299
We report herein a detailed and accurate study of the mechanism of rhodium-catalysed conversion of glycerol into 1,2-propanediol and lactic acid. The first step of the reaction is particularly debated, as it can be either dehydration or dehydrogenation. It is expected that these elementary reactions can be influenced by pH variations and by the nature of the gas phase. These parameters were consequently investigated experimentally. On the other hand, there was a lack of knowledge about the behaviour of glycerol at the surface of the metallic catalyst. A theoretical approach on a model Rh(111) surface was thus implemented in the framework of density functional theory (DFT) to describe the above-mentioned elementary reactions and to calculate the corresponding transition states. The combination of experiment and theory shows that the dehydrogenation into glyceraldehyde is the first step for the glycerol transformation on the Rh/C catalyst in basic media under He or H(2) atmosphere. 相似文献
965.
966.
Gerber I Oubenali M Bacsa R Durand J Gonçalves A Pereira MF Jolibois F Perrin L Poteau R Serp P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(41):11467-11477
The nitric acid oxidation of multiwalled carbon nanotubes leading to surface carboxylic groups has been investigated both experimentally and theoretically. The experimental results show that such a reaction involves the initial rapid formation of carbonyl groups, which are then transformed into phenol or carboxylic groups. At room temperature, this reaction takes place on the most reactive carbon atoms. At higher temperatures a different mechanism would operate, as evidenced by the difference in activation energies. Experimental data can be partially related to first-principles calculations, showing a multistep functionalization mechanism. The theoretical aspects of the present article have led us to propose the most efficient pathway leading to carboxylic acid functional groups on the surface. Starting from mono-vacancies, it ends up with the synergistic formation of dangling -COOH groups and the enlargement of the vacancies. 相似文献
967.
Donati L Leproux P Prost E Michel S Tillequin F Gandon V Porée FH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(45):12809-12819
The domino reaction of o-bromobenzamides 1a-m in the presence of K(2)CO(3) and the [PdCl(2)(PPh(3))(2)] catalyst granted a selective access to phenanthridinones 2 or to the new 1-carboxamide phenanthridinones 3 depending on the solvent, DMF or 1,4-dioxane, respectively. Investigations of the reaction parameters provided the first example of a direct correlation between the base dissociation and the solvent polarity on the selectivity observed. Moreover, mechanistic studies (NMR spectroscopy and ESI-MS monitoring) allowed us to characterize Pd(II) palladacycle 4 and biaryl species as common intermediates for these two domino processes. On that basis, C(sp(2))-C(sp(2)) bond formation is envisaged by generation of a Pd(IV) complex after oxidative addition of 1 into Pd(II) palladacycle 4, a rationale that is supported by DFT calculations. A general catalytic cycle is proposed to account for these observations. 相似文献
968.
Cecioni S Oerthel V Iehl J Holler M Goyard D Praly JP Imberty A Nierengarten JF Vidal S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(11):3252-3261
Multivalency is playing a major role in biological processes and particularly in lectin-carbohydrate interactions. The design of high-affinity ligands of lectins should provide molecules capable of interfering with these biological processes and potentially inhibit bacterial or viral infections. Azide-alkyne "click" chemistry was applied to the synthesis of dodecavalent fullerene-based glycoclusters. The conjugation could be efficiently performed from alkyne or azide functions on either partners (i.e. hexakis-fullerene adduct or glycoside). PA-IL is a bacterial lectin from the opportunistic pathogen Pseudomonas aeruginosa and is involved in the recognition of glycoconjugates on human tissues. The glycoclusters obtained were evaluated as ligands of PA-IL and for their potential for competing with its binding to glycosylated surfaces. The affinities measured by hemagglutination inhibition assay (HIA), enzyme-linked lectin assay (ELLA), and surface plasmon resonance (SPR) displayed a significant "glycoside cluster effect" with up to a 12,000-fold increase in binding when comparing a monovalent carbohydrate reference probe with a dodecavalent fullerene-based glycocluster, albeit with some differences depending on the analytical technique. 相似文献
969.
A new variable selection algorithm is described, based on ant colony optimization (ACO). The algorithm aim is to choose, from a large number of available spectral wavelengths, those relevant to the estimation of analyte concentrations or sample properties when spectroscopic analysis is combined with multivariate calibration techniques such as partial least-squares (PLS) regression. The new algorithm employs the concept of cooperative pheromone accumulation, which is typical of ACO selection methods, and optimizes PLS models using a pre-defined number of variables, employing a Monte Carlo approach to discard irrelevant sensors. The performance has been tested on a simulated system, where it shows a significant superiority over other commonly employed selection methods, such as genetic algorithms. Several near infrared spectroscopic experimental data sets have been subjected to the present ACO algorithm, with PLS leading to improved analytical figures of merit upon wavelength selection. The method could be helpful in other chemometric activities such as classification or quantitative structure-activity relationship (QSAR) problems. 相似文献
970.
Ana Filipa L.O.M. Santos André R. Monteiro Jorge M. Gonçalves William E. Acree Maria D.M.C. Ribeiro da Silva 《The Journal of chemical thermodynamics》2011,43(7):1044-1049
In this paper, the first, second and mean (N?O) bond dissociation enthalpies (BDEs) were derived from the standard (p° = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, , at T = 298.15 K, of 2,2′-dipyridil N-oxide and 2,2′-dipyridil N,N′-dioxide. These values were calculated from experimental thermodynamic parameters, namely from the standard (p° = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, , at T = 298.15 K, obtained from the standard molar enthalpies of combustion, , measured by static bomb combustion calorimetry, and from the standard molar enthalpies of sublimation, at T = 298.15 K, determined from Knudsen mass-loss effusion method. 相似文献