全文获取类型
收费全文 | 14203篇 |
免费 | 302篇 |
国内免费 | 65篇 |
专业分类
化学 | 8083篇 |
晶体学 | 132篇 |
力学 | 523篇 |
数学 | 2613篇 |
物理学 | 3219篇 |
出版年
2022年 | 197篇 |
2021年 | 221篇 |
2020年 | 230篇 |
2019年 | 246篇 |
2018年 | 244篇 |
2017年 | 218篇 |
2016年 | 341篇 |
2015年 | 287篇 |
2014年 | 344篇 |
2013年 | 873篇 |
2012年 | 641篇 |
2011年 | 736篇 |
2010年 | 478篇 |
2009年 | 446篇 |
2008年 | 613篇 |
2007年 | 549篇 |
2006年 | 497篇 |
2005年 | 435篇 |
2004年 | 455篇 |
2003年 | 358篇 |
2002年 | 361篇 |
2001年 | 264篇 |
2000年 | 236篇 |
1999年 | 180篇 |
1998年 | 143篇 |
1997年 | 166篇 |
1996年 | 206篇 |
1995年 | 158篇 |
1994年 | 151篇 |
1993年 | 192篇 |
1992年 | 189篇 |
1991年 | 194篇 |
1990年 | 145篇 |
1989年 | 139篇 |
1988年 | 155篇 |
1987年 | 213篇 |
1986年 | 184篇 |
1985年 | 229篇 |
1984年 | 207篇 |
1983年 | 166篇 |
1982年 | 197篇 |
1981年 | 201篇 |
1980年 | 194篇 |
1979年 | 202篇 |
1978年 | 193篇 |
1977年 | 180篇 |
1976年 | 160篇 |
1975年 | 175篇 |
1974年 | 139篇 |
1973年 | 132篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Existing theories of the motion of foam films in capillaries often assimilate the pressure drop over the foam films to the static capillary pressure obtained from the Young-Laplace equation. Hence, they ignore the contribution of dynamic effects associated with the rapid stretching and contraction of the foam films to the overall viscous dissipation. This paper reports an investigation of the motion of foam films in axisymmetric diverging-converging channels, taking into account surface viscosity and elasticity. First, a phenomenological theory for the motion of the foam films is developed using simple physical arguments. We show that the displacement of the film obeys a nonlinear second-order differential equation, which can be solved numerically for the (dimensionless) distance from the inlet and the pressure drop as a function of time. Experiments with foam film motion, conducted using glass diverging-converging channels (minimum radius = 3.00 +/- 0,01 mm, maximum diameter = 7,98 +/- 0,01 mm) and nitrogen foam stabilized with sodium dodecyl sulfate (SDS) in brine, are discussed. For a single film motion in the diverging channel, we find that (a) the static pressure drop is a concave-upward function of distance and decreases from 1.0 to about 0.3, whereas (b) the dynamic pressure drop is concave downward and increases from 1 to a maximum of 1.3 and then decreases to 0.7. In the converging channel both the static and dynamic pressure drops are concave-downward functions, but the dynamic pressure drop values are always higher than the static ones. For two films the motions were found to be rather sensitive to the initial arrangement in the channel. The experiments are found to be in excellent agreement with the theoretical predictions. These observations imply that the large flow resistance obtained during foam flow in granular porous media, where converging-diverging channels are abundant, is largely due to the surface elasticity and viscosity of the films. 相似文献
992.
Heilemann M Tinnefeld P Sanchez Mosteiro G Garcia Parajo M Van Hulst NF Sauer M 《Journal of the American Chemical Society》2004,126(21):6514-6515
We demonstrate the synthesis and spectroscopic characterization of an unidirectional photonic wire based on four highly efficient fluorescence energy-transfer steps (FRET) between five spectrally different chromophores covalently attached to double-stranded DNA. The DNA-based modular conception enables the introduction of various chromophores at well-defined positions and arbitrary interchromophore distances. While ensemble fluorescence measurements show overall FRET efficiencies between 15 and 30%, single-molecule spectroscopy performed on four spectrally separated detectors easily uncovers subpopulations that exhibit overall FRET efficiencies of up to approximately 90% across a distance of 13.6 nm and a spectral range of approximately 200 nm. Fluorescence trajectories of individual photonic wires show five different fluorescence intensity patterns which can be ascribed to successive photobleaching events. 相似文献
993.
2-Nitrophenylhydrazine (2-NPH) is widely used for the derivatization of carboxylic acids, aldehydes and ketones, in industrial and biological samples. These compounds react with 2-NPH to form derivatives, which are separated by high-performance liquid chromatography (HPLC) and detected with diode array detection (DAD). The UV spectra give information about the functionality of the compounds: carboxylic acid or ketone/aldehyde. Most of the eluting compounds in "known" samples are well characterised by the retention time (comparison with those of standards) of the 2-NPH derivative and their UV spectrum. The identification of different unknown 2-NPH derivatives of carboxylic acids, ketones and/or aldehydes, in industrial or biological samples, based on retention time and/or UV spectrum is not sufficient. These unknown 2-NPH compounds can be identified with on-line atmospheric pressure chemical ionisation mass spectrometry (APCI-MS) based on the molecular mass or/and the fragmentation of the derivative. A novel and specific on-line HPLC-DAD-APCI(-)-MS method is described for the determination of carboxylic acids, ketones and aldehydes, after on-line pre-column derivatization with 2-NHP. The fragmentation of different 2-NPH derivatives were investigated and the possibilities of APCI(-)-MS detection were demonstrated by the on-line identification of an unknown derivative, which turned out to be a side product between 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 2-NPH in the presence of high concentrations of a cyclic amide in the sample solution. 相似文献
994.
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
995.
Hai X Nauwelaers T Busson R Adams E Hoogmartens J Van Schepdael A 《Electrophoresis》2010,31(19):3352-3361
A rapid and sensitive electrophoretically mediated microanalysis method with field-enhanced sample injection (FESI) for in-capillary derivatization was developed to determine selenomethionine (SeMet) and selenomethionine selenoxide (SeOMet). Phthalic anhydride (PA) was selected as the derivatization reagent due to the fast reaction at room temperature and the stability of derivatives. The in-capillary derivatization was accomplished by electrophoretically mixing PA and sample plugs. PA reagent was introduced hydrodynamically into the capillary, whereas the sample solution was injected electrokinetically, thus allowing a selective preconcentration of the analytes by FESI. For FESI, the optimum sample solvent was 2 mM borate solution. The borate buffer was suitable for both in-capillary derivatization and separation of the derivatives. The combination of electrophoretically mediated microanalysis with FESI for in-capillary derivatization was successfully achieved with about 800-fold concentration sensitivity enhancement compared to direct CE-UV detection in the same setup. The present method is miniaturized and fully automated, which ensures the on-line derivatization, stacking, separation and detection in 10 min. Finally, the developed method was successfully applied to measure enzyme activities by analyzing the reaction mixtures of SeMet with human flavin-containing monooxygenases (FMO). The results showed that both FMO1 and FMO3, but not FMO5 could catalyze the Se-oxygenation of SeMet. 相似文献
996.
Hurth C Smith SD Nordquist AR Lenigk R Duane B Nguyen D Surve A Hopwood AJ Estes MD Yang J Cai Z Chen X Lee-Edghill JG Moran N Elliott K Tully G Zenhausern F 《Electrophoresis》2010,31(21):3510-3517
The microfluidic integration of an entire DNA analysis workflow on a fully integrated miniaturized instrument is reported using lab‐on‐a‐chip automation to perform DNA fingerprinting compatible with CODIS standard relevant to the forensic community. The instrument aims to improve the cost, duration, and ease of use to perform a “sample‐to‐profile” analysis with no need for human intervention. The present publication describes the operation of the three major components of the system: the electronic control components, the microfluidic cartridge and CE microchip, and the optical excitation/detection module. Experimental details are given to characterize the level of performance, stability, reliability, accuracy, and sensitivity of the prototype system. A typical temperature profile from a PCR amplification process and an electropherogram of a commercial size standard (GeneScan 500?, Applied Biosystems) separation are shown to assess the relevance of the instrument to forensic applications. Finally, we present a profile from an automated integrated run where lysed cells from a buccal swab were introduced in the system and no further human intervention was required to complete the analysis. 相似文献
997.
Nguyen Tle A Devic T Mialane P Rivière E Sonnauer A Stock N Demir-Cakan R Morcrette M Livage C Marrot J Tarascon JM Férey G 《Inorganic chemistry》2010,49(22):10710-10717
A high-throughput methodology combined with X-ray powder diffraction measurements was used to investigate the reactivity of the TetraThiaFulvalene TetraCarboxylic acid ((TTF-TC)H(4)) with divalent metals (M = Ni, Co) under various reaction conditions (stoichiometry, pH, temperature). Two new crystalline phases were identified and then studied by single crystal X-ray diffraction. Whereas the first one appears to be a simple salt, the second one, formulated {[M(H(2)O)(4)](2)(TTF-TC)}·4H(2)O, is built of 2:1 M:TTF-TC molecular complexes and labeled MIL-136(Ni, Co) (MIL stands for Materials Institute Lavoisier). The combination of thermogravimetric analysis and thermodiffraction studies reveals that MIL-136(Ni) exhibits a complex dehydration behavior. Indeed, a partial dehydration/rehydration process led to the single-crystal-to-single-crystal transformation of the molecular compound in a two-dimensional coordination polymer formulated {[Ni(2)(H(2)O)(5)(TTF-TC)]}·H(2)O (MIL-136'(Ni)). Magnetic and redox properties of MIL-136(Ni, Co) were investigated. Magnetic measurements indicate that all the magnetic coupling, intra- and intermolecular, are very weak; thus, the magnetic data of MIL-136(Ni, Co) have been interpreted in term of single-ion spin orbit coupling. Solid state cyclic voltammetry of MIL-136(Ni, Co) presents three reversible waves which were assigned to the redox activity of the TTF core and the metallic cations. In contrast to solids based on TTF linkers and alkaline ions, the MIL-136(Ni, Co) complexes do not act as excellent positive electrode materials for Li batteries, but present two reversible electron oxidation of the TTF core. These observations were tentatively related to the strength of the metal-carboxylate bond. 相似文献
998.
Rasheed Ahmad Khera Rasheed Ahmad Nguyen Thai Hung Alexander Villinger Peter Langer 《Tetrahedron》2010,66(9):1643-1652
Functionalized triarylmethanes are prepared in two steps by FeCl3-catalyzed benzylation of acetylacetone to give 3-(diarylmethyl)pentane-2,4-diones and subsequent formal [3+3] cyclization of the latter with 1,3-bis(trimethylsilyloxy)-1,3-dienes. 相似文献
999.
6,7-Dialkynyl-1,3-dimethylpteridine-2,4(1H,3H)-diones and 2,3-dialkynylquinoxalines have been shown to react with sodium azide in DMF at room temperature giving rise 9,11-dimethyl-[1,2,3]triazolo[1′,5′;1,2]pyrido[4,3-g]pteridine-8,10(9H,11H)-diones and [1,2,3]triazolo[1′,5′;1,2]pyrido[3,4-b]quinoxalines. A novel tandem cyclization involves 1,3-dipolar cycloaddition of an azide ion to the carbon-carbon triple bond followed by intramolecular nucleophilic addition of the intermediate 1,2,3-triazole N-anion to another CC bond. 相似文献
1000.
Extraction and isolation of catechins from tea 总被引:1,自引:0,他引:1
Tea is a major source of catechins, which have become well known for their antioxidant potential. Numerous human, animal, and in vitro studies have linked tea catechins with prevention of certain types of cancers, reduction of the risks for obesity, diabetes, and cardiovascular disease, and improvement of the immune system. Tea catechins are widely used in various neutraceuticals, pharmaceuticals, and cosmetics for either enhancing product shelf-life or for enhancing human health. Thus, the demand for catechins has increased considerably. Catechins have been extracted and isolated from tea leaves by numerous methods through several steps including: treatment of the tea leaves, extraction of catechins from teas into solvents, isolation of catechins from other extracted components, and drying the preparations to obtain catechin extracts in a powder form. This paper outlines the physical and chemical properties of the tea catechins and reviews the extraction steps of the various extraction methods, as a basis to improve and further develop the extraction and isolation of the tea catechins. 相似文献