首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   15944篇
  免费   674篇
  国内免费   141篇
化学   11330篇
晶体学   134篇
力学   484篇
综合类   3篇
数学   2516篇
物理学   2292篇
  2023年   120篇
  2022年   300篇
  2021年   500篇
  2020年   416篇
  2019年   479篇
  2018年   376篇
  2017年   327篇
  2016年   676篇
  2015年   493篇
  2014年   530篇
  2013年   1135篇
  2012年   964篇
  2011年   1035篇
  2010年   688篇
  2009年   606篇
  2008年   844篇
  2007年   889篇
  2006年   698篇
  2005年   723篇
  2004年   600篇
  2003年   488篇
  2002年   477篇
  2001年   215篇
  2000年   207篇
  1999年   140篇
  1998年   133篇
  1997年   153篇
  1996年   153篇
  1995年   125篇
  1994年   123篇
  1993年   131篇
  1992年   110篇
  1991年   107篇
  1990年   116篇
  1989年   90篇
  1988年   73篇
  1987年   81篇
  1986年   96篇
  1985年   135篇
  1984年   120篇
  1983年   96篇
  1982年   94篇
  1981年   92篇
  1980年   82篇
  1979年   80篇
  1978年   79篇
  1977年   53篇
  1976年   49篇
  1975年   56篇
  1974年   56篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
The formation of stable water-in-crude oil emulsions during petroleum production and refinery may create sever and costly separation problems. It is very important to understand the mechanism and factors contributing to the formation and stabilization of such emulsions for both great economic and environmental development. This article investigates some of the factors controlling the stability of water-in-crude oil emulsions formed in Burgan oil field in Kuwait. Water-in-crude oil emulsion samples collected from Burgan oil filed have been used to separate asphaltenes, resins, waxes, and crude oil fractions. These fractions were used to prepare emulsion samples to study the effect of solid particles (Fe3O4) on the stability of emulsions samples. Results indicate that high solid content lead to higher degree of emulsion stability. Stability of emulsion samples under various waxes to asphaltenes (W/A) ratios have also been tested. These tests showed that at low W/A content, the emulsions were very stable. While at a wax to asphaltene ratio above 1 to 1, the addition of wax reduced emulsion stability. Stability of emulsion samples with varying amount of water cut has also been investigated. Results indicated that stability and hence viscosity of emulsion increases as a function of increasing the water cut until it reaches the inversion point where a sharp decline in viscosity takes place. This inversion point was found to be approximately at 50% water cut for the crude oils considered in this study.  相似文献   
992.
Abstract

A three-column ion chromatographic system for the removal of humic substances from natural waters, and subsequent on-line concentration and determination of nitrate and sulfate using non-suppressed ion chromatography is presented. Humic substances are removed using disposable adsorption columns packed with chemically bonded amine silica material. The sample is directly transfered to an ion exchange column where the anions are concentrated ca 10 times. After reversing the flow, the ions are transferred to a third column where they are separated and quantified. The detection limit is less than 1 mg L?1 of nitrate or sulfate in water containing 45mgL?1 of humic acid.  相似文献   
993.
R.M.MOHAMED  E.AAZAM 《催化学报》2013,34(6):1267-1273
P‐doped TiO2 (PTIO) thin‐films with different P contents were prepared using a sol‐gel method. The thin‐film samples were characterized using various techniques. The photocatalytic activity was evaluated by decomposing butyl benzyl phthalate under visible‐light irradiation. The results showed that the transformation of anatase to the rutile phase was inhibited and grain growth of TiO2 was prevented by P doping. The results confirm that the doped P atoms existed in two chemical forms, and those incorporated in the TiO2 lattice may play a positive role in photocatalysis. The high photocatalytic activities of the PTIO thin‐films may be the result of extrinsic absorption through the creation of oxygen vacancies, rather than excitation of the intrinsic absorption band of bulk TiO2 . The PTIO can be recycled with little depression of the photocatalytic activity. After six cycles, the photocatalytic activity of the PTIO film was still higher than 98%.  相似文献   
994.
A highly sensitive, selective and simple method is described for the determination of histamine by high-performance liquid chromatography (HPLC) with fluorescence detection. The method is based on an intramolecular excimer-forming fluorescence derivatization of histamine with 4-(1-pyrene)butyric acid N-hydroxysuccinimide ester (PSE), followed by reversed-phase HPLC. Histamine, having two amino moieties in a molecule, was converted to the dipyrene-labeled derivative by reaction with PSE. The derivative afforded intramolecular excimer fluorescence (450-540 nm), which can clearly be discriminated from the monomer fluorescence (370-420 nm) emitted from PSE. Typically, a 10 micro L sample solution was mixed with 100 micro L of derivatization reagent solution, which was a mixture of 0.5 mm PSE in acetonitrile and 0.5 mm potassium carbonate in water (8:2, v/v). The derivatization was carried out at 100 degrees C for 90 min. The PSE derivative of histamine could be separated by reversed-phase ODS column with isocratic elution using acetonitrile:water (82:18, v/v) containing 0.03% triethylamine. The detection limit (singnal-to-noise ratio = 3) of histamine was 0.5 fmol for a 30 micro L injection. The method was successfully applied to the determination of histamine in human urine, and had enough selectivity and sensitivity for urinary histamine quantification.  相似文献   
995.
2-(4-Amino-substituted-3-nitrophenyl)-3-hydroxyquinolin-4(1H)-ones have been studied to evaluate their fluorescence properties and possible use as molecular fluorescent probes. The amino group was substituted with various alkyl moieties possessing a suitable terminal functional group (such as hydroxy or amino group) that could serve to bind a 3-hydroxyquinolin-4(1H)-one (3HQ) fluorescence label to a biomolecule. Besides simple hydrocarbon chains, ligands containing ethylenoxy units as optimal spacers were also tested. The structure-fluorescence properties and theoretical applicability of the studied molecules are discussed.  相似文献   
996.
997.
Two photosensitizing systems: (1) tetrakis(4-hydroxyphenyl)porphyrin (p-THPP) encapsulated in sterically stabilized liposomes (SSL) and (2) p-THPP functionalized by covalent attachment of poly(ethylene glycol) (p-THPP–PEG2000) were studied in vitro. The dark and photo cytotoxicity of these systems were evaluated on two cell lines: HCT 116, a human colorectal carcinoma cell line, and DU 145, a prostate cancer cell line and compared with these determined for free p-THPP. It was demonstrated that both encapsulation in liposomes as well as attachment of PEG chain result in pronounced reduction of the dark cytotoxicity of the parent porphyrin. The liposomal formulation showed higher than p-THPP–PEG2000 photocytotoxicity towards both cell lines used in the studies.  相似文献   
998.
The eco-friendly synthesis, spectroscopic (IR, MS, 1H and 13C NMR) study and biological (cytostatic, antiviral) activity of sodium and potassium benzeneazophosphonate complexes, obtained by reaction in the solid state under microwave irradiation of the alkali salts of ethyl [α-(4-benzeneazoanilino)-N-benzyl]phosphonic acid and [α-(4-benzeneazoanilino)-N-4-methoxybenzyl]phosphonic acid with crown ethers containing 18-membered (dibenzo-18-crown-6 and bis(4′-di-tert-butylbenzo)-18-crown-6), 24-membered (dibenzo-24-crown-8) and 30-membered (dibenzo-30-crown-10) macrocyclic rings, have been described. The simple work-up solvent free reaction is an efficient green procedure for the formation of mononuclear crown ether complexes in which the sodium/potassium ion is bound to oxygen atoms of the macrocycle and the phosphonic acid oxygen. The free crown ethers, alkali benzeneazophosphonate salts and their complexes were evaluated for their cytostatic activity in vitro against murine leukemia L1210, murine mammary carcinoma FM3A and human T-lymphocyte CEM and MT-4 cell lines, as well as for their antiviral activity against a wide variety of DNA and RNA viruses. The investigated compounds showed no specific antiviral activity, whereas all the free crown ethers and their complexes demonstrated cytostatic activity, which was especially pronounced in the case of bis(4′-di-tert-butylbenzo)-18-crown-6 and its complexes.  相似文献   
999.
In the present study, a new and versatile liquid-phase microextraction method is described. This method requires very simple and cheap apparatus and also a small amount of organic solvent. Eight microliters of 1-undecanol was delivered to the surface of solution containing analytes and solution was stirred for a desired time. Then sample vial was cooled by inserting it into an ice bath for 5 min. The solidified 1-undecanol was transferred into a suitable vial and immediately melted; then, 2 μL of it was injected into a gas chromatograph for analysis.Some polycyclic aromatic hydrocarbons (PAHs) were used as model compounds for developing and evaluating of the method performance. Analysis was carried out by gas chromatography/flame ionization detection (GC/FID).Several factors influencing the microextraction efficiency, such as the nature and volume of organic solvent, the temperature and volume of sample solution, stirring rate and extraction time were investigated and optimized. The applicability of the technique was evaluated by determination of trace amounts of PAHs in environmental samples. Under the optimized conditions, the detection limits (LOD) of the method were in the range of 0.07-1.67 μg L−1 and relative standard deviations (R.S.D.) for 10 μg L−1 PAHs were <7%. A good linearity (r2 > 0.995) in a calibration range of 0.25-300.00 μg L−1 was obtained. After 30 min extraction duration, enrichment factors were in the range of 594-1940. Finally, the proposed method was applied to the determination of trace amounts of PAHs in several real water samples, and satisfactory results were resulted. Since very simple devices were used, this new technique is affordable, efficient, and convenient for extraction and determination of low concentrations of PAHs in water samples.  相似文献   
1000.
The use of laser microprobe mass spectrometry (LMMS) for the structural characterization of thermolabile quaternary phosphonium salts has been evaluated. A comparison has been made between LM mass spectra obtained by direct analysis of “neat” organic salts and the corresponding “matrix-assisted” LM mass spectra. Main limitations of LMMS for the direct analysis of neat organic salts (i.e., no matrix) result from (1) formation of artifact ions that originate from thermal degradation and surface recombination reactions and (2) poor shot-to-shot reproducibility of the spectra. Dilution of the organic salts in a suitable, UV-absorbing matrix (e.g., nicotinic acid) significantly enhances the quality of the LM mass spectra. Improvements are: (1) an increase of the ion yield of preformed cations, (2) reduction or elimination of thermal decomposition and other deleterious surface reactions, and (3) a much better shot-to-shot spectral reproducibility. An interesting analytical feature is that these LM mass spectra, which contain only a few matrix peaks, can be obtained for subnanogram amounts of sample. The results also show that triphenylphosphonium salts with polycyclic aromatic substituents can be used as “molecular thermometers” to probe both the temperatures experienced by the sample molecules during the laser-induced desorption ionization process and the internal energies of the desorbed ion species. In this way, quaternary phosphonium salts can be used for evaluating whether improvements have been achieved by applying different sample treatments. Comparison of four different matrices (i.e., nicotinic acid, ammonium chloride, glycerol, and 3-nitrobenzylalcohol) indicates that the effectiveness of a matrix to reduce thermal degradation and to decrease the internal energies of the ions depends on the UV-absorption characteristics and the volatilization/sublimation temperature of the matrix material.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号