全文获取类型
收费全文 | 2461篇 |
免费 | 113篇 |
国内免费 | 9篇 |
专业分类
化学 | 1358篇 |
晶体学 | 37篇 |
力学 | 153篇 |
数学 | 526篇 |
物理学 | 509篇 |
出版年
2023年 | 23篇 |
2022年 | 35篇 |
2021年 | 41篇 |
2020年 | 66篇 |
2019年 | 86篇 |
2018年 | 80篇 |
2017年 | 77篇 |
2016年 | 137篇 |
2015年 | 85篇 |
2014年 | 103篇 |
2013年 | 359篇 |
2012年 | 129篇 |
2011年 | 125篇 |
2010年 | 100篇 |
2009年 | 102篇 |
2008年 | 96篇 |
2007年 | 104篇 |
2006年 | 83篇 |
2005年 | 64篇 |
2004年 | 78篇 |
2003年 | 45篇 |
2002年 | 48篇 |
2001年 | 39篇 |
2000年 | 26篇 |
1999年 | 30篇 |
1998年 | 30篇 |
1997年 | 34篇 |
1996年 | 32篇 |
1995年 | 23篇 |
1994年 | 26篇 |
1993年 | 17篇 |
1992年 | 13篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 17篇 |
1987年 | 11篇 |
1986年 | 6篇 |
1985年 | 16篇 |
1984年 | 14篇 |
1983年 | 11篇 |
1982年 | 8篇 |
1981年 | 15篇 |
1980年 | 13篇 |
1979年 | 11篇 |
1978年 | 5篇 |
1977年 | 9篇 |
1975年 | 12篇 |
1973年 | 5篇 |
1971年 | 5篇 |
1927年 | 5篇 |
排序方式: 共有2583条查询结果,搜索用时 31 毫秒
41.
α-Aspartame (L-α-aspartyl-L-phenylalanine methyl ester) is increasingly being used in wide variety of commonly consumed food products. This structure contains ester and peptide bonds. The ester linkage may hydrolyze to produce L-α-aspartyl-L-phenylalanine or cyclohydrolyze to produce the corresponding diketopiperazine ring. This ring can open to form L-α-aspartyl-L-phenylalanine and ultimately this compound can hydrolyze to L-phenylalanine and L-aspartic acid. The pH, buffer type, concentration, the presence of water and temperature are other important factors affecting its stability. Because α-aspartame can lose its sweetness under these conditions determination of aspartame and its breakdown products is extremely important for diet foods quality. The optimum mobile phase for the chromatographic separation was found to be acetonitrile-water (20:80, ν/ν) with 5.10?3 M hexanesulfonic acid and a pH of 2.6. 相似文献
42.
Summary A fully integrated chromatographic system was developed for the determination of leukotrienes in biological samples using
photodiode-array detection (PDAD), which eliminates time consuming manual sample handling steps. A special solid phase extraction,
(SPE) methodology for leucotriene metabolite stability was developed which increased the recoveries and eliminates the contamination
risk of biological samples. The inherent instability (autooxidation) of many of the leukotriene mediators, and the adsorption
effects onto exposed surfaces in vials and in the chromatographic system were found to be very important parameters to control
in order to circumvent high loss of sample analytes. By binding the cell supernatants to the functionalities of the SPE support
stabilised these mediators. Cell culture samples were eluted through a disposable C18 SPE column. The SPE columns were allowed to thaw and deposited in an automated sample handling unit (ASPEC XL). Desorption
of the analytes was followed by a second on-line SPE step, to eliminate remaining interfering matrix compounds. Typical recoveries
when stored at −70°C were in-between 55–97% except for (LTE4) which was found to be around 40% after 72 days of storage. Seven reversed-phase packings were studied. Selectivity factors,
as well as the separation efficiencies, were found to differ for the various C18 bonded silica stationary phases. This integrated on-line column liquid chromatographic system was applied to the determination
of leukotriene B4, leukotriene C4, leukotriene D4, leukotriene and E4 in human cell extracts using prostaglandin B2 as the internal standard. More than 1500 biological samples were analysed. Some validation data are presented for unattended
operations. 相似文献
43.
Ay?em Üzer 《Analytica chimica acta》2005,534(2):307-317
Contaminated land and groundwater remediation in military waste dumping sites often necessitates the use of simple, cost-effective, and rapid tests for detecting trinitrotoluene (TNT) residues in the field along with their dinitro-analogues. A simple, rapid, low-cost, and field-adaptable (on-site) colorimetric method was developed for quantifying TNT in the presence of RDX, PETN, picric acid, 2,4-DNT (dinitrotoluene), dinitrophenol, and dinitroaniline. Most commercialized methods for TNT assay-with the exception of Cold Regions Research and Engineering Laboratory of the U.S. Army (CRREL) method-use proprietary chemicals, and the color stability and intensity are highly dependent on the composition of the organic solution comprised of acetone or methanol. The developed colorimetric method is based on the extraction of TNT from water-acetone solution into an organic solvent mixture of dicyclohexylamine (DCHA)-isobutyl methyl ketone (IBMK) (10:1, v/v), filtration through a filter paper into a stoppered optical cell containing anhydrous sodium sulfate, and measurement of the absorbance of the organic extract at 531 nm after 5 min. The red-violet color of the extract was due to intermolecular charge-transfer (CT) between the electron attracting TNT and electron-donating DCHA, and the molar absorptivity for TNT in final organic solution was (1.16 ± 0.02) × 104 L mol−1 cm−1.The R.S.D. of the slope of calibration line was 0.7%. The LOD of the method in the final organic phase was 0.38 μM TNT, and LOD values expressed on the basis of original soil TNT content were 0.5, 1.3, and 1.5 ppm (μg g−1) for clay, loamy clay, and sandy soils, respectively. Unlike other spectrophotometric methods, the developed assay was basically tolerant to common cations and anions found in soil and water at 100-fold weight ratios, and to soil humic acids. Among a number of compounds that may be encountered in polynitro-explosive storage and waste reclaimation sites such as picric acid, dinitrophenol, 2,4-dinitrotoluene, dinitroaniline, RDX, PETN, and tetryl, only tetryl interfered with the developed TNT assay. Water tolerance and exploitability over a wide pH range were other superiorities over the CRREL method. The CT-complex was relatively stable, as the absorbance of the organic extract was not significantly influenced from the dilution of the water-acetone phase. Aside from the extractive-photometric procedure established for aqueous solutions, a simulated field colorimetric assay for TNT directly applicable to soil was also devised, based on direct color development in a 4:1 (v/v) acetone-dicyclohexylamine organic extract of soil at a liquid-to-solid ratio of 5 mL g−1. 相似文献
44.
Nihan?Kaya Erdal?Karadurmus Ahmet?AlicilarEmail author 《Central European Journal of Chemistry》2005,3(3):511-519
An attempt was made to study the oxidation of manganese by air in synthetic waters. A series of batch experments were performed
at differnet values of concentration, temperature and pH. Unoxidized manganese in the solution was determined by formaldoxime
spectrometric method. Results of these studies indicated that the air oxidation of manganese soluble in water can be effectively
performed in basic media and that oxidation yield increasedwith an increase in pH and concentration. The yield was very high
in the presence of manganese dioxide, sepiolite or clinoptilolite in solution and, the oxidation was almost completed especially
at high values of pH and concentration. The reaction was found to be first order with respect to Mn2+ with a very low activation energy. A yield of 62% was obtained for the air oxidation of wastewater taken from the treatment
plant of Corum Municipality. 相似文献
45.
Compton scattering normalization method is described for the analysis of uranium bearing ore respect to the usage of K X-rays of uranium. Minimum backscatter energy is obtained at a scatter angle of 180° with fixed point source geometry and collimation in appropriate conclusions. By normalizing the intensities of uranium K-lines to the Compton profile in the measured spectra, the results do not depend on several measuring parameters such as primary radiation intensity, matrix, composition, mass of the sample and measuring time. The method presented in this study indicates the convenience of uranium K-lines analysis for thick targets with an adequate measuring geometry. 相似文献
46.
Nagihan Saglam Ahmet Colak Kerim Serbest Serdar Karab?cek Saadettin Güner 《Monatshefte für Chemie / Chemical Monthly》2004,15(4):1023-1031
Nucleolytic activities of novel mononuclear Cu(II), homo- and heterodinuclear Cu(II)–Ni(II) complexes with two diester-type ligands were investigated on pCYTEXP by neutral agarose gel electrophoresis. The analyses of the cleavage products obtained electrophoretically indicate that the examined complexes induce very similar conformational changes on supercoiled DNA by converting supercoiled form to nicked form. At concentrations greater than 100M, the complexes possessed effective nucleolytic activities for 10min of incubation time. However, their nucleolytic activities did not increase significantly with longer periods of incubation. The pH-nucleolytic activity profiles of the complexes differed significantly. Metal complex induced DNA cleavage was also tested for inhibition by various radical scavengers. It could be proposed from the data that diffusible intermediate oxidants are not involved in these reactions or they are not necessary for DNA cleavage since none of antioxidants inhibited DNA cleaving activities of the complexes. 相似文献
47.
First ever non-deformylating transdiazotization of acylacetaldehydes was achieved: the reactions of 2-azido-l-ethylpyridinium tetrafluoroborate ( 4 ) with acylacetaldehydes 3 proceeded partially without deformylation to yield 16 new α-diazo-β-oxoaldehydes 1 along with diazomethyl ketones 2 , especially in the presence of NaOAc (Scheme 1, Tables 1 and 2). The product distribution was substituent-dependent and could be correlated quantitatively. This new diazotization reaction appears as an alternative, direct, and more general method for the synthesis of these diazooxoaldehydes. α-Oxocycloalkanecarbaldehydes 5 gave only traces (if any) of α-diazocycloalkanones 7 , and rearrangement products 6 were isolated (Scheme 2). Mechanisms of the reactions are discussed (Schemes 4 and 5). 相似文献
48.
In this study, a rapid pre-concentration procedure, which employs powdered activated carbon as a clean-up and pre-concentration material, is described for the gas chromatographic analysis of N-nitrosodiethylamine (NDEA) and N-nitrosodimethylamine (NDMA) in aqueous solutions. It was found that powdered activated carbon is suitable for the adsorption of volatile N-nitrosamine compounds from aqueous solutions. Adsorption efficiency with spiked beer samples (alcohol content 5% v/v) was found to be 80.5% (NDMA) and 89.4% (NDEA) and recovery of extraction from activated carbon was calculated as 82.1% (NDMA) and 89.7% (NDEA), respectively. The effect of 100µgmL–1 of tannic acid on the adsorption was also studied, and no significant effect on the adsorption and extraction of volatile N-nitrosamine compounds was found. 相似文献
49.
Süleyman Özçeli Hakan Sezgin 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(3-4):185-190
New Hofmann-diaminohexane(dahxn)-type clathrates of the form M(1,6-dahxn)Ni(CN)4.G (M = Co, Ni or Cd; G = chlorobenzene, 1,2-, 1,3 or 1,4-dichlorobenzene) were prepared inpowder form and their infrared spectra are reported. The spectral data suggest that these compounds are similar in structure to those of the Hofmann-diam-type clathrates. Their structure consists of planar polymeric layers, {M–Ni(CN)4}, formedfrom Ni(CN)4 anions coordinated to the bridging 1,6-diaminohexane molecules bound directly to the metal (M). The M atoms are bound to four N atoms of the CN ions and, the Ni atoms are surrounded by four C atoms of the CN groups in a square-planar layer. 相似文献
50.
Labeling conditions of synkavit (2-methyl-1,4-naphthoquinol disodium phosphate) with iodine-125 have been studied. In this study, labeling temperature, reaction time, successive using of iodogen coated tubes, iodogen amount and synkavit concentrations have been determined to get optimum conditions for maximum labeling. Final results showed that when the labeling temperature, reaction time, synkavit concentration, and iodogen amount were, at room temperature, 15 min (in the case of successive using of three iodogen coated tubes), 2 mg ml–1 and 5 mg, respectively; labeling yield was 90% and specific activities of the order of 555 GBq mmol–1 (15 Ci mmol–1) have been obtained. 相似文献