全文获取类型
收费全文 | 14290篇 |
免费 | 1117篇 |
国内免费 | 805篇 |
专业分类
化学 | 7314篇 |
晶体学 | 295篇 |
力学 | 1139篇 |
综合类 | 67篇 |
数学 | 1537篇 |
物理学 | 5860篇 |
出版年
2024年 | 22篇 |
2023年 | 149篇 |
2022年 | 312篇 |
2021年 | 326篇 |
2020年 | 354篇 |
2019年 | 336篇 |
2018年 | 333篇 |
2017年 | 309篇 |
2016年 | 428篇 |
2015年 | 418篇 |
2014年 | 575篇 |
2013年 | 801篇 |
2012年 | 1060篇 |
2011年 | 1171篇 |
2010年 | 872篇 |
2009年 | 870篇 |
2008年 | 852篇 |
2007年 | 738篇 |
2006年 | 733篇 |
2005年 | 575篇 |
2004年 | 540篇 |
2003年 | 439篇 |
2002年 | 398篇 |
2001年 | 614篇 |
2000年 | 460篇 |
1999年 | 343篇 |
1998年 | 268篇 |
1997年 | 225篇 |
1996年 | 246篇 |
1995年 | 174篇 |
1994年 | 177篇 |
1993年 | 116篇 |
1992年 | 115篇 |
1991年 | 121篇 |
1990年 | 104篇 |
1989年 | 83篇 |
1988年 | 68篇 |
1987年 | 44篇 |
1986年 | 45篇 |
1985年 | 49篇 |
1984年 | 37篇 |
1983年 | 25篇 |
1982年 | 39篇 |
1981年 | 32篇 |
1980年 | 28篇 |
1979年 | 20篇 |
1978年 | 25篇 |
1977年 | 19篇 |
1976年 | 18篇 |
1975年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 9 毫秒
161.
Establishing a calibration model is an important part of any mathematical method for multi-component determination. Use of a calibration model based on single spectra is subject to error, because the model spectrum chosen may not be representative of the response over the full range of the calibration. Alternative calibration models require more time to establish calibration, an these may not be convenient for real-time determinations. A novel calibration method is reported for use with Kalman filters. The method, dynamic modeling, is based on the use of libraries of calibration spectra. The set of used to describe the model at any time is based on component concentrations, estimated for the multi-component mixture, as determined from the Kalman filter, so that several spectra can be used to best describe a varying response. Through application of the dynamic modelingt to simulated and real chromatograms, it is demonstrated that use of the method decreases estimation errors cause by model data mismatches, and that full benefit can be obtained from relatively small libraries. 相似文献
162.
Jiang Ke QIN Xian Zhang BU Yu Fang WANG Zhi Yun DU Xing Yuan WANG Zhi Shu HUANG Lin MA Lin Kun AN Lian Quan GU 《中国化学快报》2005,16(11):1451-1454
The reactions of tanshinone IIA with aromatic aldehydes have been investigated and several 2, T-(substituted arylmethylene) bis (1,6,6-trimethyl-6,7,8,9-tetrahydrophenanthro[1,2-b]- furan- 10, 11-dione) derivatives were obtained, 相似文献
163.
The high-sensitivity determination of protein concentrations by the enhancement of Rayleigh light scattering of Arsenazo-DBN 总被引:1,自引:0,他引:1
A new Rayleigh light scattering (RLS) assay of protein is presented in this paper. At the optimum pH 4.10, the weak RLS of Arsenazo-DBN can be greatly enhanced by the addition of proteins due to the interaction between protein and Arsenazo-DBN. Based on this, the reactions of Arsenazo-DBN and proteins, including bovine serum albumin, human serum album, gamma-globulin, egg albumin, lysozyme and trypsin, were studied. A new quantitative determination method for proteins has been developed. The linear range for human serum albumin, for example, is 0.085-34.62 micrograms mL-1 with a detection limit of 44.8 ng mL-1. Besides high sensitivity, the method is characterized by good reproducibility, rapidity of reaction, good stability, and few interfering substances. The determination of the proteins in human serum and urine samples by this method give results very close to those obtained using Coomassie Brilliant Blue G-250 colorimetry, with relative standard deviations of 0.7-2.5%. 相似文献
164.
In this paper, the voltammetric method was used for the first time to study the effect of Cisplatin-liposome on Hela cells. The results showed the voltammetric behavior of Hela cells was irreversible and the peak current had linear relationship with the cell number. With both Cisplatin-liposome concentration and treating time increasing, the peak current decreased. The peak current decreasing was in accordance with the nuclear damage and loss of mitochondrial membrane potential revealed by two-photon laser scanning microscopy and confocal laser scanning microscopy. This voltammetric method may provide a simple way to study the electron-transfer mechanism in drug-treating cells. 相似文献
165.
Zanolari B Wolfender JL Guilet D Marston A Queiroz EF Paulo MQ Hostettmann K 《Journal of chromatography. A》2003,1020(1):75-89
The bark of catuaba (Erythroxylum vacciniifolium Martius, Erythroxylaceae), a tree native to the northern part of Brazil, was investigated for its alkaloid content. With the aim of obtaining preliminary structure information on-line, the alkaloid extract was analysed by high-performance liquid chromatography coupled to diode array UV detection, to mass spectrometry and to nuclear magnetic resonance. Interpretation of on-line spectroscopic data obtained from this extract led to structural elucidation of six new alkaloids and partial identification of 18 potentially original alkaloids bearing the same tropane skeleton esterified in positions 3 and 6 by 1-methyl-1H-pyrrol-2-carboxylic acid and/or 4-hydroxy-3,5-dimethoxybenzoic acid. 相似文献
166.
M. G. Fan Y. C. Liang Y. F. Ming J. X. Chen T. Ye Q. Y. Zhang B. A. Xu S. Jin 《Research on Chemical Intermediates》1998,24(9):961-971
Photophysical behavior of spiro[1,3,3-trimethylindolino-2,3′-naphtho[2,1-b]-1,4-oxazine] (SP1) and spiro[1,3,3,2′-tetramethylindolino-2,3′-naphtho[2,1-b]-1,4-oxazine] (SP2) were studied. The fluorescent species and their spectra of SP1 and SP2 in polar solvents (acetonitrile and methanol) and non-polar solvent (cyclohexane) were investigated. The fluorescence decay
in polar solvents was studied by picosecond time-correlated single photon counting. In most cases, fluorescence decay obeyed
triexponential decay kinetics. The major fluorescent species is an excited intermediate which has similar conformation as
its precursor (1
SP
*) formed after the bond cleavage between spirocarbon and oxygen in oxazine ring. The effects of molecular structure and solvent
polarity on fluorescence spectra and fluorescence decay lifetime were studied. 相似文献
167.
BF3-OEt2 decompostion of azides or leads to the coupling product Schiff base imine intermediates. 相似文献
168.
169.
Poon KW Liu W Chan PK Yang Q Chan TW Mak TC Ng DK 《The Journal of organic chemistry》2001,66(5):1553-1559
Up to eight redox-active ferrocenyl units have been incorporated, through the unsaturated ethynyl linkers, on the periphery of a series of cyclic tetrapyrrole derivatives including zinc(II) phthalocyanine and 2,3-naphthalocyanine, and nickel(II) meso-diphenylporphyrin. The synthesis of the former two macrocycles 4 and 7 involves the Sonogashira coupling reaction of ferrocenylethyne with 4,5-dichlorophthalonitrile (1) or 6,7-dibromonaphthalonitrile (5), respectively, followed by a base-promoted cyclization. The meso-bis(ferrocenylethynyl)porphyrin 11 has been prepared from the dibromo analogue 10 also by a palladium-catalyzed coupling reaction. These novel macrocyclic compounds have been spectroscopically and electrochemically characterized. As revealed by cyclic voltammetry, the ferrocenyl moieties appear to be electrochemically independent in these complexes and there is no significant electronic coupling among the iron(II) centers. 相似文献
170.
A high-performance capillary electrophoresis with electrochemical detection (CE-ED) method has been employed for the determination of six bioactive ingredients in traditional Chinese herbs, Herba cepbalanoplosis segeti and Herba cirsii japonici. The effects of several factors such as the acidity and concentration of running buffer, the separation voltage, the applied potential and the injection time on CE-ED were investigated. Under the optimum conditions, the six analytes could be well separated within 21 min in a 75 cm length capillary at the separation voltage of 15 kV in a 50 mmol L–1 borax running buffer (pH 8.4). A 300 m diameter carbon disk electrode was used as the working electrode positioned carefully opposite the outlet of the capillary in a wall-jet configuration at potential of +950 mV (vs. SCE). Good linear relationship was established between peak current and concentration of analytes over two orders of magnitude with detection limits (S/N=3) ranged from 1.5×10–7 to 6.0×10–7 g mL–1 for all six analytes. This proposed method has been successfully applied for the analysis of traditional Chinese herbs after a relatively simple extraction procedure, further on, for the differentiation of these above two seemingly identical herbs based on their electropherograms or characteristic electrochemical profiles. 相似文献