全文获取类型
收费全文 | 17960篇 |
免费 | 2998篇 |
国内免费 | 2635篇 |
专业分类
化学 | 13772篇 |
晶体学 | 164篇 |
力学 | 1062篇 |
综合类 | 206篇 |
数学 | 1896篇 |
物理学 | 6493篇 |
出版年
2024年 | 63篇 |
2023年 | 383篇 |
2022年 | 558篇 |
2021年 | 632篇 |
2020年 | 780篇 |
2019年 | 707篇 |
2018年 | 637篇 |
2017年 | 523篇 |
2016年 | 869篇 |
2015年 | 833篇 |
2014年 | 1049篇 |
2013年 | 1341篇 |
2012年 | 1584篇 |
2011年 | 1609篇 |
2010年 | 1182篇 |
2009年 | 1132篇 |
2008年 | 1239篇 |
2007年 | 1070篇 |
2006年 | 972篇 |
2005年 | 867篇 |
2004年 | 753篇 |
2003年 | 636篇 |
2002年 | 651篇 |
2001年 | 521篇 |
2000年 | 463篇 |
1999年 | 431篇 |
1998年 | 321篇 |
1997年 | 258篇 |
1996年 | 280篇 |
1995年 | 242篇 |
1994年 | 178篇 |
1993年 | 163篇 |
1992年 | 134篇 |
1991年 | 103篇 |
1990年 | 109篇 |
1989年 | 68篇 |
1988年 | 62篇 |
1987年 | 56篇 |
1986年 | 36篇 |
1985年 | 32篇 |
1984年 | 16篇 |
1983年 | 10篇 |
1982年 | 15篇 |
1981年 | 10篇 |
1980年 | 6篇 |
1979年 | 4篇 |
1971年 | 1篇 |
1957年 | 2篇 |
1936年 | 1篇 |
1916年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
92.
Simultaneous analysis of oxidized and reduced glutathione in cell extracts by capillary zone electrophoresis 总被引:1,自引:0,他引:1
Yang Q Krautmacher C Schilling D Pittelkow MR Naylor S 《Biomedical chromatography : BMC》2002,16(3):224-228
Glutathione (GSH) and glutathione disulfide (GSSG) levels in cells constitute a thiol redox system. They can be used as an indicator of oxidative stress of the cell. In this study, a capillary zone electrophoresis (CZE) method is described that enables quantitation of GSH and GSSG from cellular extracts. The CZE buffer used was 20 mM ammonium acetate containing 5% (v/v) acetic acid at pH 3.1 in conjunction with a polybrene coated capillary operated in reverse polarity mode. Effects of different acids used to prepare cell samples were investigated on CZE performance. The acids include meta phosphoric acid (MPA), trichloroacetic acid (TCA), phosphoric acid (PA) and sulfosalicylic acid (SSA) and are used to stabilize GSH and GSSG before performing CZE analysis. The method features a limit of detection of 4 microM and a limit of quantitation of 12 microM for both GSSG and GSH and recoveries of 94% for GSH and 100% for GSSG. Quantitative analysis of GSSG and GSH in HaCaT cell extracts (5% SSA, w/v) was performed with this method and changes in the ratio of GSH to GSSG in N-ethylmaleimide treated cell sample was observed by comparing with control cell samples. 相似文献
93.
Hu H Qiao M Xie F Fan K Lei H Tan D Bao X Lin H Zong B Zhang X 《The journal of physical chemistry. B》2005,109(11):5186-5192
The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C 1s peak has disappeared, leaving nickel sulfide on the surface. 相似文献
94.
Zhang WW Li HF Liu L Xie JL Lu CS Zhou Y Ren XM Meng QJ 《Journal of colloid and interface science》2003,261(1):82-87
A series of thiol-functionalied azobenzene derivatives (RAzoCnSH: R=H for n=3-6, abbreviated as AzoCnSH; R=CH(3)CONH for n=4, abbreviated as aaAzoC4SH) on gold electrodes were prepared and their self-assembly and electrochemical properties were studied by cyclic voltammetry. They all formed uniform and reproducible self-assembled monolayers (SAMs) on gold and showed well-behaved voltammetric responses in aqueous solution. Both the length of the alkyl chain spacer and the H-bonding of the end acetamino group had effects on the stability and the electrochemical kinetics of the SAMs, and the effect of the H-bonding was dominant. The surface coverage of the SAMs (AzoCnSH) is gradually increased with an increase of the alkyl chain spacer length, whereas the presence of the terminal acetamino group leads to a greater increase of the surface coverage. At a low scan rate, voltammetric responses corresponding to an irreversible two-electron, two-proton reduction/oxidation of the trans-azobenzene redox center were obtained in the range of +300 mV and -800 mV, which exhibited very large peak-to-peak splitting. At a high scan rate of 500 mV/s, two steps of reversible one-electron, one-proton reduction/oxidation corresponding to the cis-isomer in azobenzene-thiol SAMs (n is odd) was clearly observed between +300 and -200 mV. The apparent electron-transfer rate is decreased with increasing distance between the azobenzene redox center and the gold electrode. The existence of the end acetamino group which restricted the conformational change during the redox process also led to a decrease of the standard rate constant, and this restriction effect is more predominant than the distance effect. 相似文献
95.
96.
稀土在鼠肝中的物种分布 总被引:23,自引:0,他引:23
采用 ICP-MS、微量蛋白层析分离技术 ,研究了长时间、低剂量混合稀土及短时间、高剂量硝酸镧分别对大鼠及小鼠作用后 ,稀土在鼠肝中的代谢累积及其物种分布 .结果表明 ,鼠肝中各稀土含量随给药剂量的增加而增大 ,其累积速度大小顺序为 La>Ce>Nd>Pr;经柱层析分离未得到与稀土特异结合的鼠肝蛋白 ;稀土可与多种鼠肝蛋白 (包括多种重要的酶 )结合 ,在一定条件下 ,稀土与其结合蛋白可发生解离 相似文献
97.
Study of urinary nucleosides as biological marker in cancer patients analyzed by micellar electrokinetic capillary chromatography 总被引:10,自引:0,他引:10
Thirteen normal and modified nucleosides, primarily degradation products of transfer ribonucleic acid (tRNA), were evaluated as potential tumor markers for cancer patients. Their urinary concentrations were determined by means of micellar electrokinetic capillary chromatography (MEKC) in the urine from 54 healthy adults and 70 cancer patients, then quantitatively expressed as a function of creatinine excretion. It was found that urinary nucleosides for cancer patients were on the average significantly higher than those for healthy controls, however, no significant differences were found between male and female or between different ages. Based on 13 urinary nucleoside concentrations, principal component analysis (PCA) could be used to classify 72% of cancer patients from the healthy controls. The present study shows that the precise measurement of urinary nucleosides by MEKC in combining with PCA technique may provide a clinically useful approach for diagnosis of cancer. 相似文献
98.
八乙酰乳糖与一缩二乙二醇或二缩三乙二醉承BF3.Et2O催化下反应生成相应的β- 糖苷,后者在同样的催化剂存在下再与八乙酰乳糖反应生成对称的β-构型二聚体。糖苷与二聚体在甲醇钠/甲醇溶液中脱去乙酰基生成目标化合物用于抗癌转移活性研究。 相似文献
99.
Binding of wogonin to human serum albumin: a common binding site of wogonin in subdomain IIA 总被引:4,自引:0,他引:4
Tian J Liu J Xie J Yao X Hu Z Chen X 《Journal of photochemistry and photobiology. B, Biology》2004,74(1):39-45
The binding of wogonin to human serum albumin (HSA) has been studied by spectroscopic method including circular dichroism (CD), infrared spectra (IR) and fluorescence spectra. The fluorescence properties of HSA were examined in presence of wogonin and the fluorescence intensity of HSA was significantly decreased in the presence of wogonin. The binding parameters of wogonin were studied from the fluorescence decreasing of HSA by the fluoremetric titrations. The Stern-Volmer plots indicated that the binding of wogonin to HSA at 296, 303, 310 K is characterized by one binding site with the binding constant K(S-V) at 1.872 x 10(5), 1.561 x 10(5), 1.392 x 10(5), respectively, which are good agreement with the results from the Scatchard plots. The binding process was exothermic, enthalpy driven and spontaneous, as indicated by the thermodynamic analyses, and the major part of the binding energy is hydrophobic interaction, which were consistent with the result of molecule modelling study, and there are also a numbers of hydrogen bonds between wogonin and HSA. Furthermore, the displacement experiments indicate that wogonin can bind to the subdomain IIA, that is, the site I of HSA, which is also good agreement with the result of molecule modelling study. 相似文献
100.
In this study, local least squares (LLS) and principal component analysis (PCA) were applied to deal with the disturbances in a data set of chromatographic fingerprints after necessary data transformations. It has been demonstrated that PCA with standard normal variate (SNV) transformation of data led to meaningful classification of 33 different Erigeron breviscapus herbal samples. The result was also corroborated by variance squares discriminant method. The quality of herbal objects was further evaluated, and the causes of this fact have been explained from a chemical point of view. At the same time, it implied an idea for qualitative evaluation of the herbal objects with a common class pattern of chromatographic fingerprints. 相似文献