全文获取类型
收费全文 | 20092篇 |
免费 | 3397篇 |
国内免费 | 2280篇 |
专业分类
化学 | 14529篇 |
晶体学 | 261篇 |
力学 | 1225篇 |
综合类 | 186篇 |
数学 | 2056篇 |
物理学 | 7512篇 |
出版年
2024年 | 40篇 |
2023年 | 451篇 |
2022年 | 556篇 |
2021年 | 690篇 |
2020年 | 807篇 |
2019年 | 775篇 |
2018年 | 629篇 |
2017年 | 601篇 |
2016年 | 934篇 |
2015年 | 911篇 |
2014年 | 1061篇 |
2013年 | 1370篇 |
2012年 | 1802篇 |
2011年 | 1888篇 |
2010年 | 1247篇 |
2009年 | 1106篇 |
2008年 | 1293篇 |
2007年 | 1279篇 |
2006年 | 1129篇 |
2005年 | 1006篇 |
2004年 | 720篇 |
2003年 | 628篇 |
2002年 | 568篇 |
2001年 | 430篇 |
2000年 | 409篇 |
1999年 | 470篇 |
1998年 | 355篇 |
1997年 | 369篇 |
1996年 | 309篇 |
1995年 | 296篇 |
1994年 | 302篇 |
1993年 | 246篇 |
1992年 | 196篇 |
1991年 | 198篇 |
1990年 | 177篇 |
1989年 | 112篇 |
1988年 | 86篇 |
1987年 | 89篇 |
1986年 | 60篇 |
1985年 | 44篇 |
1984年 | 43篇 |
1983年 | 24篇 |
1982年 | 25篇 |
1981年 | 18篇 |
1980年 | 13篇 |
1975年 | 2篇 |
1957年 | 4篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
221.
222.
Based on gaseous compound introduction as 1-phenyl-3-methyl-4-benzoylpyrazolone[5](PMBP) chelate of aluminum by electrothermal vaporization in ICP-AES, a method for determination of trace aluminum was developed. Trace aluminum was vaporized at temperature of 1000 degrees C, and the vaporization behavior of aluminum chelate was detailedly investigated. Under the optimum conditions, the detection limit of aluminum was 0.6 ng ml(-1), and the relative standard deviation for 0.1 mug ml(-1) aluminum was 4.7% (n=8). The proposed method was applied to the determination of trace aluminum in rice flour reference materials, and the results well agreed with the reference values. 相似文献
223.
224.
Chen-Xi Zhang Zhi-Liang Liu Dai-Zheng Liao Zong-Hui Jiang Shi-Ping Yan 《Journal of Molecular Structure》2003,650(1-3):21-26
A novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H2O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H2O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py. 相似文献
225.
含氰基侧基聚芳醚砜的合成与表征 总被引:1,自引:0,他引:1
汉2,6-二卤苯甲腈、4,4′-二氯二苯砜、4,4′-二羟基二苯砜、间苯二酚、对苯二酚、酚酞及双酚A为主要原料,合成了含不同结构单元和不同氰基含量的含氰基侧基的聚芳醚砜,并采用IR、^13CNMR等分析手段对其结构进行了表征,同时研究了结构单元和氰基含量对聚芳醚砜性能的影响。 相似文献
226.
227.
Mets motifs, which refer to methionine-rich sequences found in the high-affinity copper transporter Ctr1, also appear in other proteins involved in copper trafficking and homeostasis, including other Ctrs as well as Pco and Cop proteins isolated from copper-resistant bacteria. To understand the coordination chemistry utilized by these proteins, we studied the copper binding properties of a peptide labeled Mets7-PcoC with the sequence Met-Thr-Gly-Met-Lys-Gly-Met-Ser. By comparing this sequence to a series of mutants containing noncoordinating norleucine in place of methionine, we confirm that all three methionine residues are involved in a thioether-only binding site that is selective for Cu(I). Two independent methods, one based on mass spectrometry and one based on rate differences for the copper-catalyzed oxidation of ascorbic acid, provide an effective K(D) of approximately 2.5 microM at pH 4.5 for the 1:1 complex of Mets7-PcoC with Cu(I). These results establish that a relatively simple peptide containing an MX(2)MX(2)M motif is sufficient to bind Cu(I) with an affinity that corresponds well with its proposed biological function of extracellular copper acquisition. 相似文献
228.
Fluorometric investigation of the interaction of bovine serum albumin with surfactants and 6-mercaptopurine 总被引:2,自引:0,他引:2
Hu YJ Liu Y Jiang W Zhao RM Qu SS 《Journal of photochemistry and photobiology. B, Biology》2005,80(3):235-242
Fluorescence quenching in solutions of bovine serum albumin has been investigated in the presence of 6-mercaptopurine and ionic surfactants. Spectroscopic analysis of the emission quenching at different temperatures revealed that the quenching mechanism of bovine serum albumin by 6-mercaptopurine was dynamic quenching mechanism. The Stern–Volmer quenching model has been successfully applied, and the activation energy of the interaction between 6-mercaptopurine and bovine serum albumin as much as 4.26 kJ mol−1 was calculated. The distance r between donor (bovine serum albumin) and acceptor (6-mercaptopurine) was obtained according to fluorescence resonance energy transfer (FRET). The result of synchronous fluorescence spectra shows that the conformation of bovine serum albumin has been changed at the present of 6-mercaptopurine. 相似文献
229.
A method has been developed for the speciation of trace dissolved Fe(II) and Fe(III) in water by coupling gallic acid (GA) modified nanometer-sized alumina micro-column separation with inductively coupled plasma mass spectrometry (ICP-MS). The separation of Fe(II) and Fe(III) was achieved based on the obvious difference in reaction kinetics between Fe(II) and Fe(III) with GA. Fe(III) was selectively retained on the micro-column at pH 5.5-6.5, while Fe(II) could not be retained by the micro-column at the whole tested pH range of 1.0-6.5, and passed through the micro-column. The Fe(II) can be determined by ICP-MS directly without preconcentration/separation procedure, while Fe(III) retained on the micro-column was then eluted with 1.0 mL of 1 mol L(-1) HCl and determined by ICP-MS. The parameters affecting the separation of Fe(II) and Fe(III) were investigated systematically and the optimum separation conditions were established. Under the optimized conditions, the detection limits of 0.48 microg L(-1) and 0.24 microg L(-1) with relative standard deviation of 5.6% and 4.3%(C= 5 microg L(-1), n= 7) for Fe(II) and Fe(III) were found, respectively. No obvious effect on the speciation of Fe(II) and Fe(III) was found with the change of the ratio of Fe(II) and Fe(III) from 0 ratio 10 to 10 ratio 0. The proposed method was applied for the determination of trace Fe(II) and Fe(III) in environmental water and the recoveries for spiked samples were found to be in the range of 97-105%. 相似文献
230.
In order to improve the photosensitizing activity of HB further, the complex of 5,8-di-Br-HB with Al(3+) was first designed and synthesized in high yield. 5,8-di-Br-HB forms a 2:1 type (metal-ligand ratio) complex with Al(3+) measured by molar ratio and continuous variation methods. The new photosensitizer was characterized by UV-Vis, IR, 1H NMR and elemental analysis measurements. Based on the above experimental results, we first proposed a polymer-like structural model of the complex. The water-solubility and red absorption of the [Al(2)(5,8-di-Br-HB)Cl(4)](n) complex are both enhanced over hypocrellin B. In addition, the EPR and spectrophotometric measurements demonstrate that semiquinone anion radical of [Al(2)(5,8-di-Br-HB)Cl(4)](n) can be produced by [Al(2)(5,8-di-Br-HB)Cl(4)](n) photosensitization. The generation efficiency of ([Al(2)(5,8-di-Br-HB)Cl(4)](n))(.-) is almost equal to that of HB(.-). These results obtained indicated that [Al(2)(5,8-di-Br-HB)Cl(4)](n)was at least a favorable Type I phototherapeutic agent. 相似文献