全文获取类型
收费全文 | 3797篇 |
免费 | 700篇 |
国内免费 | 559篇 |
专业分类
化学 | 2595篇 |
晶体学 | 62篇 |
力学 | 258篇 |
综合类 | 23篇 |
数学 | 583篇 |
物理学 | 1535篇 |
出版年
2024年 | 3篇 |
2023年 | 89篇 |
2022年 | 82篇 |
2021年 | 132篇 |
2020年 | 183篇 |
2019年 | 143篇 |
2018年 | 162篇 |
2017年 | 173篇 |
2016年 | 183篇 |
2015年 | 183篇 |
2014年 | 223篇 |
2013年 | 301篇 |
2012年 | 348篇 |
2011年 | 368篇 |
2010年 | 231篇 |
2009年 | 273篇 |
2008年 | 275篇 |
2007年 | 232篇 |
2006年 | 268篇 |
2005年 | 183篇 |
2004年 | 122篇 |
2003年 | 109篇 |
2002年 | 106篇 |
2001年 | 86篇 |
2000年 | 72篇 |
1999年 | 79篇 |
1998年 | 66篇 |
1997年 | 50篇 |
1996年 | 59篇 |
1995年 | 37篇 |
1994年 | 39篇 |
1993年 | 30篇 |
1992年 | 26篇 |
1991年 | 30篇 |
1990年 | 24篇 |
1989年 | 12篇 |
1988年 | 10篇 |
1987年 | 13篇 |
1986年 | 7篇 |
1985年 | 5篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1973年 | 2篇 |
1957年 | 2篇 |
1929年 | 2篇 |
1926年 | 2篇 |
排序方式: 共有5056条查询结果,搜索用时 15 毫秒
61.
Bar G Bennati M Nguyen HH Ge J Stubbe JA Griffin RG 《Journal of the American Chemical Society》2001,123(15):3569-3576
High-frequency pulsed EPR and ENDOR have been employed to characterize the tyrosyl radical (Y*)-diiron cofactor in the Y2-containing R2 subunit of ribonucleotide reductase (RNR) from yeast. The present work represents the first use of 140-GHz time domain EPR and ENDOR to examine this system and demonstrates the capabilities of the method to elucidate the electronic structure and the chemical environment of protein radicals. Low-temperature spin-echo-detected EPR spectra of yeast Y* reveal an EPR line shape typical of a tyrosyl radical; however, when compared with the EPR spectra of Y* from E. coli RNR, a substantial upfield shift of the g(1)-value is observed. The origin of the shift in g(1) was investigated by 140-GHz (1)H and (2)H pulsed ENDOR experiments of the Y2-containing subunit in protonated and D(2)O-exchanged buffer. (2)H ENDOR spectra and simulations provide unambiguous evidence for one strongly coupled (2)H arising from a bond between the radical and an exchangeable proton of an adjacent residue or a water molecule. Orientation-selective 140-GHz ENDOR spectra indicate the direction of the hydrogen bond with respect to the molecular symmetry axes and the bond length (1.81 A). Finally, we have performed saturation recovery experiments and observed enhanced spin lattice relaxation rates of the Y* above 10 K. At temperatures higher than 20 K, the relaxation rates are isotropic across the EPR line, a phenomenon that we attribute to isotropic exchange interaction between Y* and the first excited paramagnetic state of the diiron cluster adjacent to it. From the activation energy of the rates, we determine the exchange interaction between the two irons of the cluster, J(exc) = -85 cm(-)(1). The relaxation mechanism and the presence of the hydrogen bond are discussed in terms of the differences in the structure of the Y*-diiron cofactor in yeast Y2 and other class I R2s. 相似文献
62.
63.
The bridged tri-imidazoliums 3.3X^--5.3X^-(X^-=PF6^-,Br^-,I^-)and bis-imidazoliums 6.2PF6^- were synthesized by N-quaternization of imidazole derivative 1 in acetonitrile under reflux.UV spectroscopic titration experiments showed that the halide salts and hexafluorophosphate salts of these imidazoliums exhibited good recognition toward anions in water and in acetonitrile,respectively. 相似文献
64.
Ge JP Wang J Zhang HX Wang X Peng Q Li YD 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(6):1889-1894
Three-dimensional, orthogonal lead sulfide (PbS) nanowire arrays and networks have been prepared by using a simple, atmospheric pressure chemical vapor deposition (APCVD) method. These uniform nanowires (average diameter 30 nm) grow epitaxially from the surface of the initial PbS crystal seeds and form orthogonal arrays and networks in space. The growth mechanism has been explored, and the process was classified as homogeneous, epitaxial growth in the 200 directions. Furthermore, Raman spectra of PbS nanowires are reported here, and their characteristic Raman peak (190 cm(-1), no shoulder) could be used as a unique probe for the study of PbS nanomaterials. 相似文献
65.
Wei Ge ZHANG Ying Hua JIN Ping QI Kai BAO Jin Guang LIN Nai Li WANG Xin Shen YAO 《中国化学快报》2006,17(1):9-11
Erythromycin has been extensively used in the treatment of bacterial infections for over 50 years1. In addition to the antimicrobial effect, the quite unique antiinflammatory activity of the erythromycin derivatives has attracted much attention as new the… 相似文献
66.
自组装DNA与[Co(phen)3]2+/3+相互作用的表面增强拉曼光谱法研究 总被引:3,自引:0,他引:3
对金基体上自组装ssDNA及dsDNA与钴邻菲啉配合物离子([Co(phen)3]2+/3+)相互作用进行电化学现场表面增强拉曼光谱(SERS)研究,获得相互作用位点及相互作用模式的信息.dsDNA与[Co(phen)3]2+/3+存在一定的嵌插作用,即配合物通过配体邻菲啉(phen)环以嵌插模式结合在碱基A-T及G-C富集区,同时与磷酸二酯键PO2结合,并伴随dsDNA螺旋构象由B型向A型转变;而[Co(phen)3]2+/3+则是以静电模式与ssDNA的磷酸二酯键PO2及脱氧核糖组成的骨架相互作用. 相似文献
67.
血清中Mo、Se、Mn、Cu、Zn与食管癌的关系探讨 总被引:1,自引:0,他引:1
通过对18例食管癌患者以及80例对照组血清中Mo、Se、Mn、Cu、Zn的测定分析,发现食管瘤患者血硒含量明显低于对照组,二者之间有极显著性差异(P<0.01)。而血铜、铜/锌比值食管癌组明显高于对照组,差异有显著性(P<0.05)。Mo、Mn、Zn元素的含量在二组之间无显著性差异(P>0.05).提示血清硒铜与食管癌有关。 相似文献
68.
Uniform and sphere-like nanoparticles of crystalline Pr3+-doped CaTiO3 have been prepared from complex polymer precursor at 600°C, in which, metal atoms are previously dispersed by citric acid in ethylene glycol solvent. The decomposition process of the precursor, crystallization, and particle sizes of CaTiO3 have been investigated by using thermal analysis, powder X-ray diffraction and transmission electron microscopy. Diffuse reflectance spectra, photoluminescence and decay curve indicate that a strong red emission located at the nearly NTCS “ideal red” site is deduced from the energy transfer from the band gap absorption to doping Pr3+ ions. The thermoluminescence curves exhibit that a potential long phosphorescent material based on Pr3+-doped CaTiO3 will be explored in future. 相似文献
69.
Polyurethanes are one kind of relic protection materials commonly used. During artificial photo-ageing, three polyurethanes, HDI-based polyurethane, MDI-based polyurethane and TDI-based polyurethane, have been considered to undergo UV radiation. Photochemical degradation of the polyurethanes has been monitored by means of Fourier transform infrared spectroscopy with attenuated total reflection accessory (FTIR-ATR). It was proved that the mechanism of the photochemical degradation of polyurethanes might be the scissions of carbamate (urethane) groups and the re-reactions of radical groups formed in the scission reactions. From the experiment results HDI-based polyurethane, an aliphatic diisocyanate, could be considered to be more suitably used as relic protection materials among these three polyurethanes for its ageing products with less color. 相似文献
70.
A new approach to indolizines has been developed using a 5-endo-trig iodocyclization of allylic esters followed by isomerization and dehydroiodination facilitated by triethylamine at rt. This mild procedure enabled us to synthesize a number of highly substituted indolizines in good yields. 相似文献