全文获取类型
收费全文 | 106159篇 |
免费 | 4541篇 |
国内免费 | 3077篇 |
专业分类
化学 | 43740篇 |
晶体学 | 1045篇 |
力学 | 8494篇 |
综合类 | 273篇 |
数学 | 34921篇 |
物理学 | 25304篇 |
出版年
2024年 | 105篇 |
2023年 | 590篇 |
2022年 | 908篇 |
2021年 | 949篇 |
2020年 | 1112篇 |
2019年 | 1083篇 |
2018年 | 11095篇 |
2017年 | 10858篇 |
2016年 | 7203篇 |
2015年 | 2089篇 |
2014年 | 1812篇 |
2013年 | 2340篇 |
2012年 | 6296篇 |
2011年 | 12924篇 |
2010年 | 7177篇 |
2009年 | 7546篇 |
2008年 | 8225篇 |
2007年 | 10256篇 |
2006年 | 1684篇 |
2005年 | 2495篇 |
2004年 | 2429篇 |
2003年 | 2718篇 |
2002年 | 1727篇 |
2001年 | 800篇 |
2000年 | 841篇 |
1999年 | 800篇 |
1998年 | 766篇 |
1997年 | 715篇 |
1996年 | 853篇 |
1995年 | 618篇 |
1994年 | 538篇 |
1993年 | 480篇 |
1992年 | 423篇 |
1991年 | 383篇 |
1990年 | 304篇 |
1989年 | 260篇 |
1988年 | 215篇 |
1987年 | 193篇 |
1986年 | 184篇 |
1985年 | 164篇 |
1984年 | 130篇 |
1983年 | 97篇 |
1982年 | 82篇 |
1981年 | 74篇 |
1980年 | 64篇 |
1979年 | 61篇 |
1978年 | 53篇 |
1975年 | 44篇 |
1914年 | 45篇 |
1909年 | 41篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
草酸锰分解过程的机理函数判别和动力学研究 总被引:6,自引:1,他引:6
用等温热重和线性升温热重分析法研究了草酸锰热分解过程,提出了判断其机理函数的3步判别法。经实验和理论分析证明,该反应受随机成核和晶核随后生长的过程(A_3a机理)支配,其活化能E=103.95 kJ/mol,频率因子A=4.448×10~8min~(-1).动力学补偿效应为IgA=0.09661E-1.2856 相似文献
992.
Zhen-Qian Zhang Hong Li Juan Xu Su Yao Zheng-He Xu Jin-Gang Liu Liang-Nian Ji 《Transition Metal Chemistry》2007,32(6):776-780
The effects of copper ion on the interaction of [Ru(bpy)2HPIP]2+(bpy = 2,2′-bipyridine, HPIP = 2-(2-hydroxyphenyl) imidazo [4,5-f] [1, 10] phenanthroline) with DNA have been investigated
by electronic absorption spectroscopy and fluorescence spectroscopy. HPIP ligand of the complex with an intramolecular hydrogen
bond can bind Cu2+ in the absence of DNA, as revealed by the absorbance and fluorescence decrease for [Ru(bpy)2HPIP]2+. The resultant heterometallic complex binds to DNA via intercalation of HPIP into the DNA base pairs and its DNA-binding ability is stronger than [Ru(bpy)2HPIP]2+ itself. The DNA bound [Ru(bpy)2HPIP]2+ cannot bind Cu2+ at low Cu2+ concentration and the intramolecular hydrogen bond in HPIP is located inside the DNA helix. While the Cu2+ concentration is relative high, Cu2+ can quench the fluorescence of DNA bound [Ru(bpy)2HPIP]2+. The quenching reason is proposed. 相似文献
993.
以大孔微硅胶作基体,经γ-氨丙基三乙氧基硅烷活化与间隔臂氯代环内烷反应后,再与预先合成的四(对羟基苯基)卟啉配体键合,构成电荷转移型亲和色谱固定相。以PH=7.0的磷酸盐缓冲溶液作流动相,成功实现对一些核苷酸的高效液相亲和色谱分离。 相似文献
994.
S. K. Huang M. H. Rood S. H. Zhao 《Journal of the American Society for Mass Spectrometry》1997,8(9):996-1009
Fast atom bombardment (FAB) mass spectrometry provides useful structural information about salen complexes and salen-based oxo transfer catalysts that are not appreciably soluble in organic solvents. It was discovered that initial dissolution of these complexes in trifluoroacetic acid was crucial for producing good FAB mass spectra. Trifluoroacetic acid helps dissolve the salen-based catalysts, concentrates the analyte molecules at the matrix surface, and most importantly, suppresses the reduction process, which is a well-known phenomenon when protic matrices are used. The best FAB matrices for these catalysts were found to be thioglycerol and “magic bullet.” However, dechlorination occurred under the acid conditions for complexes containing iron chloride and manganese chloride. Demetalation also occurred for nickel-containing oxo transfer salen-based complexes. When the salen-based complexes are soluble in LC solvents, they can be analyzed easily by atmospheric pressure chemical ionization (APCI) mass spectrometry without the employment of relatively nonvolatile matrices. In addition, APCI/MS provides much more sensitive detection for manganese-salen complexes when compared with FAB results. No dechlorination or demetalation were observed when a negative ion mode APCI was employed. To our knowledge, this is the first time that an intact molecule of this type of complex has been observed by mass spectrometry. 相似文献
995.
在硅磷酸镧中Ce^3+离子对Tb^3+离子的敏化 总被引:1,自引:0,他引:1
实验表明在La2O3·0.01SiO2·0.95P2O5基质中Ce^3 对Tb^3 有强的敏化作用。254nm紫外光激发下温度对Tb^3 激活的Ce^3 、Tb^3 共激活试样的发射强度的Ce^3 、Tb^3 共激活的试样Tb^3 的^5D4→^7F6:5:4跃迁的发射强度随湿度的变化。计算了Ce^3 到Tb^3 的能量传递效率。初步探讨了Ce对Tb的能量传递机理。 相似文献
996.
G. Ortega Zarzosa S. A. Palomares Sánchez J. R. Martánez Facundo Ruiz M. G. Sánchez-Loredo 《Journal of Sol-Gel Science and Technology》2005,35(1):5-11
Composites containing Pd aggregates dispersed in amorphous silica are of interest from both a fundamental and applied point of view because of their attractive catalytic properties. The silica powders added with palladium, prepared by the sol-gel method, were studied using X-ray diffraction, and IR- and UV-Vis-spectrophotometry. Silica xerogel samples were prepared using a ethanol/H2O/TEOS molar ratio of 4:11.6:1 and loaded with sodium tetrachloropalladate. The silica xerogel microstructure of the powders was studied as a function of annealing temperature. Attention was paid to the evolution of the glass matrix as well as the palladium aggregates in the SiO2 matrix. We found in our samples partial crystallization of the glass matrix in form of quartz and cristobalite phases with palladium oxide and metallic palladium phase at 1000∘C. The Rietveld refinement method was used in order to determine the percentage of the phase contents. 相似文献
997.
DongJunWANG QunLUO DanDanJIA XiaoDongLI XinQiouWANG YongHuang ZhenZHEN XinHouLIU 《中国化学快报》2003,14(12):1306-1308
The hydrolysis of tetraethoxysilane (TEOS) occurred on the surface of poly(methyl methacrylate) (PMMA) microshperes immediately after these microshperes were prepared in TEOS. Micron-sized hollow SiO2 spheres were obtained by calcination of the coated PMMA microshperes. It was found that the final hollow spheres were constituted by small SiO2 particles. 相似文献
998.
Novel chiral iPr-tris(oxazoline)/Cu(ClO4)2 x 6H2O catalyzed coupling of terminal acetylenes and nitrones to afford cis-disubstituted beta-lactams is described; the choice of base proves essential to both the diastereoselectivity and the enantioselectivity. 相似文献
999.
1000.
Jun Zhang Kaimin Liu Gengmei Xing Tongxiang Ren Shukuan Wang 《Journal of Radioanalytical and Nuclear Chemistry》2007,272(3):605-609
Gd@C82(OH)40 has been developed as a new generation of MRI contrast agent. But recently, it was found that Gd@C82(OH)
x
with a larger number of OH (x>36) would lead to cage break and hence, release of highly toxic Gd ions. We synthesized the more stable Gd@C82(OH)
x
with less OH-number, Gd@C82(OH)16, and studied its proton relaxivity and MRI images. The results indicate that Gd@C82(OH)16 also gives high proton relaxivity, even higher than that of (NMG)2-Gd-DTPA. The bio-distribution indicated that Gd@C82(OH)16 tends to be entrapped in the liver and kidney and remained in tissue for about 2 hours. The results suggest that the more
stable metallofullerene derivative Gd@C82(OH)16 can be the potential candidate of the new MRI contrast agent. 相似文献