全文获取类型
收费全文 | 61121篇 |
免费 | 10262篇 |
国内免费 | 7468篇 |
专业分类
化学 | 44491篇 |
晶体学 | 784篇 |
力学 | 3546篇 |
综合类 | 478篇 |
数学 | 7155篇 |
物理学 | 22397篇 |
出版年
2024年 | 119篇 |
2023年 | 1167篇 |
2022年 | 1718篇 |
2021年 | 2160篇 |
2020年 | 2535篇 |
2019年 | 2429篇 |
2018年 | 2036篇 |
2017年 | 1959篇 |
2016年 | 2985篇 |
2015年 | 2966篇 |
2014年 | 3564篇 |
2013年 | 4541篇 |
2012年 | 5526篇 |
2011年 | 5661篇 |
2010年 | 4015篇 |
2009年 | 3824篇 |
2008年 | 4186篇 |
2007年 | 3683篇 |
2006年 | 3311篇 |
2005年 | 2817篇 |
2004年 | 2238篇 |
2003年 | 1779篇 |
2002年 | 1836篇 |
2001年 | 1464篇 |
2000年 | 1252篇 |
1999年 | 1258篇 |
1998年 | 1010篇 |
1997年 | 914篇 |
1996年 | 916篇 |
1995年 | 822篇 |
1994年 | 697篇 |
1993年 | 598篇 |
1992年 | 480篇 |
1991年 | 442篇 |
1990年 | 360篇 |
1989年 | 263篇 |
1988年 | 202篇 |
1987年 | 183篇 |
1986年 | 175篇 |
1985年 | 153篇 |
1984年 | 99篇 |
1983年 | 107篇 |
1982年 | 60篇 |
1981年 | 49篇 |
1980年 | 32篇 |
1979年 | 32篇 |
1977年 | 23篇 |
1976年 | 22篇 |
1975年 | 23篇 |
1972年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
Nd—Al双金属活性体的组成及其对共轭双烯烃的聚合 总被引:1,自引:0,他引:1
稀土Ziegler-Natta催化剂活性体对双烯烃配位聚合的研究已有很多报道。作者曾从NdCl_3·3P_(350)~(**)-Al(i-Bu)_3体系分离出Nd-Al双金属活性体。本文从NdCl_3·3P_(350)-HAl(i-Bu)_2和Al(C_2H_5)_3反应体系中分离出一系列Nd-Al双金属活性体,用元素分析方法研究了这些活性体的组成,并综合考察了在无助催化剂AlR_3存在下从不同烷基铝获得的活性体本身对共轭双烯烃的定向聚合能力。 单体、溶剂、HAl(i-Bu)_2、Al(C_2H_5)_5及活性体的合成,聚合方法,聚合物表征均按文献[4]。 相似文献
992.
The application of polyfluorenes in polymeric light-emitting diodes has been hampered because of the charge injection difficulties and the troublesome formation of a tailed emission band at long wavelengths (>500 nm) during device fabrication and operation, leading to both a color instability and reduced efficiency. The incorporation of the phenothiazine units has been proven to significantly enhance the hole injection and charge carrier balance and at the same time efficiently suppress the keto defect emission. In this contribution, we apply quantum-chemical techniques to investigate poly[10-(N-(2'-methyl)phenothiazine-3,7-diyl) and its fluorene copolymer poly[10-(N-(2'-methyl)phenothiazine-3,7-diyl)-co-alt-2,7-(9,9-dimethylfluorene)] (PFPTZ) and gain a detailed understanding the influence of phenothiazine units on the electronic and optical properties of fluorene derivatives. Density functional theory (DFT) and time-dependent DFT approaches are employed to study the neutral molecules, HOMO-LUMO gaps (Delta(H-L)), the lowest excitation energies (E(g)'s), positive and negative ions, as well as the IPs and EAs, focusing on the superiority of the electronic and optical properties attributed to the introduction of electron-donating moiety phenothiazine (PTZ) through comparing with pristine polyfluorene. The outcomes show that the highly nonplanar conformation of phenothiazine ring in the ground state preclude sufficiently close intermolecular interactions essential to forming aggregates or excimers. Furthermore, the HOMO energies lift about 0.4 eV, and thus, the IPs decrease about 0.3 eV in PFPTZ, suggesting the significant improved hole-accepting and transporting abilities, due to the electron-donating properties of phenothiazine ring by the presence of electron-rich sulfur and nitrogen heteroatoms and highly nonplanar characters, resulting in the enhanced performances in both efficiency and brightness compared with pristine polyfluorene. In addition, even though the introduction of electron-donating moiety PTZ onto fluorene leads to a slight bathochromic shift in absorption and emission spectra, the copolymer still exhibited strong blue emission. 相似文献
993.
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
994.
Fabrication and characterization of miniature, flexible, planar biosensors for monitoring l-lactate accumulation in an ischemic myocardium are described. Three configurations of Au-based electrodes were fabricated by a photolithographic technique on flexible polyimide Kapton((R)) foil. All sensors are based on an immobilized lactate oxidase with amperometric detection of the enzymatically produced hydrogen peroxide at a platinum-electroplated-gold base electrode polarized at 0.5 V versus Ag/AgCl. An inner electropolymeric layer is used to prevent electrode fouling and to reject the interference effects of easily oxidizable molecules. In addition, a diffusion controlling outer layer that greatly enhances the linear dynamic range of the sensor, is obtained by casting a polyurethane external film. The developed sensor was evaluated in vitro and proved to have high selectivity, good operational stability, good accuracy and precision (average recovery = 102.3 +/- 0.4% for control sera), fast response time (t(95) = 20 s) and high upper limit of the linear dynamic range (25-80 mM, with sensitivity of 1.7-0.4 nA mM(-1) respectively at PO(2) = 15 mmHg). Subsequently, the sensor was brought into direct contact with the surface of the rabbit papillary muscle and used for continuous quantitative monitoring of extracellular lactate accumulation during no-flow ischemia. 相似文献
995.
顺磁性聚酯金属配合物的合成及其驰豫性能的研究 总被引:2,自引:0,他引:2
本文通过二乙三胺五乙酸(DTPA)或乙二胺四乙酸(EDTA)的双酸酐与二元醇或二元酚进行聚合反应,制备了两个系列共15种新的聚酯型大分子配体及其顺磁性金属配合物,用核磁、红外光谱以及元素分析表征了配体和配合物的结构。初步试验结果表明,与相应的小分子金属配合物相比,聚酯金属配合物具有较高的弛豫性能。 相似文献
996.
3类手性配体d-10-樟脑磺酸及其衍生物,α-(-)-羟蒎酮及其衍生物,又恶唑啉6衍生物分别与铜(Ⅱ)形成手性铜配合物,催化重氮乙酸酯与1,1-二苯乙烯或异丁烯的环丙烷化加成反应,得到光学活性环丙羧酸酯,不对称诱导最高可达95%e.e.。 相似文献
997.
998.
999.
1000.
Sm(NO_3)_3·6H_2O热分解过程的研究工作虽有文献报道,但结果不尽相同。文献[2]不同于文献[1,3],认为分解过程中存在无水盐阶段;文献[3]不同于文献[1,2],认为分解过程中存在低水合物。而且文献尚缺低水合物热分解机理的报道。我们也曾做过一些工作,但脱水阶段也不详尽。为此,我们详细地研究了Sm(NO_3)_3·nH_2O(n= 相似文献