全文获取类型
收费全文 | 19704篇 |
免费 | 3295篇 |
国内免费 | 2307篇 |
专业分类
化学 | 13691篇 |
晶体学 | 178篇 |
力学 | 1132篇 |
综合类 | 121篇 |
数学 | 2726篇 |
物理学 | 7458篇 |
出版年
2024年 | 87篇 |
2023年 | 429篇 |
2022年 | 647篇 |
2021年 | 724篇 |
2020年 | 852篇 |
2019年 | 777篇 |
2018年 | 695篇 |
2017年 | 661篇 |
2016年 | 984篇 |
2015年 | 960篇 |
2014年 | 1099篇 |
2013年 | 1465篇 |
2012年 | 1683篇 |
2011年 | 1755篇 |
2010年 | 1231篇 |
2009年 | 1097篇 |
2008年 | 1248篇 |
2007年 | 1104篇 |
2006年 | 977篇 |
2005年 | 883篇 |
2004年 | 703篇 |
2003年 | 613篇 |
2002年 | 683篇 |
2001年 | 543篇 |
2000年 | 438篇 |
1999年 | 429篇 |
1998年 | 343篇 |
1997年 | 311篇 |
1996年 | 331篇 |
1995年 | 291篇 |
1994年 | 233篇 |
1993年 | 163篇 |
1992年 | 165篇 |
1991年 | 158篇 |
1990年 | 123篇 |
1989年 | 94篇 |
1988年 | 54篇 |
1987年 | 57篇 |
1986年 | 71篇 |
1985年 | 47篇 |
1984年 | 32篇 |
1983年 | 26篇 |
1982年 | 15篇 |
1981年 | 11篇 |
1980年 | 4篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1969年 | 1篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
131.
A new potential tetradentate ligand, 1,4-bis(N-1-methylimidazol-2-ylmethyl)-1,4-diazacycloheptane (l), together with its CuII complex [CulCl]ClO4 (1), has been reported. The crystal structure of 1, determined by single-crystal X-ray analysis, shows that it is in chiral P212121 space group. The CuII centre is penta-coordinated in square pyramidal geometry and the diazacycloheptane (DACH) ring adopts normal boat configuration. The most striking feature of this complex is the formation of a 3D network bridged through the C-H?Cl hydrogen bonds with the perchlorate anions in the cavities, and stabilized via π-π stacking interactions along the a-direction. The solution behaviour of 1 has been further investigated by UV/Vis and ESR techniques. 相似文献
132.
Under acidic conditions tellurium(IV) formed a complex with ammonium pyrrolidine dithiocarbamate (APDC). The tellurium(IV) complex was completely retained on a non-polar Isolute silica-based octadecyl (C(18)) sorbent-containing solid-phase extraction (SPE) cartridge, while the uncomplexed Te(VI) passed through the cartridge and remained as a free species in the solution. Only partial Te(IV) was retained on the SPE cartridge for samples without addition of APDC. On the basis of different retention behaviours of the complexed Te(IV) and uncomplexed Te(VI), a simple and highly sensitive method is proposed for the determination of total tellurium and Te(VI) by SPE separation and inductively coupled plasma mass spectrometry (ICP-MS) detection. The Te(IV) concentration was calculated as the difference between total tellurium and Te(VI) concentrations. The detection limit (3 sigma) is 3 ng L(-1) tellurium. Factors affecting the separation and detection of tellurium species were investigated. Coexisting ions did not show significant interferences with the Te(IV)-APDC complex retention and the subsequent ICP-MS detection of Te. The method has been successfully applied to the tellurium speciation analysis in waters with spiked recoveries for Te(IV) and Te(VI) of 86.0-108% and 87.1-97.4%, respectively. 相似文献
133.
为建立快速、简便、灵敏的分光光度法测定血清锌 ,在表面活性剂TritonX -1 0 0存在下 ,用 2 -(5 -溴 -2 -吡啶偶氮 ) -5 -[N ,N -二羧基甲基 ]苯酚 (5 -Br-PADCAP)作显色剂 ,不去蛋白分光光度法测定血清锌。结果表明 ,锌络合物最大吸收波长为 5 5 7nm ,线性范围 0~ 5 0 0μmol L ,摩尔吸光系数为 1 1 2× 1 0 5L·mol-1·cm-1。回收率为 99 9% ,批内变异系数 (CV)为2 1 % ,批间变异系数为 2 9% ,与原子吸收分光光度法 (x)比较具有良好的相关性 ,y =1 0 1 0x-0 1 5 4,r=0 991 8,P >0 0 5。可见本法测定血清锌不必去蛋白、用血量少、方法简便、灵敏可靠 ,适合临床应用 相似文献
134.
Liu H Hu Y Yang S Guo W Lu X Zhao L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(21):6392-6406
We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations. 相似文献
135.
136.
137.
Feng Liu Si Guo Yuan Xiao Li Wang A.E Polikarpov A.A. Shunkevich 《中国化学快报》2007,18(5):588-590
A fibrous sorbent possessing abundant micropore structure was firstly prepared via post-crosslinking reaction on the PP-ST-DVB original fiber. Its micromorphology and sorptive properties were investigated, and the results demonstrated that the novel fibrous hypererosslinked sorbent has narrow pore-size distribution, small average porous radius (1.90 nm), high specific surface area (362.31 m^2/g), and fine sorptive properties for small organic molecules. 相似文献
138.
The electron-correlation and self-interaction corrected generalized exchange local-spin-density functional theory with the Gopinathan, Whitehead, and Bogdanovic Fermi-hole parameters has been employed to give self-consistent field calculations for the quark atoms, the first- and second-order positive ions, and the first- and second-order negative ions of the quark atoms with fractional nuclear charges $ Z = N \pm \frac{1}{3} $ and $ Z = N \pm \frac{2}{3} $. A special technique to obtain the converged second-order negative ions is discussed. The first and second ionization potentials and electron affinities are calculated by the differences of the total energies between the ionized and nonionized systems and compared with the empirical inter-extrapolation results. The agreement between the present calculations and the inter-extrapolated results is excellent for the ionization potentials and reasonably good for the electron affinities of the quark atoms. Finally, the calculated ionization potentials and electron affinities are used in obtaining the electronegativities and hardnesses for these quark atoms. 相似文献
139.
Xiao Zhen Liu Fei Wang Dong Dong Luo Xing Guo Guang Qing Lei 《中国化学快报》2007,18(11):1339-1341
The hydroxyl group of carbocyclic nucleosides was inversed when the compounds were treated with Me_3SiCl,KCN and a catalytic amount of NaI in DMF/CH_3CN. 相似文献
140.
Behaviour of organic pollutants in paper and board samples intended to be in contact with food 总被引:1,自引:0,他引:1
This paper deals with the study of volatile compounds present in a set of three paper and board (P&B) samples of different composition, surface treatment, grammage and thickness. The volatile compounds released by the packaging material (P&B) can be trapped on the food and may then affect the safety and health of consumers. To evaluate if the recycled P&B could be used as food packaging material, adsorption studies have been performed with a selection of chemical substances. The adsorption isotherms are provided. Partition coefficients between paper and air have been calculated for a series of volatile compounds used as model compounds to represent different families of contaminants commonly present in P&B. Values from 4 to 3243 were obtained at different temperatures. The analysis of volatile compounds have been carried out by automatic headspace coupled on-line with GC/MS in SIM mode. The results obtained are shown and discussed. 相似文献