全文获取类型
收费全文 | 6543篇 |
免费 | 503篇 |
国内免费 | 360篇 |
专业分类
化学 | 4025篇 |
晶体学 | 58篇 |
力学 | 312篇 |
综合类 | 40篇 |
数学 | 831篇 |
物理学 | 2140篇 |
出版年
2024年 | 17篇 |
2023年 | 77篇 |
2022年 | 240篇 |
2021年 | 215篇 |
2020年 | 259篇 |
2019年 | 210篇 |
2018年 | 175篇 |
2017年 | 167篇 |
2016年 | 262篇 |
2015年 | 274篇 |
2014年 | 258篇 |
2013年 | 437篇 |
2012年 | 436篇 |
2011年 | 511篇 |
2010年 | 326篇 |
2009年 | 322篇 |
2008年 | 378篇 |
2007年 | 365篇 |
2006年 | 328篇 |
2005年 | 282篇 |
2004年 | 229篇 |
2003年 | 195篇 |
2002年 | 168篇 |
2001年 | 142篇 |
2000年 | 86篇 |
1999年 | 100篇 |
1998年 | 61篇 |
1997年 | 53篇 |
1996年 | 69篇 |
1995年 | 57篇 |
1994年 | 71篇 |
1993年 | 56篇 |
1992年 | 49篇 |
1991年 | 39篇 |
1990年 | 41篇 |
1989年 | 30篇 |
1988年 | 22篇 |
1987年 | 23篇 |
1986年 | 18篇 |
1985年 | 30篇 |
1984年 | 40篇 |
1983年 | 16篇 |
1982年 | 35篇 |
1981年 | 19篇 |
1980年 | 22篇 |
1979年 | 37篇 |
1978年 | 26篇 |
1976年 | 23篇 |
1975年 | 15篇 |
1974年 | 20篇 |
排序方式: 共有7406条查询结果,搜索用时 0 毫秒
91.
M. Di Serio B. Apicella G. Grieco P. Iengo L. Fiocca R. Po E. Santacesaria 《Journal of molecular catalysis. A, Chemical》1998,130(3):128-240
Kinetic and catalytic aspects of DMT transesterification reaction, key step in the industrial production of polyethylenterephtalate (PET), have been deepened also through the use of model molecules such as CH3COO–Ph–X. These molecules give the same reactions with ethylene glycol occurring in the DMT transesterification too. The use of model molecules in the study of this reaction seems therefore to be promising in perspective. As we observed, however, the nature of the para-substituent X has a very strong influence on the reaction rate, when salts of bivalent metals such as Zn, Cd, Co, Mg, Mn, are used as catalysts, while this influence is much smaller when a tetravalent metal, as Ti, is used. This fact suggests that the transesterification mechanism operating in the two cases is different and this suggestion has been confirmed by applying Hammett's approach to the available kinetic data. Experimental kinetic runs were all performed at 193°C, by withdrawing small samples of the reaction mixture at different reaction times. These samples were gaschromatographically analyzed. We found volcano shaped curves of the reaction rates as a function of the metal ion acidities and we obtained different trends with a maximum of activity shifted from a metal to another for different substrates. A comparison of the kinetic results obtained, respectively, with the model molecules and DMT will be reported too. 相似文献
92.
Summary A high-performance liquid chromatography (HPLC) assay for estriol in nonpregnancy urine is described. After Enzymic hydrolysis, the estriol is extracted from urine by the sorbent trap technique utilizing graphitized carbon black (Carbopack B). After some washing steps, estriol is desorbed by a suitable solvent system. After solvent removal, the sample is injected into an HPLC column for estriol quantification. Analytical recovery of estriol was 96.1%. The precision of the method was 2.6 and 4.9% respectively at 145 and 10.6ng/ml of urine. The limit of sensitivity was set at 0.8 ng/ml of urine. The mean contents of estriol in the follicular and luteal phases were respectively 11.3 and 38.8 ng/ml of urine.Dedicated to Prof. Dr. A. Liberti on the occasion of his 70th birthday. 相似文献
93.
We performed ab initio molecular orbital (MO) calculations using Hartree—Fock SCF, and second- and fourth-order Møller—Plesset perturbation theory for hydrogen migration reactions on the singlet vinyl fluoride potential energy surface. We used different basis sets and polarization functions to obtain the stationary point geometries and activation barriers. Basis set and the polarization function extension have small effects, while the correlation energy evaluation leads to new conclusions for one of the studied reactions: the product singlet CHCH2F is not a true local minimum on the potential energy surface. 相似文献
94.
Zhao L Zhu G Zhang D Di Y Chen Y Terasaki O Qiu S 《The journal of physical chemistry. B》2005,109(2):764-768
Using 1,2-bis(trimethoxysilyl)ethane as organosiloxane precursor and a triblock copolymer surfactant, Pluronic F127, as template, a highly ordered mesoporous organosilica with large cagelike pores has been successfully synthesized. Its structure was resolved to be 3-D cubic Fmm by high-resolution transmission electron microscopy. The intergrowth of hexagonal close-packed and cubic close-packed phases was observed in this material. The effect of different siliceous precursors on the mesostructure was also investigated. 相似文献
95.
UVB irradiation of normal human skin favors the development of type-2 T-cells in vivo and in primary dermal cell cultures 总被引:1,自引:0,他引:1
Di Nuzzo S Sylva-Steenland RM Koomen CW Nakagawa S van Breemen M de Rie MA Das PK Bos JD Teunissen MB 《Photochemistry and photobiology》2002,76(3):301-309
To determine the effect of UVB exposure on the balance of type-1 or type-2 T-cells in skin, we examined the expression of key markers interferon (IFN)-gamma and interleukin (IL)-4 in cryostat sections. IFN-gamma mRNA was clearly detectable in nonirradiated control skin, and IFN-gamma protein was found in 2% of the dermal CD3pos T-cells, whereas IL-4 mRNA was hardly detectable, and no IL-4 protein was found. In contrast, IL-4 mRNA expression increased upon irradiation, and IL-4 was found in 2% of the T-cells at day 2 after UVB-exposure. Concomitantly, IFN-gamma mRNA expression decreased, and IFN-gamma protein became absent. We also analyzed T-cells present in primary dermal cell cultures, which were used as an in vitro equivalent of the in vivo situation. As compared with T-cells from control skin, T-cells in dermal cell cultures from UVB-exposed skin displayed an increased IL-4 and decreased IFN-gamma expression. No such skewing occurred when the T-cells from irradiated skin were cloned in the absence of a dermal microenvironment. Except for an occasional positive T-cell, type-1-associated cell-surface markers (CCR5, CXCR3) or type-2 markers (CCR3, CD30, CRTH2) were undetectable in situ. But these markers were expressed on cultured dermal T-cells from UVB-exposed and control skin at a comparable level, but did not correlate with the IFN-gamma and IL-4 production. Altogether, UVB-induced changes of the dermal microenvironment favor the development of type-2 T-cells. 相似文献
96.
CH2F2…H2O中强π型二级氢键 总被引:1,自引:3,他引:1
通过从头计算,用较大基组6-311+G(2d,2p),在MP2水平上计算得到CH2F2…H2O体系的优化几何构型,与实验结构一致.其中∠F…H-O=116.5°,偏离普通氢键之键角达到63.5°.为探讨产生氢键巨大弯曲的原因,采用点电荷扫描的办法,探测CH2F2…H2O体系中H2O的O原子上的两对孤电子对的方向,发现了一个强的π型二级氢键相互作用.使用这种新的相互作用方式说明了产生这一巨大氢键弯曲的原因,并且在MP4水平上使用Counterpoise技术计算了π型二级氢键的稳定化能. 相似文献
97.
Mario Di Braccio Giorgio Roma Gian Carlo Grossi Giovanni Ciarallo 《Journal of heterocyclic chemistry》1992,29(1):25-31
The reaction of 2-[(N-acyl, N-alkyl or phenyl)amino]-4H-pyrido[1,2-a]pyrimidin-4-ones 8a-g with the N,N-dimethylformamide/phosphorus oxychloride Vilsmeier reagent 1 (95°, 90 minutes) afforded 1-alkyl or phenyl-2H-dipyrido[1,2-a:2′,3′-d]pyrimidine-2,5(1H)?diones, 3-alkyl substituted or not, 10a-g . The starting compounds 8 were prepared by treating 2-amino-4H-pyrido[1,2-a]pyrimidin-4-ones N-alkyl substituted 7a,b or N-phenyl substituted 4 with excess anhydrides (130°, 7 hours) when the 2-(alkylamino) derivatives 7 were used in the reaction, compounds 8 were obtained along with very small amounts of 3-acyl-2-(alkylamino)-4H-pyrido[1,2-a]pyrimidin-4-ones 9 . 相似文献
98.
99.
100.