全文获取类型
收费全文 | 729篇 |
免费 | 25篇 |
国内免费 | 2篇 |
专业分类
化学 | 576篇 |
晶体学 | 13篇 |
力学 | 14篇 |
数学 | 41篇 |
物理学 | 112篇 |
出版年
2023年 | 5篇 |
2022年 | 5篇 |
2021年 | 13篇 |
2020年 | 3篇 |
2019年 | 14篇 |
2018年 | 7篇 |
2017年 | 7篇 |
2016年 | 11篇 |
2015年 | 13篇 |
2014年 | 19篇 |
2013年 | 29篇 |
2012年 | 43篇 |
2011年 | 40篇 |
2010年 | 29篇 |
2009年 | 21篇 |
2008年 | 30篇 |
2007年 | 41篇 |
2006年 | 31篇 |
2005年 | 37篇 |
2004年 | 35篇 |
2003年 | 45篇 |
2002年 | 54篇 |
2001年 | 16篇 |
2000年 | 15篇 |
1999年 | 7篇 |
1998年 | 6篇 |
1997年 | 17篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 8篇 |
1992年 | 6篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 16篇 |
1984年 | 8篇 |
1983年 | 7篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 10篇 |
1979年 | 14篇 |
1978年 | 5篇 |
1977年 | 12篇 |
1976年 | 4篇 |
1975年 | 5篇 |
1974年 | 3篇 |
1972年 | 2篇 |
排序方式: 共有756条查询结果,搜索用时 31 毫秒
11.
The reaction of alpha,beta-unsaturated imines with CO and alkenes in the presence of Ru(3)(CO)(12) as a catalyst results in a three-component coupling reaction that gives alpha,alpha-disubstituted beta,gamma-unsaturated gamma-butyrolactams. The reaction proceeds via a two-step sequence involving the initial formation of ketone derivatives by catalytic carbonylation at the beta-olefinic C-H bonds of alpha,beta-unsaturated imines, followed by the (uncatalyzed) intramolecular nucleophilic attack of the imine nitrogen on the ketonic carbon to generate a tetrahedral intermediate, which then undergoes a 1,2-ethyl migration. The reaction of a cyclic unsaturated imine, derived from the reaction of (1R)-(-)-myrtenal with tert-butylamine, gives a beta-aminocyclopentene derivative, which is formed by an aldol-type condensation of the initially formed ketone, indicating the initial formation of ethyl ketone. 相似文献
12.
Takakazu Yamamoto Junichi Ishizu Sanshiro Komiya Yoshiyuki Nakamura Akio Yamamoto 《Journal of organometallic chemistry》1979,171(1):103-112
13C NMR data are given for a series of phosphinenickel(0) complexes of ethyl methacrylate (ema), Ni(PR3)2(CH2=C(CH3)COOC2H5) (PR3 = PPh3 (Ia), PEtPh2 (Ib), PEt2Ph (Ic), PMe2Ph (Id), PEt3 (Ie)). The olefinic carbon signals of ema shift upfield by 71.5–86.5 ppm on coordination, the magnitude of the upfield shift increasing with increase in the bacisity of the phosphine ligand. The effect of the basicity of PR3 is discussed on the basis of the back-bonding from Ni to ema. Variable temperature1H NMR studies reveal that the ema of Id, the complex having the least sterically demanding phosphine ligands, exchanges with free ema in toluene on the NMR time scale. The dependence of the rate of exchange on the concentration of ema shows that the exchange proceeds through anSN2 mechanism. The activation parameters are: ΔH273≠ 2.75 kcal/mol, ΔG273≠ 12.7 kcal/mol, ΔS273≠ ?37 e.u. The31P NMR spectra of the complexes show two doublets when the exchange is frozen out, indicating the inequivalence of the two phosphine ligands in the ema-coordinated complex. The difference in the31P chemical shifts of the two coordinated tertiary phosphines increases with increase in the basicity of the PR3 ligand. 相似文献
13.
14.
15.
N-Lithioketimines, generated in situ from 2-substituted benzonitriles and t-BuLi, reacted with carbon monoxide to afford five-, six- or seven-membered cyclic products, involving participation by the ortho substituents. The reactions represent new selective transformations of carbonyllithium intermediate which previously were observed to lead to complicated reactions. 相似文献
16.
Photoluminescence enhancement of PEG-modified YAG:Ce3+ nanocrystal phosphor prepared by glycothermal method 总被引:1,自引:0,他引:1
Y3Al5O12:Ce3+ (YAG:Ce3+) nanocrystals were synthesized in 1,4-butylene glycol (BG) with and without poly(ethylene glycol) (PEG) by the glycothermal method. The internal quantum efficiency of the photoluminescence (PL) corresponding to the 5d --> 4f transition of Ce3+ in the YAG:Ce3+ nanocrystal increased from 21.3 to 37.9% by addition of PEG, while no appreciable change in the primary particle size, the crystallite size, and the lattice distortion was recognized by transmission electron microscopy and X-ray diffractometry. The thermogravimetry-differential thermal analysis, Fourier transform infrared absorption spectroscopy and 1H --> 13C cross-polarization magic angle spinning nuclear magnetic resonance (CP-MAS NMR) confirmed the preferential coordination of PEG to the YAG:Ce3+ nanocrystal. 27Al single-pulse excitation MAS NMR reveals that the ratio of the 4-fold coordination site to the 6-fold coordination site increased from 0.53 to 0.72 by addition of PEG. We conclude that the surface modification of the YAG:Ce3+ nanocrystal by PEG induces the surface passivation, the prevention of the oxidation of Ce3+ to Ce4+, the promotion of the incorporation of Ce3+ into YAG and the local structural rearrangement, resulting in the PL enhancement. 相似文献
17.
18.
We report a simple preparation of Pd particles dispersed mesoporous carbons. The carbons were prepared by steam activation of carbonized vinylidene chloride/methyl acrylate copolymer (poly(VDC/MA)) containing yttrium acetylacetonate (Y(acac)(3)) and palladium acetylacetonate (Pd(acac)(2)). The resulting carbons consist of high contents of mesopore and uniformly dispersed fine Pd particles. We measured the catalytic activities of the carbons obtained for hydrogenation of methyl linoleate. The Pd particles dispersed in mesoporous activated carbons obtained from poly(VDC/MA) containing both Y(acac)(3) and Pd(acac)(2) showed high catalytic activities, compared with the microporous activated carbon obtained from poly(VDC/MA) containing only Pd(acac)(2). Especially Pd particles dispersed in mesoporous carbons exhibited excellent selectivity for hydrogenation of diene (methyl linoleate) to monoene (methyl oleate). 相似文献
19.
The difference in the electron correlation between H- and other two-electron atoms is clarified by the introduction of the r12 term in the wave function. By using the expansion of r12, a certain modification of the usual electron correlation factor 1 + Cr12 is introduced and its effectiveness is examined. Calculations are carried out for the ground state and the three lowest excited states (23S, 23P and 21P). The peculiar electron correlation in the ground state of H? is shown by looking at the Coulomb hole for closed- and open-shelf models in comparison with those for other two-electron atoms. 相似文献
20.
Four different types of amine-attached MCM-48 silicas were prepared and investigated for CO(2) separation from N(2). Monomeric and polymeric hindered and unhindered amines were attached to the pore surface of the MCM-48 silica and characterized with respect to their CO(2) sorption properties. The pore structures and amino group content in these modified silicas were investigated by XRD, FT-IR, TGA, N(2) adsorption/desorption at 77 K and CHN/Si analysis, which confirmed that in all cases the amino groups were attached to the pore surface of MCM-48 at 1.5-5.2 mmol/g. The N(2) adsorption/desorption analysis showed a considerable decrease of the pore volume and surface area for the MCM-48 silica containing a polymeric amine (e.g., polyethyleneimine). The CO(2) adsorption rates and capacities of the amine-attached MCM-48 samples were studied employing a sorption microbalance. The results obtained indicated that in addition to the concentration of surface-attached amino groups, specific interactions between CO(2) and the surface amino groups, and the resultant pore structure after amine group attachment have a significant impact on CO(2) adsorption properties of these promising adsorbent materials. 相似文献