首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   925篇
  免费   28篇
  国内免费   4篇
化学   753篇
晶体学   7篇
力学   9篇
数学   32篇
物理学   156篇
  2023年   6篇
  2022年   6篇
  2021年   14篇
  2020年   18篇
  2019年   18篇
  2018年   10篇
  2017年   5篇
  2016年   18篇
  2015年   17篇
  2014年   26篇
  2013年   51篇
  2012年   55篇
  2011年   62篇
  2010年   35篇
  2009年   35篇
  2008年   52篇
  2007年   69篇
  2006年   46篇
  2005年   55篇
  2004年   47篇
  2003年   41篇
  2002年   25篇
  2001年   14篇
  2000年   8篇
  1999年   7篇
  1998年   7篇
  1996年   15篇
  1995年   7篇
  1994年   7篇
  1992年   10篇
  1990年   4篇
  1989年   5篇
  1987年   9篇
  1986年   8篇
  1985年   13篇
  1984年   8篇
  1982年   11篇
  1981年   6篇
  1980年   11篇
  1979年   5篇
  1978年   6篇
  1977年   6篇
  1976年   5篇
  1975年   3篇
  1974年   5篇
  1970年   5篇
  1969年   6篇
  1968年   10篇
  1967年   14篇
  1966年   10篇
排序方式: 共有957条查询结果,搜索用时 78 毫秒
861.
Photocyclization reactions were carried out on ethyl 2-(8-oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetates 1a-e and ethyl 2-(5-oxo-6,7,8,9-tetrahydro-5H-benzocyclohepten-4-yloxy)acetates 2a-e in acetonitrile. Irradiation of 1a-e gave naphtho[1,8-bc]furanols 3a-e and naphtho[1,8-bc]furans 4a-e in 33–83% yields and ethyl acrylates 5b-d were produced in 3–25% yields during irradiation of 1b-d . On the other hand, 2a-e afforded cyclohepta[ad|benzofuranols 6a-e and cyclohepta[ad]benzofurans 7a-e in 44–87% yields. Ethyl acrylates 8b-d were also produced in 7–43% yields from irradiation of 2b-d . Substituent effects on photocyclization and reaction pathways are discussed.  相似文献   
862.
Radiation-induced postpolymerization of nitroethylene in 2-methyltetrahydrofuran glass has been studied and discussed in reference to the results obtained from ESR measurements. No postpolymerization occurred at the temperature below ?150°C. In the temperature range between ?135°C and ?78°C, the polymer yield decreased with increasing postpolymerization temperature. The polymer yield increased linearly with the increase of the preirradiation dose in the range below 0.9 × 106 r. The mean value for chain initiation was estimated to be about 1.3. The following correlations were observed between the results of the postpolymerization and ESR measurements. The postpolymerization started in the temperature range between ?140°C and ?135°C, where the ESR spectrum due to the anion radicals of nitroethylene disappeared. The polymer yield of the postpolymerization decreased with the photoirradiation at ?196°C before warming the samples in parallel with the photobleachability of the anion radicals observed in the glassy mixture by the ESR method. It was concluded from these results that the radiation-induced postpolymerization was initiated by the anion radicals of nitroethylene formed by the capture of electons.  相似文献   
863.
The copolymerization of tetraoxane with various olefins by BF3·O(C2H5)2 in ethylene dichloride at 30°C has been studied. The gas chromatographic technique was employed for the determination of concentration of each compound. The rate of tetraoxane consumption was decreased by the addition of olefins in the order of; no addition > trans-stilbene > styrene > 1,1-diphenylethylene > 2-chloroethyl vinyl ether > cyclohexene ≥ indene ≥ α-methylstyrene. The formation of the methanol-insoluble copolymer of tetraoxane and olefin was not confirmed. However, 4-methyl-4-phenyl-1,3-dioxane and 4,4-diphenyl-1,3-dioxane were formed in the reaction of tetraoxane with α-methylstyrene and 1,1-diphenylethylene, respectively. 4,4-Diphenyl-1,3-dioxane was identified on the basis of the molecular weight measurement, elemental analysis and NMR and infrared spectroscopy. On the other hand, 1,3-dioxane derivatives were not formed in the reaction of tetraoxane with α,β-disubstituted olefins. Monomer composition dependence of the copolymerization of tetraoxane with 1,1-diphenylethylene or α-methylstyrene has been studied. The amount of 4,4-diphenyl-1,3-dioxane formed reached a maximum at a monomer composition of 1:1 in the reaction of tetraoxane with 1,1-diphenylethylene. The formation of cyclic dimer of α-methylstyrene was suppressed by tetraoxane.  相似文献   
864.
Poly-3,3-bis(chloromethyl)oxetane (poly-BCMO) was irradiated at ?196°C with electron beams and ultraviolet light, and observed ESR spectra were compared. A three-line spectrum (coupling constant of about 21 gauss) and a two-line spectrum (coupling constant of about 18 gauss) were observed after irradiation with electron beams in vacuo. They were attributed to free radicals and respectively. On the other hand, a three-line spectrum (coupling constant of about 20 gauss) and an asymmetric singlet spectrum were observed after ultraviolet irradiation in vacuum. They were assigned to free radicals and ? CH2? O·, respectively. Mechanisms of radical formation were discussed in each case. When poly-BCMO was irradiated with electron beams at ?196°C in the presence of air, peroxy radicals were produced after subsequent treatment at ?78°C. The reaction between alkyl radicals and oxygen molecules was found to be diffusion-controlled.  相似文献   
865.
The cis- and trans-propenyl alkyl ethers were polymerized by a homogeneous catalyst [BF3·O(C2H5)2] and a heterogeneous catalyst [Al2(SO4)3–H2SO4 complex]. Methyl, ethyl, isopropyl, n-butyl and tert-butyl propenyl ethers were used as monomers. The steric structure of the polymers formed depended on the geometric structures of monomer and the polymerization conditions. In polymerizations with BF3·O(C2H5)2 at ?78°C., trans isomers produced crystalline polymers, but cis isomers formed amorphous ones except for tert-butyl propenyl ether. On the other hand, highly crystalline polymers were formed from cis isomers, but not from the trans isomers in the polymerization by Al2(SO4)3–H2SO4 complex at 0°C. The x-ray diffraction patterns of the crystalline polymers obtained from the trans isomers were different from those produced from the cis isomers, except for poly(methyl propenyl ether). The reaction mechanism was discussed briefly on these basis of these results.  相似文献   
866.
867.
Dependence of all-optical poling efficiency on carrier-envelope phase (CEP) could be measured using photoisomerization of dye molecules which are covalently bound to a polymer main chain and have large difference in static dipole moment between the ground state and excited state. Increased chromophore density leads to an order of magnitude reduction in signal-detection time from a dye doped polymer. Analysis of all-optical poling experiments with CEP changes clearly showed the presence of polarization restoring force to zero polarization. This enables resetting of SH activity in the all-optical poling process to be used for fast response loop of CEP stabilization. Phenomenological model could explain well the difference in the growth-and-decay dynamics of poling between sample of dye doped in polymer studied previously and that grafted to a polymer main chain used in the present paper.  相似文献   
868.
[IrCl(cod)]2 catalyzed the oxidative esterification of a variety of aldehydes with methanol as a solvent in combination with K2CO3 under mild conditions (rt, 12 h). The oxidative esterification reaction of aliphatic aldehydes also took place with olefinic alcohols as reagents in toluene under similar conditions.  相似文献   
869.
870.
Long-range propagation characteristics of an annular beam were examined from the viewpoint of lidar application. The annular beam permits to use a reflecting telescope for transmission and improves the transmission efficiency because it can pass through the telescope without the obstruction of the telescope’s secondary mirror. As the annular beam can enlarge up to the telescope diameter, it can be eye-safe and its divergence is also reduced.The annular beam generated by a couple of Axicon prisms; conical prisms, transforms its beam shape into the central peak narrow beam; nearly non-diffractive beam, through the far-field propagation. We evaluated how the central peak intensity and its width of the transformed beam change in long-range of 3-100 km. The difficulty of the optical arraignment and the requirement of the beam quality to obtain the enough performance of the beam shape transformation were also examined theoretically and experimentally for the lidar application. The stability of the transformed beam was also confirmed in the atmospheric fluctuation.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号