全文获取类型
收费全文 | 119049篇 |
免费 | 8432篇 |
国内免费 | 14593篇 |
专业分类
化学 | 91585篇 |
晶体学 | 1757篇 |
力学 | 4146篇 |
综合类 | 1108篇 |
数学 | 13524篇 |
物理学 | 29954篇 |
出版年
2024年 | 165篇 |
2023年 | 921篇 |
2022年 | 2678篇 |
2021年 | 2479篇 |
2020年 | 3000篇 |
2019年 | 2868篇 |
2018年 | 2572篇 |
2017年 | 3687篇 |
2016年 | 4090篇 |
2015年 | 3569篇 |
2014年 | 4540篇 |
2013年 | 9328篇 |
2012年 | 7966篇 |
2011年 | 6678篇 |
2010年 | 5634篇 |
2009年 | 7387篇 |
2008年 | 7486篇 |
2007年 | 7885篇 |
2006年 | 7215篇 |
2005年 | 6219篇 |
2004年 | 5828篇 |
2003年 | 4833篇 |
2002年 | 6018篇 |
2001年 | 3660篇 |
2000年 | 3460篇 |
1999年 | 3170篇 |
1998年 | 2711篇 |
1997年 | 2195篇 |
1996年 | 1904篇 |
1995年 | 1803篇 |
1994年 | 1579篇 |
1993年 | 1290篇 |
1992年 | 1243篇 |
1991年 | 845篇 |
1990年 | 737篇 |
1989年 | 667篇 |
1988年 | 517篇 |
1987年 | 421篇 |
1986年 | 384篇 |
1985年 | 315篇 |
1984年 | 331篇 |
1983年 | 176篇 |
1982年 | 268篇 |
1981年 | 204篇 |
1980年 | 224篇 |
1979年 | 221篇 |
1978年 | 181篇 |
1977年 | 129篇 |
1976年 | 118篇 |
1973年 | 83篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
951.
952.
3,4-Dihydro-5(1H)-pyrromethenones are easier attacked at themeso-position by electrophiles than 5(1H)-pyrromethenones. This is demonstrated both by aMannich-type-substitution or deuterium-exchange-experiments and by the addition of O-, S-, and N-Nucleophiles to the exocyclic double bond of the model-dihydropyrromethenone (Z)-1 under very mild reaction conditions. Applying these results to the chemistry of 2,3-dihydro-bilatrienes-abc, their chemical characteristics—especially their tautomeric behavior and their dominant C-5-selectivity towards electrophiles—become better understandable. 相似文献
953.
An additive procedure (SIBFA) is developed for the rapid computation of conformational energy variations in very large molecules. The macromolecule is built out of constitutive molecular fragments and the intramolecular energy is computed as a sum of interaction energies between the fragments. The electrostatic and the polarization components are calculated using multicenter multipole expansions of theab initio SCF electron density of the fragments. The repulsion component is obtained as a sum of bond and lone pair interactions.Tests of the procedure on a series of model compounds containing ether oxygens and pyridine-like nitrogens are reported and compared with the results of correspondingab initio SCF calculations. The resulting methodology is compatible with the simultaneous computation of intermolecular interactions. 相似文献
954.
Jenn-Lin Lin 《中国化学会会志》1984,31(4):395-399
The reaction of 3-(4-phenyl-2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PPDT) and tetraphenylborate (TPB) with cobalt (II) has been studied to determine the optimum conditions for the extraction and quantitative spectrophotometry determination of this metal. The ternary complex is extracted into molten naphthalene at pH 3.6–7.4. The solid naphthalene containing the cobalt associated complex is separated by filtration and dissolved in acetonitrile. Beer's law is obeyed in the concentration range 8–140 μg cobalt in 10 ml of acetonitrile solution. The molar absorptivity and sensitivity are 4.2×103 l·mol?1·cm?1 and 0.01408 μg/cm2, respectively. The other factors such as pH, amounts of reagents and naphthalene, shaking and standing times, and the effect of diverse ions are studied. The method has been applied to the determination of cobalt in iron steel alloys. 相似文献
955.
956.
Samaresh Jana 《Tetrahedron letters》2005,46(7):1155-1157
A novel and efficient methodology has been developed for the construction of synthetically important tri-substituted tetrahydrofuran derivatives from bromo-alkenes and bromo-alkynes by radical cyclization reactions using the radical initiator Cp2TiCl, generated in situ from commercially available titanocene dichloride and Zn dust in tetrahydrofuran under argon. 相似文献
957.
E. V. Tulyakova O. A. Fedorova Yu. V. Fedorov G. Jonusauskas A. V. Anisimov 《Russian Chemical Bulletin》2007,56(11):2166-2174
Using 1H NMR spectroscopy and steady-state and time-resolved electronic spectroscopy, the optical properties of mono-and bis(styryl)pyridinium
perchlorates and their complexes with Mg2+, Ba2+ cations were studied. The stability constants of the complexes were determined using spectrophotometric titration. The formation
of inclusion complexes for Mg2+ and sandwich type complexes for Ba2+ results in fluorescence enhancement and increases the lifetimes of the excited states of the initial bis-styryl ligands.
The variation of position of the styryl fragment in the pyridinium aromatic ring gives rise to photochromic crown ethers with
different optical and photophysical characteristics and is also an easy route to bis(crown-ethers) of symmetrical and unsymmetrical
structure.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2092–2100, November, 2007. 相似文献
958.
This article describes the buildup of hydrogen bonded multilayer film of poly(2-vinylpyridine) (P2VP) and poly(acrylic acid) (PAA), and the influence of polymer molecular weight on the formation of microporous film by post-base treatment. The formation of a microporous film involved a two-step mechanism: the release of PAA from P2VP/PAA multilayer, and the reorganization of the remaining P2VP on the substrate. Fourier transform infrared spectroscopy (FT-IR) indicated that the release of PAA from hydrogen bonded multilayer was a rapid process, which was almost independent of the molecular weight of PAA. Furthermore, the molecular weight of P2VP had a great effect on micropore formation by immersing the P2VP/PAA multilayer in basic solution. The rate of micropore formation increased with increasing molecular weight. We anticipate that a comparative study on P2VP/PAA films containing high or low molecular weight polymer provides a way to control the surface morphology, and will be helpful and constructive for the forthcoming discussion about the formation of the microporous film. 相似文献
959.
E. Tomaszewicz 《Thermochimica Acta》2006,447(1):69-74
Reactivity in the solid state between CoWO4 and some rare-earth metal tungstates RE2WO6 (RE = Sm, Eu, Gd) was investigated by the XRD method. Two families of new isostructural cobalt and rare-earth metal tungstates, Co2RE2W3O14 and CoRE4W3O16, were synthesized. The Co2RE2W3O14 phases are formed by heating in air the CoWO4 and RE2WO6 compounds mixed at the molar ratio 2:1, while the CoRE4W3O16 phases are synthesized at the molar ratio of CoWO4/RE2WO6 equals to 1:2. The Co2RE2W3O14 phases as well as the CoRE4W3O16 compounds crystallize in the orthorhombic system. The Co2RE2W3O14 and CoRE4W3O16 compound melt above 1150 °C. A melting manner of the Co2RE2W3O14 and CoRE4W3O16 compounds was determined in an inert atmosphere. The formation of CoWO4−x phase was observed during heating in an inert atmosphere. 相似文献
960.
聚N—异丙基丙烯酰胺溶液的温度依赖关系 总被引:5,自引:0,他引:5
用自由基聚合法合成了聚N-异丙基丙烯酰胺(PNIPAAM)样品,用乌氏粘度计考查了该聚合物的四氢呋喃(THF)溶液和水溶液的粘度与温度的依赖关系。发现PNIPAAM-THF体系的特性粘数随温度升高而增大,PNIPAAM-H2O体系的特性粘数-温度曲线表现出较为复杂的变化规律。并用实验确定的特性粘数对合成样品的分子量进行了表征Mn=8.44×10^5g·mol^-1。 相似文献