全文获取类型
收费全文 | 7747篇 |
免费 | 321篇 |
国内免费 | 34篇 |
专业分类
化学 | 6322篇 |
晶体学 | 54篇 |
力学 | 99篇 |
数学 | 930篇 |
物理学 | 697篇 |
出版年
2024年 | 6篇 |
2023年 | 80篇 |
2022年 | 291篇 |
2021年 | 433篇 |
2020年 | 236篇 |
2019年 | 237篇 |
2018年 | 199篇 |
2017年 | 164篇 |
2016年 | 317篇 |
2015年 | 230篇 |
2014年 | 318篇 |
2013年 | 489篇 |
2012年 | 533篇 |
2011年 | 582篇 |
2010年 | 394篇 |
2009年 | 299篇 |
2008年 | 481篇 |
2007年 | 455篇 |
2006年 | 421篇 |
2005年 | 324篇 |
2004年 | 279篇 |
2003年 | 204篇 |
2002年 | 183篇 |
2001年 | 98篇 |
2000年 | 67篇 |
1999年 | 48篇 |
1998年 | 55篇 |
1997年 | 43篇 |
1996年 | 55篇 |
1995年 | 39篇 |
1994年 | 34篇 |
1993年 | 38篇 |
1992年 | 32篇 |
1991年 | 33篇 |
1990年 | 25篇 |
1989年 | 32篇 |
1988年 | 21篇 |
1987年 | 22篇 |
1986年 | 28篇 |
1985年 | 45篇 |
1984年 | 24篇 |
1983年 | 17篇 |
1982年 | 29篇 |
1981年 | 21篇 |
1980年 | 22篇 |
1979年 | 12篇 |
1978年 | 6篇 |
1977年 | 9篇 |
1976年 | 9篇 |
1932年 | 5篇 |
排序方式: 共有8102条查询结果,搜索用时 15 毫秒
111.
112.
Di-2-pyridylketone semicarbazone as ligand in metal complexes: synthesis and X-ray crystal structure
Luigi P. Battaglia Pier Giovanni Berzolla Anna Bonamartini Corradi Corrado Pelizzi 《Journal of chemical crystallography》1993,23(12):973-979
A series of complexes of di-2-pyridylketone semicarbazone (Hdips) and Mn(II), Co(II), Co(III), Ni(II) and Cu(II) nitrates were synthesized and characterized by means of IR spectroscopy and for cobalt and nickel by X-ray crystal structures. The results are in agreement with the formulae: Mn(Hdips)2(NO3)2·2H2O, [Co(Hdips)2](NO3)2·H2O (I), [Ni(Hdips)2](NO3)2·H2O (II), Cu(Hdips)(NO3)2·2H2O, [Co(dips)2](NO3)·2H2O (III). The structure of I and II are monoclinic, space groupP21/c, with, I,a=15.980(4),b=11.531(2),c=16.170(2)Å;=104.20(2)°,Z=4,R=0.032; II,a=16.109(5),b=11.480(3),c=16.135(6)Å;=104.15(2)°,Z=4,R=0.069. Compound III is also monoclinic, space groupP21/c witha=12.173(5),b=15.619(5),c=15.338(8)Å;=111.40(4)°,Z=4,R=0.059. In these complexes the ligand is tridentate via carbonylic oxygen, semicarbazone and pyridine nitrogens forming each two five membered chelate rings with the metal in a distorted octahedral geometry. 相似文献
113.
Munsch TE Slipchenko LV Krylov AI Wenthold PG 《The Journal of organic chemistry》2004,69(17):5735-5741
The electronic structure of dehydro-m-xylylene anion (DMX-) has been investigated by using chemical reactivity studies and electronic structure calculations. DMX- has been generated in the gas phase via the sequential reaction of trimethyl-3,5-bis(trimethylsilylmethyl)phenylsilane with F- and two molecules of F2. Reactivity and thermochemical properties of the ion indicate a phenyl-like anion (1a), consistent with theoretical predictions. Density functional calculations predict a nonplanar triplet anion, with an allenic singlet anion slightly higher in energy. The driving force for the out-of-plane distortion is more efficient charge delocalization that is achieved at lower symmetry. 相似文献
114.
Complete double photoelectron spectra are presented for 18 small molecules where the location of charges in the cations and dications is relatively clearly defined. The data demonstrate the importance of a coulombic repulsion contribution to the double ionisation energies. Examination of data for a wide range of molecules leads to a new empirical rule to calculate double ionisation energies from the molecules’ single ionisation energies and maximum dimensions. Where single and double ionisation energies are known the rule allows the deduction of plausible intercharge distances. 相似文献
115.
Anna Daghetti Carlo Gatti Sergio Trasatti 《Journal of Electroanalytical Chemistry》1985,196(1):179-197
Three isotherms are considered: Frumkin's Bennes' and Mohilner's. The relationship between the interaction parameters in the first two and the adsorbate activity coefficient in the last is discussed. The significance of various standard states for the definition of ΔG° ads is analysed. The operational derivation of ΔG°ads in the three cases and the relationship between the resulting three quantities are illustrated. The isotherms have been used to describe the adsorption of 1,4-dioxane on a polarized Hg electrode. The analysis has been carried out both at constant potential and constant charge. The picture emerging in each of the three cases is discussed in the light of the results obtained in the other two. It is concluded that the three approaches give the same qualitative information about the interfacial behaviour of dioxane, especially as far as the effect of the electric field and the particle-particle lateral interaction are concerned. The usefulness of the Frumkin isotherm for analysing promptly experimental adsorption data is thus maintained. Limitations of the present approach are discussed. 相似文献
116.
An efficient and environmentally friendly method preparing 2H-azirines in good yield has been achieved by microwave irradiation of vinyl azides in solvent free conditions. 相似文献
117.
Krzysztof Stolarczyk Renata Bilewicz Anna Skwierawska Jan F. Biernat 《Journal of inclusion phenomena and macrocyclic chemistry》2004,49(1-2):173-179
Properties of monolayers of azocrown compound self-assembled on gold substrates were studied using voltammetry and scanning tunneling microscopy. The surface concentrations of this compound in monolayers were determined from the area of the voltammetric reduction peaks. The area per one molecule estimated from voltammetry experiments is 0.65 nm2. This value was comparable with the limiting molecular area of the compound in the Langmuir–Blodgett film at the air–water interface. We also observed the presence of gold clusters and other gold structures by STM when a gold electrode modified with azocrown compound was dipped into the tetrachloroaurate solution. Even better spectra of clusters were obtained following one voltammetric scan in the range 0.5 to ?0.6 V. After more cycles or if we condition the electrode at 0.4 V the clusters aggregate into wires. 相似文献
118.
Anna Kowalska Zygmunt Kowalski Andrzej Kotarba Andrzej Barański 《Mikrochimica acta》1990,100(5-6):349-353
The analytical procedure of determination of Fe(II) in the presence of Fe(III) in milligram samples is proposed. A solid sample is dissolved in hydrochloric acid in argon atmosphere. Subsequently, the pH-value of the solution is fixed and Fe(III) complexed by phosphoric buffer. At the next step Fe(II) is oxidized by -molybdosilicic acid. Finally, the intensity of colouring caused by the reduced form of the acid is measured at the wavelength 770 nm. The proper treatment of the sample during oxidation, and immediately before, is decisive for the accuracy of the analysis. The method was verified by means of the analysis of synthetic magnetite. The theoretical content of Fe(II) was 24.12%, the determined one was 24.02 ± 0.10%. The method was applied to the determination of the homogeneity of an iron catalyst for ammonia synthesis. 相似文献
119.
反应挤出法合成S/B多嵌段共聚物的研究 总被引:11,自引:0,他引:11
在阴离子引发体系下 ,以双螺杆挤出机为反应器 ,采用丁二烯、苯乙烯混和单体加料方式 ,本体法一步合成了S B多嵌段共聚物 .考察了螺杆转速、进料速率以及不同丁苯配比对反应挤出合成PS及S B嵌段共聚物聚合转化率的影响 .用1 H NMR、IR、DMA、TEM等方法对S B嵌段共聚物进行了表征 ,结果表明共聚物由多个微小的丁二烯嵌段和少量无规段组成 .当丁二烯含量少至 15 %左右时 ,其嵌段可回缩成球状 ,粒径大约在 30~ 5 0nm .该材料的韧性随着共聚物中丁二烯含量的增加而逐渐提高 ,特别是断裂延伸率的提高尤为显著 相似文献
120.
Anna B. DenisovaVyacheslav Ya. Sosnovskikh Wim Dehaen Suzanne ToppetLuc Van Meervelt Vasiliy A. Bakulev 《Journal of fluorine chemistry》2002,115(2):183-192
Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c. 相似文献