全文获取类型
收费全文 | 267篇 |
免费 | 16篇 |
国内免费 | 10篇 |
专业分类
化学 | 180篇 |
晶体学 | 3篇 |
力学 | 1篇 |
数学 | 73篇 |
物理学 | 36篇 |
出版年
2022年 | 5篇 |
2021年 | 3篇 |
2020年 | 4篇 |
2018年 | 4篇 |
2017年 | 9篇 |
2016年 | 7篇 |
2015年 | 13篇 |
2014年 | 8篇 |
2013年 | 23篇 |
2012年 | 8篇 |
2011年 | 18篇 |
2010年 | 6篇 |
2009年 | 17篇 |
2008年 | 11篇 |
2007年 | 16篇 |
2006年 | 15篇 |
2005年 | 13篇 |
2004年 | 11篇 |
2003年 | 4篇 |
2002年 | 4篇 |
2001年 | 4篇 |
2000年 | 7篇 |
1999年 | 4篇 |
1998年 | 6篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1987年 | 4篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1969年 | 1篇 |
1965年 | 1篇 |
1964年 | 1篇 |
1960年 | 1篇 |
1958年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有293条查询结果,搜索用时 15 毫秒
31.
The kinetics of CO(2) uptake by the cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+ complex cation and the acid hydrolysis of the cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]- complex anion (where BaraNH(2) denotes methyl 3-amino-2,3-dideoxy-b-D-arabino-hexopyranoside) were studied using the stopped-flow technique. The reactions under study were investigated in aqueous solution in the 288-308 K temperature range. In the case of the reaction between CO(2) and cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+ cation variable pH values (6.82-8.91) and the constant ionic strength of solution (H+, Na+, ClO(4)- = 1.0) were used. Carbon dioxide was generated by the reaction between sodium pyruvate and hydrogen peroxide. The acid hydrolysis of cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]- was investigated for varying concentrations of H+ ions (0.01-2.7 M). The obtained results enabled the determination of the number of steps of the studied reactions. Based on the kinetic equations, rate constants were determined for each step. Finally, mechanisms for both reactions were proposed and discussed. Based on the obtained results it was concluded that the carboxylation (CO(2) uptake) reactions of cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+ and the decarboxylation (acid hydrolysis) of the cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]- are the opposite of each other. 相似文献
32.
Alicja Wawrzynów Adam Liwo Ewa Kaczmarczyk Lech Chmurzyński 《Journal of solution chemistry》1998,27(5):463-472
Cationic heteroconjugation equilibria of more than ninety systems consisting of substituted pyridines, their N-oxides, and trimethylamine N-oxide, i. e., in systems with mixed hydrogen bridges of type OHN+ (NHO+) were studied in propylene carbonate. Both experimental systems without proton transfer, BH+/B1, and those with proton transfer, B1H+/B, were explored. The stability of the mixed hydrogen bridges, OHN+ (NHO+), is compared with that of the OHC+-type bridges. The influence of the difference in basicity of the conjugate base of the proton donor and the proton acceptor on the presence of the proton transfer equilibria, and, consequently, the possibility of determination of the cationic heteroconjugation constant values is discussed. 相似文献
33.
Dagmara Jacewicz Aleksandra Dąbrowska Agnieszka Łapińska Lech Chmurzyński 《Transition Metal Chemistry》2006,31(5):575-579
The cis-[Cr(phen)2(O2CO)]+ ion was prepared through the displacement of two molecules of water from the cis-[Cr(phen)2(OH2)2]3+ by the bidentate carbonate anion. It underwent two-phase hydrolysis reactions under acidic conditions (0.1 < [H+] < 2.7 m) at 5, 10, 15, 20 and 25 °C. Via slow carbonato chelate ring opening (first step k1slow) and a second fast decarboxylation(k2fast value). The first step was preceded by protonation of the coordinate bidentate carbonate ligand. The second step exhibited
no pH dependence, while k1slow values increased with acid concentration that suggested the presence of both protonated and deprotonated reactant species.
Based on these observations we have proposed a hydrolysis mechanism featuring H2O-induced ring-opening of the coordinate CO32− group in the first step k1slow followed by loss of CO32− from two intermediates, [Cr(phen)2(O2COH)]2+ (k1slow) and [Cr(phen)2(OH2)(O2COH)]2+ (k2fast). 相似文献
34.
Zbigniew Kisiel Lech Pszczó?kowski Manfred Winnewisser Eric Herbst 《Journal of Molecular Spectroscopy》2005,233(2):231-243
We report the results of a comprehensive reinvestigation of the rotational spectrum of diethyl ether based on broadband millimetre-wave spectra recently recorded at The Ohio State University and in Warsaw, covering the frequency region 108-366 GHz. The data set for the ground vibrational state of trans-trans diethyl ether has been extended to over 2000 lines and improved spectroscopic constants have been determined. Rotational spectra in the first excited vibrational states of the three lowest vibrational modes of trans-trans-diethyl ether, ν20, ν39, and ν12 have been assigned. The v20 = 1 and v39 = 1 states are near 100 cm−1 in vibrational term value and are coupled by a strong c-axis Coriolis interaction, which gives rise to many spectacular manifestations in the rotational spectrum. All of these effects have been successfully fitted for a dataset comprising over 3000 transitions, leading to precise determination of the energy difference between these states, (ΔE/hc)=10.400222(5) cm−1. A newly developed software package for assignment and analysis of broadband spectra is described and made available. 相似文献
35.
Janusz Dabrowski Krystyna Kamieska-Trela Lech Kozerski 《Magnetic resonance in chemistry : MRC》1974,6(9):499-502
Carbon-13 magnetic resonance spectra of the s-cis and s-trans rotamers of enamino ketones and thiones of the general formula \documentclass{article}\pagestyle{empty}\begin{document}${\rm X =}\mathop {\rm C}\limits^{\rm 1} {\rm (}\mathop {\rm R}\limits^{\rm 1} {\rm)}\mathop {\rm C}\limits^{\rm 2} {\rm H =}\mathop {\rm C}\limits^{\rm 3} {\rm HN}\mathop {{\rm R}_{\rm 2}}\limits^{\rm 4}$\end{document} (where × = O or S and R-1, R-4 = alkyl) have been obtained. With dimethylaminoacrolein and its thione analogue, restricted rotation could only be observed in the latter. The chemical shift differences between rotamers and homologues are attributed to changes in conjugation and to induced bond polarisation, both these factors resulting from steric strain. In particular, nonplanar deformations of the s-trans rotamers are deduced from their C-2 chemical shift values. 相似文献
36.
D.n.m.r. studies have been performed involving the measurement of rates of trans-cis isomerization of aliphatic enamino ketones of the type R? CO? CH?CH? NHR1, by means of equilibration experiments and the method of finding the coalescence temperature. Simultaneous observation of the rates of dynamic N? H proton exchange and isomerization processes by the latter method has facilitated the assignment of the rate-determining reaction step in the title compounds studied in aprotic solvents. Thermodynamic parameters are discussed and the dipolar transition state to isomerization in a nonpolar solvent indicated. The dynamic behaviour of all protons undergoing exchange between the possible sites in the molecule are discussed in the light of our own experiments and other recent data. 相似文献
37.
O-Protonation of secondary enamino ketones in TFA or concentrated mineral acids in various solvents is the kinetically favoured course of reaction leading ultimately to stable 2,5- or 3,4-disubstituted pyridinium salts. The mechanism of formation of the salts involves electrophilic attack by the C-3 carbon atom on C-2 or N-nucleophilic centres of the O-protonated molecule. 相似文献
38.
39.
Benzene, halobenzenes, and a number of more or less deactivated arenes,including nitrobenzene, readily reacted in anhydrous HIO3/AcOH/Ac2O/conc. H2SO4 mixtures to probably give ArIO2 intermediates or other hypervalent species (not isolated). The final reaction mixtures were poured into excess aq. Na2SO3 solution (a reductant) to give the purified iodinated products in 39-83% yields. 相似文献
40.