全文获取类型
收费全文 | 376篇 |
免费 | 11篇 |
国内免费 | 7篇 |
专业分类
化学 | 301篇 |
力学 | 15篇 |
数学 | 28篇 |
物理学 | 50篇 |
出版年
2023年 | 1篇 |
2022年 | 7篇 |
2021年 | 20篇 |
2020年 | 19篇 |
2019年 | 9篇 |
2018年 | 21篇 |
2017年 | 15篇 |
2016年 | 31篇 |
2015年 | 17篇 |
2014年 | 30篇 |
2013年 | 63篇 |
2012年 | 25篇 |
2011年 | 25篇 |
2010年 | 12篇 |
2009年 | 19篇 |
2008年 | 20篇 |
2007年 | 20篇 |
2006年 | 8篇 |
2005年 | 9篇 |
2004年 | 7篇 |
2003年 | 3篇 |
2002年 | 3篇 |
2001年 | 3篇 |
1997年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有394条查询结果,搜索用时 15 毫秒
51.
Electrochemical oxidation of catechol and its derivatives ( 1a–d ) has been studied in the presence of 4‐amino‐3‐thio‐1,2,4‐triazole ( 3 ) at various pHs. Some electrochemical techniques such as cyclic voltammetry using the diagnostic criteria derived by Nicholson and Shain for various electrode mechanisms and controlled‐potential coulometry were used. Results indicate the participation of catechols ( 1a–d ) with 3 in an intramolecular cyclization reaction to form the corresponding 1,2,4‐triazino[5,4‐b]‐1,3,4‐thiadiazine derivatives. In various scan rates, based on an electron transfer–chemical reaction–electron transfer–chemical reaction mechanism, the observed homogeneous rate constants (kobs) for Michael addition reaction were estimated by comparing the experimental cyclic voltammetric responses with the digital simulated results. The oxidation reaction mechanism of catechols ( 1a–d ) in the presence of 4‐amino‐3‐thio‐1,2,4‐triazole ( 3 ) was also studied. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 340–345, 2007 相似文献
52.
Electrochemical oxidation of some catecholamines such as dopamine ( 1 ), L ‐dopa ( 2 ), and methyldopa ( 3 ) has been studied in various pH values, using cyclic voltammetry. The results indicate participation of catecholamines ( 1–3 ) in intramolecular cyclization reaction to form the corresponding o‐quinone derivatives ( 1d–3d ). In various pHs, based on ECE mechanism, the observed homogeneous rate constants (kobs) of cyclization reaction were estimated by comparing the experimental cyclic voltammetric responses with the digital‐simulated results. Also, the cyclization rate constants (kcyc) were calculated using microscopic acidic dissociation constant of ammonium groups. The significant differences in electrochemical behavior, kobs and kcyc, of L ‐dopa ( 2 ) and methyldopa ( 3 ) with dopamine ( 1 ) are due to the effects of the side chain carboxyl group. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 37: 17–24, 2005 相似文献
53.
An efficient ionic liquid with both Brønsted acidic and Lewis basic sites, namely 1,4-dimethyl-1-(4-sulphobutyl)piperazinium hydrogen sulphate (IL1), was synthesised and characterised. IL1 is a “green”, homogeneous and reusable catalyst for: i) the synthesis of pyranopyrazoles (Va-Vj)and benzopyrans (VIa-VIj and VIIa-VIIf) at ambient temperature under solvent-free conditions and ii) the synthesis of amino-2-chromenes (VIIIa-VIIIi and IXa-IXi) and dihyropyrano[c]chromenes (Xa-Xi) at 80 °C under solvent-free conditions. The reactions were rapid with excellent product yields. In addition, the double Brønsted acid, 1,4-dimethyl-1,4-bis(4-sulphobutyl)piperazinium hydrogen sulphate (IL2), was prepared to evaluate the cooperation efficiency of their Brønsted acidic and Lewis basic sites as compared with the double Brønsted acidic sites in IL1. 相似文献
54.
We show that for an inverse semigroup S with the set idempotents E acting on S trivially from left and by multiplication from right, any bounded module derivation from \(\ell ^1(S)\) to \(({\ell ^1(S)}/{J})^*=J^{\perp }\) is inner, where J is the closed ideal generated by elements of the form \(\delta _{set}-\delta _{st}\) with \(s,t\in S\) and \(e\in E\). 相似文献
55.
Lesarri A Vega-Toribio A Suenram RD Brugh DJ Nori-Shargh D Boggs JE Grabow JU 《Physical chemistry chemical physics : PCCP》2011,13(14):6610-6618
The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several (37)Cl and (13)C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C(1)-C(2)-O-C(3)) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 3:1. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect. 相似文献
56.
Behzad Ramin Salehi Rad Mohammad Reza Nematollahi Nader 《Methodology and Computing in Applied Probability》2019,21(4):1045-1056
Methodology and Computing in Applied Probability - We consider a queueing system where some customers decide to simultaneously wait in two queues, rather than in a single queue, to receive their... 相似文献
57.
We study the weak module amenability of Banach algebras which are
Banach module over another Banach algebra with compatible actions.
As an example we show that the semigroup algebra of a commutative inverse
semigroup is always weakly amenable as a module over the semigroup
algebra of its subsemigroup of idempotents. 相似文献
58.
59.
M.H. Abraham Davood Farshbaf Dadjour C.J. Holloway 《Journal of organometallic chemistry》1973,52(2):C27-C28
In the reaction of mercuric carboxylates with tetraalkyltins in methanol, rate constrants for attack of the species (RCO2)2 Hg increase along the series R = t-Bu < Et < Me < Ph < ClCH2CH2 < MeOCH2 < ClCH2 which suggests an open transition state for these SE2 substitutions. 相似文献
60.
Nematollahi D Workentin MS Tammari E 《Chemical communications (Cambridge, England)》2006,(15):1631-1633
We describe the synthesis and kinetic evaluation of compounds from [4 + 2] alone and [4 + 2] followed by [2 + 2] cycloaddition reactions of electrochemically generated o-benzoquinone with 1,3-cyclopentadiene. 相似文献