全文获取类型
收费全文 | 1569篇 |
免费 | 35篇 |
国内免费 | 3篇 |
专业分类
化学 | 926篇 |
晶体学 | 30篇 |
力学 | 45篇 |
数学 | 150篇 |
物理学 | 456篇 |
出版年
2024年 | 10篇 |
2023年 | 9篇 |
2022年 | 25篇 |
2021年 | 32篇 |
2020年 | 44篇 |
2019年 | 44篇 |
2018年 | 41篇 |
2017年 | 34篇 |
2016年 | 52篇 |
2015年 | 41篇 |
2014年 | 51篇 |
2013年 | 106篇 |
2012年 | 95篇 |
2011年 | 98篇 |
2010年 | 76篇 |
2009年 | 63篇 |
2008年 | 84篇 |
2007年 | 67篇 |
2006年 | 55篇 |
2005年 | 42篇 |
2004年 | 29篇 |
2003年 | 26篇 |
2002年 | 30篇 |
2001年 | 11篇 |
2000年 | 17篇 |
1999年 | 11篇 |
1998年 | 11篇 |
1997年 | 12篇 |
1995年 | 13篇 |
1994年 | 12篇 |
1993年 | 14篇 |
1992年 | 13篇 |
1991年 | 17篇 |
1990年 | 10篇 |
1987年 | 9篇 |
1985年 | 17篇 |
1984年 | 18篇 |
1983年 | 18篇 |
1982年 | 12篇 |
1981年 | 18篇 |
1980年 | 19篇 |
1979年 | 13篇 |
1978年 | 20篇 |
1977年 | 20篇 |
1976年 | 27篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 13篇 |
1972年 | 7篇 |
1958年 | 7篇 |
排序方式: 共有1607条查询结果,搜索用时 78 毫秒
51.
(C6H5)3MX2 (M = As, Sb; X = OCOCF3 and M = Sb, Bi; X = SO3F, SO3CF3) compounds prepared by the interaction of triphenylmetal(V) substrates with (CF3CO)2O, (CF3SO2)2O and (FSO2)2O have been characterized by molecular weight determination, elemental and spectroscopic (IR, 1H and 19F NMR, mass) analyses. 相似文献
52.
Background correction has been shown to be an effective and indispensable modification in the spectrophotometric determination of ascorbic acid. The decomposition of ascorbic acid in pharmaceutical samples was carried out by incubation with sodium hydroxide to give products that were insensitive to ultraviolet light. The rapid oxidation in air of ascorbic acid, especially in dilute solutions, was avoided by the use of the flow injection principle for spectrophotometric determination and by employing a carrier stream of an anti-oxidizing nature consisting of 6 micrograms ml(-1) of 2-mercaptoethanol in 0.25% sulphuric acid. The optimized method with a single channel manifold made use of a carrier stream flow rate of 1.1 ml min(-1), an injection volume of 50 microl, a delay coil of 50 cm (0.5 mm i.d.) and detection at 245 nm. The throughput was at least 180 injections h(-1). The proposed flow injection method yielded results for the analysis of 0-20 micrograms ml(-1) of ascorbic acid that were 99-102% (relative standard deviation 0.6% or better) in agreement with those produced by comparable methods involving titration with iodine, chloranil or 2,6-dichlorophenolindophenol [4-(2,6-dichloro-4-hydroxyphenylimino)cyclohexa-2,5-dieno ne], and high-performance liquid chromatography. When the agreement was not good (as low as 14% with respect to the method being compared), this was traced to the presence of substances which are known to interfere in one or other of the methods of comparison. 相似文献
53.
54.
55.
56.
Summary Triisopropoxy bis(O,O-dialkyl dithiophosphates), (i-PrO)3M[S2P(OR)2]2 (M = Nbv, Tav; R = n-Pr, i-Pr, i-Bu and Ph) have been prepared by reacting the appropriate triisopropoxymetal(V)dichloride, (i-PrO)3MCl2 (1 mol) with sodium/ammonium dialkyl dithiophosphates (2 mols)in THF. The monomeric products which are viscous liquids, soluble in common organic solvents and highly susceptible to hydrolysis, were characterized by i.r. and n.m.r. spectra which indicate a bidentate mode of attachment of dithiophosphato groups to the metal. 相似文献
57.
BaSeO3·2·5H2O(I), PbSeO3· 2H2O(II) and CdSeO3·3.5H2O(III) were prepared and analysed. Their hygroscopicity and solubility was investigated. These compounds have high thermal Stability, as shown by their TG and DTA data. IR spectra show multi-dentate coordination of selenite to cations, due to considerable splitting of the asymmetric v3 and v4 bands of SeO
3
2
– in the 780-730 cm–1 and 420-325 cm–1 region.Tentative structures have been proposed involving bridging oxygen atoms.
Zusammenfassung BaSeO3-2.5H2O(I), PbSeO3 · 2H2O(II) und CdSeO3· 3.5H2O(III) wurden hergestellt, analysiert sowie deren Hygroskopizität und Löslichkeit untersucht. TG- und DTA-Untersuchungen erweisen die hohe thermische Stabilität dieser Verbindungen. Die IR-Spektren zeigen mehrzählige Koordination von Selenit zu Kationen, was aus einer beträchtlichen Aufspaltung der antisymmetrischenv 3 undv 4 Banden von SeO 3 2 – im Bereich 780-730cm–1 bzw. 420-325 cm–1 hervorgeht. Es wurden versuchsweise Strukturen mit überbrückenden Sauerstoffatomen vorgeschlagen.
BaSeO3· 2,5H2O, PbSeO3 · 2H2O CdSeO3 · 3,5H2O . . - , v 3 v 4 SeO 3 2 }- 780-730 420-325 –1. , .相似文献
58.
Procedures are described for the determination of organic compounds with iodine trichloride under Andrews's titration conditions. Samples are directly titrated with iodine trichloride or first reacted with an excess of iodine monochloride, with subsequent titration of the iodine formed. The direct titration is done initially in feebly acid medium, then the acidity is raised (biotin, methionine, cystine and thiomersal). Pre-oxidation with iodine monochloride is used if the organic compound reacts slowly [tryptophan and arsenic(III) compounds] or is determined in bicarbonate medium (hydroxylamine and thiosemicarbazide). The ferrocyanide formed by the reduction of ferricyanide (by thiourea and allylthiourea) can also be titrated. Arsenic(V) compounds are determined after reduction to arsenic(III), and iodine in organic compounds is converted into iodide by alkaline fusion into iodide and the iodide titrated. 相似文献
59.
Aromatic primary amines are determined by injection into dilute hydrochloric acid carrier which merges sequentially with 4-N-methylaminophenol and dichromate. The purple-red color formed by oxidative coupling of amines with 4-N-methylaminophenol is measured at 530 nm. In contrast to the manual procedure, the flow-injection procedure avoided errors arising from the instability of the coupling intermediate, oxidation of the amine, and too great an excess of the oxidant. The method improves the selectivity for certain amines in the presence of those which are sterically hindered or have an electron-deficient aromatic nucleus. Nitrite is determined by diazotization of sulfanilamide and quantifying the residual sulfanilamide by oxidative coupling. The sample thourghout for the assay of amines (0.05–20 μg ml?1 NH2-N) and nitrite (1–10 μg ml?1 NO2--N) was 120 h?1. A system for the consecutive determination of aromatic primary amines and nitrite is decribed. 相似文献
60.
Hui Yang Xing Chen Guoxiang Hu Wan-Ting Chen Siobhan J. Bradley Weijie Zhang Gaurav Verma Thomas Nann De-en Jiang Paul E. Kruger Xiangke Wang He Tian Geoffrey I. N. Waterhouse Shane G. Telfer Shengqian Ma 《Chemical science》2020,11(13):3523
Optimizing interfacial contacts and thus electron transfer phenomena in heterogeneous electrocatalysts is an effective approach for enhancing electrocatalytic performance. Herein, we successfully synthesized ultrafine β-Mo2C nanoparticles confined within hollow capsules of nitrogen-doped porous carbon (β-Mo2C@NPCC) and found that the surface layer of molybdenum atoms was further oxidized to a single Mo–O surface layer, thus producing intimate O–Mo–C interfaces. An arsenal of complementary technologies, including XPS, atomic-resolution HAADF-STEM, and XAS analysis clearly reveals the existence of O–Mo–C interfaces for these surface-engineered ultrafine nanostructures. The β-Mo2C@NPCC electrocatalyst exhibited excellent electrocatalytic activity for the hydrogen evolution reaction (HER) in water. Theoretical studies indicate that the highly accessible ultrathin O–Mo–C interfaces serving as the active sites are crucial to the HER performance and underpinned the outstanding electrocatalytic performance of β-Mo2C@NPCC. This proof-of-concept study opens a new avenue for the fabrication of highly efficient catalysts for HER and other applications, whilst further demonstrating the importance of exposed interfaces and interfacial contacts in efficient electrocatalysis.Ultrafine β-Mo2C nanostructures encapsulated in N-doped carbon capsules featuring O–Mo–C interfaces as the active sites for HER have been unveiled. 相似文献