全文获取类型
收费全文 | 1667篇 |
免费 | 215篇 |
国内免费 | 43篇 |
专业分类
化学 | 1658篇 |
晶体学 | 4篇 |
力学 | 29篇 |
综合类 | 3篇 |
数学 | 33篇 |
物理学 | 198篇 |
出版年
2024年 | 7篇 |
2023年 | 64篇 |
2022年 | 41篇 |
2021年 | 45篇 |
2020年 | 70篇 |
2019年 | 53篇 |
2018年 | 36篇 |
2017年 | 48篇 |
2016年 | 95篇 |
2015年 | 90篇 |
2014年 | 128篇 |
2013年 | 97篇 |
2012年 | 106篇 |
2011年 | 106篇 |
2010年 | 75篇 |
2009年 | 123篇 |
2008年 | 95篇 |
2007年 | 93篇 |
2006年 | 65篇 |
2005年 | 50篇 |
2004年 | 46篇 |
2003年 | 31篇 |
2002年 | 31篇 |
2001年 | 13篇 |
2000年 | 20篇 |
1999年 | 24篇 |
1998年 | 47篇 |
1997年 | 15篇 |
1996年 | 13篇 |
1995年 | 15篇 |
1994年 | 9篇 |
1993年 | 11篇 |
1992年 | 13篇 |
1991年 | 12篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1986年 | 8篇 |
1985年 | 6篇 |
1984年 | 14篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1967年 | 8篇 |
排序方式: 共有1925条查询结果,搜索用时 15 毫秒
21.
22.
Eric J.L. McInnes Grigore A. Timco Richard E.P. Winpenny 《Coordination chemistry reviews》2005,249(23):2577-2590
Studies of two distinct classes of chromium(III) cage complexes are discussed. The first are compact oxo- and carboxylate cages, made by heating precursors to high temperature under a flow of nitrogen. One of these cages, [Cr12O9(OH)3(O2CCMe3)15], has an S = 6 spin ground state which proves a very interesting subject for study by EPR and MCD spectroscopy. Use of other carboxylates leads to other octa- and dodeca-nuclear complexes. The second class of compounds are homo- and hetero-metallic wheels and chains bridged by fluoride and carboxylates. These include the first heterometallic anti-ferromagnetically coupled ring systems and are being widely studied in areas as diverse as magnetic cooling and quantum information processing. The mechanism by which these unusual cyclic and acyclic structures form is discussed. 相似文献
23.
Heinz Günter Viehe Robert Mernyi Lucien Stella Zdenek Janousek 《Angewandte Chemie (International ed. in English)》1979,18(12):917-932
The 100 yers old Wurster's salts have long been recognized as compounds with redical cations. Their unusual stabilization derives partly form capto-dative (cd) substitution. This principle is now discussed as one factor of radical stabilization and it is applied to simple methine derivatives. cd-Substitution has synthetically useful applications: cd-substituents on a carbon atom allow its selective dehydrodimerization. Olefines with geminal and thus cross-conjugated cd-substituents are “radicophilic” and permit twofold carbon radical addition. cd-Substituted olefines are useful antioxidants, polymerization inhibitors and are promising agents in the control of biological radical reactions. Generally, many reactions of cd-substituted molecules appear to involve radicals. 相似文献
24.
In this study, SbxSn1?xO2 (0 ≤ x ≤ 0.5) compositions were synthesized by the ceramic method from Sb2O3‐SnO2 and Sb2O5‐SnO2 mixtures and characterized by Differential thermal analysis (DTA) and thermogravimetric analysis (TG), X‐ray diffraction, UV‐V‐NIR spectroscopy and CIE L*a*b* (Commission Internationale de l'Eclairage L*a*b*) parameters measurements. Solid solutions with cassiterite structure were obtained at 1300 °C. These solid solutions are stable into glazes. From Sb2O3, light gray coloured materials were obtained. From Sb2O5, bluish gray coloured materials were obtained at 1300 °C/6h when x ≥ 0.3. SbxSn1?xO2 with 0.3 ≤ x < 0.5, T = 1300 °C and Sb2O5 might be established as compositional range, fired temperature and antimony precursor to obtain gray ceramic pigments in this system. 相似文献
25.
Monochrome coloured glass beads of the Merovingians (5th–7th cent. AD) have been examined by different analytical methods. The elemental composition of a large number of mostly unprepared
beads have been measured non-destructively by X-ray fluorescence analysis. After subtracting the content of the colouring
oxides of the glass beads and normalising the residual values to 100% an identical soda-lime-glass matrix was obtained. X-ray
diffraction was used for the identification of the crystalline colouring and opacifying pigments (SnO2, Cu, Cu2O, PbSnO3), and scanning electron microscopy as well as electron probe microanalysis were applied to study the microstructure and the
composition of white, brown, green, orange and yellow coloured glass beads. Oxidised metals, alloys (lead, copper, bronze,
brass and mixtures of them) and iron smelting slag have been identified as raw materials to colour the soda-lime-glass. 相似文献
26.
Thomas Kauffmann 《Angewandte Chemie (International ed. in English)》1982,21(6):410-429
Aside from elements of the 2nd row, and one element of the 3rd row of the periodic system—Si, P, S, and Se, respectively, whose organoelement groups such as Me3Si and Ph3P⊕ have proven useful in numerous organic syntheses—other elements of the 3rd as well as 4th and 5th row (Ge, As, Sn, Sb, Te, Pb, Bi) can also be used as components of synthetically useful organoelement groups, the elements As, Sn, and Pb, in particular, offering certain advntages over the others. Some of these organoelement groups are suitable equivalents for Li- or halogen-substituents attached to carbon; they stabilize carbanionic centers (minimum of this effect at the 3rd-row elements), and owing to their suitability as leaving groups in β-eliminations, also open up interesting synthetic possibilities. The thermally unduced syn- and silica-gel induced anti-elimination of Ph3Sn, Ph2Sb, Ph3Pb, together with β-OH, are novel. With the newly synthesized compounds PhnEl—Ch2—Li (El = Sn, Pb, As, Sb, Bi) and other α- and β-lithiated RnEl- and Ph2As(O)-reagents such organoelement groups can be introduced into organic compounds and exploited in organic and organoelement synthesis. 相似文献
27.
To screen for organic pigments, like fringelites or porphyrins, in sediments and fossil specimen, a simple diffuse reflectance UV-vis spectroscopic determination was developed. In contrast to common inorganic pigments, like Fe2O3, these pigments exhibit well-structured characteristic absorption peaks which allow their recognition. This method was then used to identify fringelite H in a non-crinoidSolenopora species from the Jurassic. Reflectance FTIR spectroscopy proved not to be useful for this purpose. 相似文献
28.
Ulrich Schllkopf 《Angewandte Chemie (International ed. in English)》1977,16(6):339-348
Being both nucleophilic and electrophilic, α-metalated isocyanides can add to polar double bonds, forming heterocycles. They are also synthons for α-metalated primary amines. This article describes recent or improved procedures for their use in organic synthesis: (1) In heterocyclic syntheses to give 2-oxazolines, 2-imidazolines, 2-thiazolines, oxazoles and oligooxazoles, thiazoles, triazoles, imidazolinones, pyrroles, 5,6-dihydro-1,3-oxazines and -thiazines, and (via cycloaddition with nitrones) 2-imidazolidinones. (2) In the field of formylaminomethylenation, for example transformation of estrone methyl ether and a keto sugar into the corresponding α-formylaminoacrylic esters, and the conversion of aldehydes and ketones by 3- and 4-pyridyl-methyl isocyanides into N-(1-pyridyl-1-alkenyl)formamides and their hydrolysis to 3- and 4-acylpyridines. (3) In connection with the use of α-metalated isocyanides as synthons for α-metalated primary amines, the author demonstrates how they may be used for preparation of 1,2- and 1,3-amino alcohols, 1,2-diamines, 2,3-diaminoalkanoic acids and for synthesis of higher amino acids starting from simple amino acids. 相似文献
29.
Summary Analytical conditions were established permitting the enabling separation of the cis-trans stereoisomers of selected synthetic pyrethroids with help of thin-layer and gas chromatography. Using the example of permethrin the possibility of isomeric separation in an oilbased commercial formulationis also illustrated. 相似文献
30.
Patrizia Ciminiello Carmela Dell'Aversano Martino Forino Federico Umberto Santelia Emmanuel N. Pitsinos 《Tetrahedron》2006,62(33):7738-7743
The analysis of a batch of toxic mussels (Mytilus galloprovincialis) from the Northern Adriatic Sea led to the isolation of a novel oxazinin, oxazinin-4. Its structure including the relative stereochemistry has been elucidated through extensive NMR analysis. A synthetic route to oxazinins has been crucial in establishing the absolute stereochemistry of oxazinin-4 and for reassigning the absolute C-2 configuration of oxazinin-1 and -2 previously isolated from toxic shellfish and stereostructurally characterized. 相似文献