全文获取类型
收费全文 | 563篇 |
免费 | 29篇 |
国内免费 | 3篇 |
专业分类
化学 | 458篇 |
晶体学 | 4篇 |
力学 | 11篇 |
数学 | 79篇 |
物理学 | 43篇 |
出版年
2022年 | 9篇 |
2021年 | 12篇 |
2020年 | 8篇 |
2019年 | 10篇 |
2018年 | 10篇 |
2017年 | 2篇 |
2016年 | 14篇 |
2015年 | 22篇 |
2014年 | 15篇 |
2013年 | 25篇 |
2012年 | 41篇 |
2011年 | 57篇 |
2010年 | 29篇 |
2009年 | 32篇 |
2008年 | 39篇 |
2007年 | 31篇 |
2006年 | 30篇 |
2005年 | 27篇 |
2004年 | 24篇 |
2003年 | 27篇 |
2002年 | 19篇 |
2001年 | 9篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1964年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有595条查询结果,搜索用时 0 毫秒
101.
102.
Recent results on the selective reduction of cyclic vinylphosphine oxides and vinylphosphinates, as well as their refunctionalization by the use of borane, are summarized. The selective reduction of the phosphorus moiety of unsaturated phosphonates, phosphinates, and phosphine oxides is also discussed. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:161–167, 2001 相似文献
103.
104.
105.
Stereoselective Synthesis of the Halaven C14–C26 Fragment from D‐Quinic Acid: Crystallization‐Induced Diastereoselective Transformation of an α‐Methyl Nitrile 下载免费PDF全文
Francis Belanger Dr. Charles E. Chase Dr. Atsushi Endo Dr. Francis G. Fang Dr. Jing Li Steven R. Mathieu Dr. Annie Z. Wilcoxen Huiming Zhang 《Angewandte Chemie (International ed. in English)》2015,54(17):5108-5111
Crystallization‐induced diastereoselective transformation (CIDT) of an α‐methyl nitrile completes an entirely non‐chromatographic synthesis of the halichondrin B C14–C26 stereochemical array. The requisite α‐methyl nitrile substrate is derived from D ‐quinic acid through a series of substrate‐controlled stereoselective reactions via a number of crystalline intermediates that benefit from a rigid polycyclic template. Therefore, all four stereogenic centers in the Halaven C14–C26 fragment were derived from the single chiral source D ‐quinic acid. 相似文献
106.
Annie Praud-Tabaries 《Tetrahedron letters》2009,50(14):1645-6755
A terpenoid-like library containing 1,4-disubstituted-(1H)-1,2,3-triazoles was prepared by means of 1,3-dipolar cycloaddition of geranyl and farnesyl azides with a set of terminal alkynes, in order to design a new class of potentially active anti-biofilm compounds. Reactions were optimized to proceed under mild conditions and in high yields. Two compounds were found to possess interesting activity against Pseudoalteromonas sp. biofilm. This process is suitable for combinatorial chemistry of marine natural product-like compounds. 相似文献
107.
Linke-Schaetzel M Anson CE Powell AK Buth G Palomares E Durrant JD Balaban TS Lehn JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(7):1931-1940
A series of butterfly-type molecular constructs has been prepared in good yield by using a double Stille coupling synthetic protocol. They are composed of a terpyridine (terpy) scaffold and two wings composed of appended porphyrins that are capable of switching from an extended W geometry to a compact U geometry upon cation coordination of the terpy unit. The porphyrin moieties exist in the constructs either as free bases or they can be sequentially metallated, thus giving rise to wings of different "colours". Stationary and time-resolved emission studies of the HZn, ZnAu and Zn2Au constructs show that the electronic properties are strongly dependent on the geometry. In the extended W conformation an energy-transfer process is seen from the free base to the Zn-metallated porphyrin. In the U conformation in Zn2Au the donor luminescence resulting from the singlet excited state of the Zn wing is strongly, quenched not only due to the heavy atom effect but also due to a fast electron-transfer process to the ground state of the Au wing. Furthermore, the binding of (alpha,omega)-diamine substrates to the Zn(II)-porphyrin sites can also influence the conformation of the system. For the Zn2Zn construct, single-crystal diffraction experiments with synchrotron radiation allowed the structure to be solved by direct methods and fully refined; it shows the expected U conformation. The central Zn atom is six-coordinate, whereby the zinc atom is coordinated by the eta3-terpy ligand as well by monodentate and semi-chelating acetate anions. The structure is made rigid by hydrogen bonds involving the aqua ligands on the outer Zn centres and acetate oxygen atoms. The present system thus represents a double-trigger-modulated optomechanical switching device with selective substrate binding for either metal atoms or tailored ligands. Both energy- and electron-transfer processes can be controlled opening a means of improving the on/off ratio in future constructs. 相似文献
108.
The Staudinger ligation provides a means to form an amide bond between a phosphinothioester and azide. This reaction holds promise for the ligation of peptides en route to the total chemical synthesis of proteins. (Diphenylphosphino)methanethiol is the most efficacious of known reagents for mediating the Staudinger ligation of peptides, providing high (> 90%) isolated yields for equimolar couplings in which a glycine residue is at the nascent junction. Surprisingly, the yields are lower (< 50%) for non-glycyl couplings due to an aza-Wittig reaction that diverts the reaction toward a phosphonamide byproduct. Here, the partitioning of the reaction toward Staudinger ligation (and away from the aza-Wittig reaction) is shown to increase with increasing electron density on phosphorus. This electron density can be tuned either by installing functional groups on the phenyl substituents of (diphenylphosphino)methanethiol or by changing the polarity of the solvent. Installing p-methoxy groups and using a solvent of low polarity (such as toluene or dioxane) provide especially high (> 80%) isolated yields for the ligation of two non-glycyl residues. These conditions retain the high chemoselectivity of the reaction and do not lead to a substantial change in reaction rate. The traceless Staudinger ligation is now poised to enable the iterative ligation of peptides with little regard for their sequence, as well as the synthesis of amide bonds for other purposes. 相似文献
109.
110.
S Schmidt D Prodius G Novitchi V Mereacre GE Kostakis AK Powell 《Chemical communications (Cambridge, England)》2012,48(79):9825-9827
A new family of hexanuclear ferric-lanthanide [Fe(III)(4)Ln(III)(2)(Htea)(4)(Piv)(6)(N(3))(4)] clusters, where Ln(III) = Er(1) and Lu(2) is reported. Variable temperature solid-state magnetic susceptibility studies of 1 and 2 reveal the presence of ferromagnetic (1) or competing anti- and ferromagnetic exchange interactions (2) between the constituent Fe(III) ions. 相似文献