全文获取类型
收费全文 | 166篇 |
免费 | 12篇 |
专业分类
化学 | 141篇 |
数学 | 18篇 |
物理学 | 19篇 |
出版年
2022年 | 6篇 |
2021年 | 4篇 |
2020年 | 3篇 |
2019年 | 6篇 |
2018年 | 6篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 12篇 |
2014年 | 6篇 |
2013年 | 10篇 |
2012年 | 20篇 |
2011年 | 10篇 |
2010年 | 7篇 |
2009年 | 12篇 |
2008年 | 8篇 |
2007年 | 10篇 |
2006年 | 8篇 |
2005年 | 2篇 |
2004年 | 6篇 |
2003年 | 3篇 |
2002年 | 4篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 4篇 |
1996年 | 2篇 |
1994年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有178条查询结果,搜索用时 0 毫秒
1.
2.
B. W. Wenclawiak Torsten Hees Corinna E. Z?ller Hans-Peter Kabus 《Fresenius' Journal of Analytical Chemistry》1997,358(4):471-474
An on-line system of supercritical fluid extraction (SFE) and high performance liquid chromatography (HPLC) via solid phase
extraction (SPE) is described for the determination of palladium and rhodium 2,2,6,6-tetramethyl-3,5-heptanedione-(thd) as
well as rhodium-acetylacetonate-(acac) and benzylacetonate-(bzac) chelates. The chelates were extracted with supercritical
CO2 from sand and humic acid, concentrated on SPE cartridges and analysed with HPLC. Two cartridge materials were tested and
compared to off-line trapping. The percentage of the breakthrough and cartridge retained material were measured in liquid
dichloromethane. The SFE conditions could be optimized to separate metal chelates during the extraction. The supercritical
fluid (SF) behaviour of different ligands on rhodium were investigated.
Received: 19 July 1996/Revised: 11 December 1996/Accepted: 14 December 1996 相似文献
3.
Dieter Seebach Laurent Schaeffer Franois Gessier Pascal Bindschdler Corinna Jger Delphine Josien Sascha Kopp Grald Lelais YogeshR. Mahajan Peter Micuch Radovan Sebesta BerndW. Schweizer 《Helvetica chimica acta》2003,86(6):1852-1861
Multigram amounts of suitably protected β2‐amino acids with 17 of the 20 proteinogenic side chains are prepared by diastereoselective reactions of Li, B, or Ti enolates of the corresponding 3‐acyl‐4‐isopropyl‐5,5‐diphenyloxazolidin‐2‐ones (acyl‐DIOZ; 1 ) with appropriate electrophiles (amidomethylation, hydroxyalkylation, (benzyloxycarbonyl)methylation) in yields of 55–90% and with diastereoselectivities of 80 to >97% (Scheme). The primary products 2 – 8 thus obtained are converted to protected β2‐amino acids by standard procedures (Table 1). Many of the DIOZ derivatives are highly crystalline compounds (31 X‐ray crystal structures in Table 2). The chiral auxiliary DIOZ, readily prepared in either enantiomeric form, is recovered with high yield. 相似文献
4.
Werner H Schwab P Bleuel E Mahr N Windmüller B Wolf J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(24):4461-4470
A series of carbenerhodium(I) complexes of the general composition [(eta5-C5H5)Rh(=CRR')(L)] (2a-2i) with R = R'= aryl and L = SbiPr3 or PR3 has been prepared from the square-planar precursors trans-[RhCl(=CRR')(L)2] and NaC5H5 in excellent yields. Reaction of the triisopropylsibane derivative 2a. which contains a rather labile Rh-Sb bond, with CO, PMe3, and CNR (R = Me, CH2Ph, tBu) leads to the displacement of the SbiPr3 ligand and affords the substitution products [(eta5-C5H5)Rh(=CPh2)(L)] (3-7). In contrast, treatment of the triisopropylphosphane compound 2c with CO and CNtBu leads to the cleavage of the Rh=CPh2 bond and gives besides [(eta5-C5H5)Rh(PiPr3)(L)] (10, 12) by metal-assisted C-C coupling diphenylketene Ph2C=C=O (11) or the corresponding imine Ph2C=C=NtBu (13). While the reaction of 2a, c with C2H4 yields [(eta5-C5H5)Rh(C2H4)(L)] (14, 15) and the trisubstituted olefin Ph2C=CHCH3 (16), treatment of 2a, c with RN3 leads to the cleavage of both the Rh-EiPr3 and Rh=CPh2 bonds and gives the chelate complexes [(eta5-C5H5)Rh(kappa2-RNNNNR)] (19, 20). The substitution products 3 (L=CO) and 4 (L= PMe3) react with an equimolar amount of sulfur or selenium by addition of the chalcogen to the Rh=CPh2 bond to generate the complexes [(eta5-C5H5)Rh(kappa2-ECPh2)(L)] (21-24) with thio- or selenobenzophenone as ligand. Similarly, treatment of 3 with CuCl affords the unusual 1:2 adduct [(eta5-C5H5)(CO)Rh(mu-CPh2)(CuCl)2] (25), which reacts with NaC5H5 to form [(eta5-C5H5)(CO)Rh(muCPh2)Cu(eta5-C5H5)] (26). The molecular structures of 3 and 22 have been determined by X-ray crystallography. 相似文献
5.
Corinna Kerst Rabah Boukherroub William J. Leigh 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):215-246
The far-UV (193 nm) laser flash photolysis of nitrogen-saturated isooctane solutions of 1,1-dimethylsiletane allows the direct detection of 1,1-dimethylsilene as a transient species, which (at low laser intensities) decays with pseudo-first-order kinetics (τ 10 μs) and exhibits a UV absorption spectrum with λmax 255 nm. Characteristic rapid quenching is observed for the silene with methanol (kMcOH = (4.9 ± 0.2) × 109 M−1 s−1), tert-butanol (kBuOH = (1.8 ± 0.1) × 109 M−1 s−1) and oxygen (kO2 = (2.0 ± 0.5) × 108 M−1 s−1). The Arrhenius activation parameters for the reaction with methanol have been determined to be Ea = −2.6 ± 0.6 kcal mol−1 and log A = 7.7 ± 0.3. 相似文献
6.
Synthesis of Inorganic Structural Isomers By Diffusion‐Constrained Self‐Assembly of Designed Precursors: A Novel Type of Isomerism 下载免费PDF全文
Marco Esters Matti B. Alemayehu Zachary Jones Dr. N. T. Nguyen Dr. Michael D. Anderson Corinna Grosse Prof. Saskia F. Fischer Prof. David C. Johnson 《Angewandte Chemie (International ed. in English)》2015,54(4):1130-1134
The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe2: [(PbSe)1.14]4[NbSe2]4, [(PbSe)1.14]3[NbSe2]3[(PbSe)1.14]1[NbSe2]1, [(PbSe)1.14]3[NbSe2]2[(PbSe)1.14]1[NbSe2]2, [(PbSe)1.14]2[NbSe2]3[(PbSe)1.14]2[NbSe2]1, [(PbSe)1.14]2[NbSe2]2[(PbSe)1.14]1[NbSe2]1[(PbSe)1.14]1[NbSe2]1, [(PbSe)1.14]2[NbSe2]1[(PbSe)1.14]1[NbSe2]2[(PbSe)1.14]1[NbSe2]1. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance. 相似文献
7.
Catherine Pale-Grosdemange Corinna Feil Michel Rohmer Karl Poralla 《Angewandte Chemie (International ed. in English)》1998,37(16):2237-2240
Tetracyclic triterpenes (for example, 3 ) are formed as minor products of the cyclization of squalene ( 1 ) by squalene/hopene cyclase; they have also been found in vivo. The identification of these side products offers new insight into the complex biosynthesis of the hopane skeleton, and proves that the enzyme has no absolute control of the conformation of the acyclic substrate squalene and that tetra- and pentacyclic carbocationic intermediates are involved (for example, 2 ) in the cyclization process. 相似文献
8.
Volker Seibert Corinna Prohl Ida Schoultz Edward Rhee Rebecca Lopez Kareem Abderazzaq Chunshui Zhou Dieter A Wolf 《BMC biochemistry》2002,3(1):22-15
Background
SCF ubiquitin ligases share the core subunits cullin 1, SKP1, and HRT1/RBX1/ROC1, which associate with different F-box proteins. F-box proteins bind substrates following their phosphorylation upon stimulation of various signaling pathways. Ubiquitin-mediated destruction of the fission yeast cyclin-dependent kinase inhibitor Rum1p depends on two heterooligomerizing F-box proteins, Pop1p and Pop2p. Both proteins interact with the cullin Pcu1p when overexpressed, but it is unknown whether this reflects their co-assembly into bona fide SCF complexes. 相似文献9.
The Activation of Sulfur Hexafluoride at Highly Reduced Low‐Coordinate Nickel Dinitrogen Complexes 下载免费PDF全文
Dipl.‐Chem. Patrick Holze Dipl.‐Chem. Bettina Horn Prof. Dr. Christian Limberg Dipl.‐Chem. Corinna Matlachowski Dr. Stefan Mebs 《Angewandte Chemie (International ed. in English)》2014,53(10):2750-2753
The greenhouse gas sulfur hexafluoride is the common standard example in the literature of a very inert inorganic small molecule that is even stable against O2 in an electric discharge. However, a reduced β‐diketiminate nickel species proved to be capable of converting SF6 into sulfide and fluoride compounds at ambient standard conditions. The fluoride product complex features an unprecedented [NiF]+ unit, where the Ni atom is only three‐coordinate, while the sulfide product exhibits a rare almost linear [Ni(μ‐S)Ni]2+ moiety. The reaction was monitored applying 1H NMR, IR and EPR spectroscopic techniques resulting in the identification of an intermediate nickel complex that gave insight into the mechanism of the eight‐electron reduction of SF6. 相似文献
10.
Ralf Seemann Jean-Baptiste Fleury Corinna C. Maass 《The European physical journal. Special topics》2016,225(11-12):2227-2240
Self-propelled droplets are a special kind of self-propelled matter that are easily fabricated by standard microfluidic tools and locomote for a certain time without external sources of energy. The typical driving mechanism is a Marangoni flow due to gradients in the interfacial energy on the droplet interface. In this article we review the hydrodynamic prerequisites for self-sustained locomotion and present two examples to realize those conditions for emulsion droplets, i.e. droplets stabilized by a surfactant layer in a surrounding immiscible liquid. One possibility to achieve self-propelled motion relies on chemical reactions affecting the surface active properties of the surfactant molecules. The other relies on micellar solubilization of the droplet phase into the surrounding liquid phase. Remarkable cruising ranges can be achieved in both cases and the relative insensitivity to their own ‘exhausts’ allows to additionally study collective phenomena. 相似文献