全文获取类型
收费全文 | 278篇 |
免费 | 12篇 |
国内免费 | 2篇 |
专业分类
化学 | 229篇 |
力学 | 9篇 |
数学 | 12篇 |
物理学 | 42篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2020年 | 3篇 |
2019年 | 2篇 |
2018年 | 1篇 |
2017年 | 2篇 |
2016年 | 6篇 |
2015年 | 5篇 |
2014年 | 6篇 |
2013年 | 6篇 |
2012年 | 18篇 |
2011年 | 16篇 |
2010年 | 12篇 |
2009年 | 9篇 |
2008年 | 12篇 |
2007年 | 21篇 |
2006年 | 8篇 |
2005年 | 14篇 |
2004年 | 12篇 |
2003年 | 10篇 |
2002年 | 8篇 |
2001年 | 10篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 16篇 |
1995年 | 4篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1990年 | 9篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 13篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1975年 | 1篇 |
1972年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1959年 | 1篇 |
1958年 | 1篇 |
1891年 | 1篇 |
1882年 | 1篇 |
排序方式: 共有292条查询结果,搜索用时 15 毫秒
81.
Dierk Knittel 《Journal of Electroanalytical Chemistry》1985,195(2):345-356
The electrochemical reduction of SO2 in dimethylformamide at Pt electrodes finally leads to the red species S3O2?6 via the blue complex S2O·?4. The UV-VIS absorption coefficients are determined: ?(S2O·?4) = (224 ± 25) × 105 cm2 mol?1; ?(S3O2?6) = (0.64 + 0.07) × 105 cm2 mol?1. A calculation of the complexing constant of SO2 with free SO·?2 radical based on potential shifts confirms this constant to be in the range of 200–700 1 mol?1.Two potentiometric titration methods (viz: with allylbromide and tetraethylammoniumtribromide) for analysis of electrolytically generated SIII-oxo-anions in DMF are presented. Reactions of those anions with aromatic aldehydes and trials for trapping of possibly formed SO are described. 相似文献
82.
Gais HJ Bruns PR Raabe G Hainz R Schleusner M Runsink J Babu GS 《Journal of the American Chemical Society》2005,127(18):6617-6631
Variable-temperature (1)H and (13)C NMR spectroscopy of the sulfonimidoyl-substituted allyltitanium(IV) complexes E-1a-c and Z-1a-c, which carry diethylamino groups at the Ti atom, revealed a fast 1,3-C,N-shift of the Ti atom, leading to an equilibrium between the epimeric Calpha-titanium allyl complexes A and C and the N-titanium allyl aminosulfoxonium ylide B. Based on these findings a model for the reactions of E-1a-c and Z-1a-c with aldehydes is proposed, which features regio- and diastereoselective reactions of the N-titanium ylide B at the alpha-position and the Calpha-titanium complex A at the gamma-position. Model ab initio calculations of the methylene and allyl (dimethylamino)sulfoxonium ylides 10 and 14, respectively, revealed short Calpha-S bonds, a stabilization by both electrostatic interaction and negative hyperconjugation, and a low Calpha-S rotational barrier. The ylides preferentially adopt Calpha-S and Calpha-N conformations in which the lone pair orbital at the Calpha atom is periplanar to the S=O bond and that at the N atom periplanar to the Calpha-Ph bond. Variable-temperature NMR spectroscopy of the sulfonimidoyl-substituted alkyltitanium(IV) complex 16, which carries diethylamino groups at the Ti atom, revealed a dynamic behavior leading to a complete topomerization of all four methylene hydrogens of the Calpha-ethyl groups. Two fast processes are held responsible for the topomerization of the hydrogens of 16. The first one is a reversible intramolecular beta-hydride elimination/alkene-Ti-H insertion with the intermediate formation of a complex between (Et(2)N)TiH and a 1-alkenyl sulfoximine, and the second one consists of a reversible 1,3-C,N-shift of the Ti atom in combination with a Calpha-S bond rotation. Interestingly, the room-temperature NMR spectra of the corresponding sulfonimidoyl-substituted alkyltitanium(IV) complex 17, which carries isopropoxy groups at the Ti atom, give no indication of a similar dynamic behavior of this complex. 相似文献
83.
Stereocontrol in Dinuclear Triple Lithium‐Bridged Titanium(IV) Complexes: Solving Some Stereochemical Mysteries 下载免费PDF全文
Prof. Dr. Markus Albrecht Dr. Elisabeth Isaak Dr. Verena Moha Prof. Dr. Gerhard Raabe Dr. Roland Fröhlich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6650-6658
Compounds 1 a – f ‐H2 form “monomeric” triscatecholate titanium(IV) complexes [Ti( 1 a – f )3]2?, which in the presence of Li cations are in equilibrium with the triple lithium‐bridged “dimers” [Li3(Ti( 1 a – f )3)2]?. The equilibrium strongly depends on the donor ability of the solvent. Usually, in solvents with high donor ability, the stereochemically labile monomer is preferred, whereas in nondonor solvents, the dimer is the major species. In the latter, the stereochemistry at the complex units is “locked”. The configuration at the titanium(IV) triscatecholates is influenced by addition of chiral ammonium countercations. In this case, the induced stereochemical information at the monomer is transferred to the dimer. Alternatively, the configuration at the metal complexes can be controlled by enantiomerically pure ester side chains. Due to the different orientation of the ester groups in the monomer or dimer, opposite configurations of the triscatecholates were observed by circular dichroism (CD) spectroscopy for [Ti( 1 c – e )3]2? or [Li3(Ti( 1 c – e )3)2]?. A surprising exception was found for the dimer [Li3(Ti( 1 f )3)2]?. Herein, the dimer is the dominating species in weak donor (methanol), as well as strong donor (DMSO), solvents. This is due to the bulkiness of the ester substituent destabilizing the monomer. Due to the size of the substituent in [Li3(Ti( 1 f )3)2]? the esters have to adopt an unusual conformation in the dimer resulting in a stereocontrol of the small methyl group. Following this, opposite stereocontrol mechanisms were observed for the central metal‐complex units of [Li3(Ti( 1 c – e )3)2]? or [Li3(Ti( 1 f )3)2]?. 相似文献
84.
Schleusner M Gais HJ Koep S Raabe G 《Journal of the American Chemical Society》2002,124(26):7789-7800
Selective addition of the chiral, sulfonimidoyl substituted bis(allyl)titanium complexes 5a-d, which are configurationally labile in regard to the Calpha-atoms, to N-toluenesulfonyl (Ts)-, N-2-trimethylsilylethanesulfonyl (SES)-, and N-tert-butylsulfonyl (Bus) alpha-imino ester (9a-c) in the presence of Ti(OiPr)(4) and ClTi(OiPr)(3) afforded with high regio- and diastereoselectivities in good yields the (syn, E)-configured beta-alkyl-gamma,delta-unsaturated alpha-amino acid derivatives 2a-g, which carry a chiral, electron-withdrawing nucleofuge at the delta-position and a cyclohexyl, an isopropyl, a phenyl, and a methyl group at the beta-position. Addition of the cyclic bis(allyl)titanium complex 14 to N-Bus alpha-imino ester 9c afforded with similar high regio- and diastereoselectivities the (E)- and (Z)-configured amino acid derivatives (E)-8 and (Z)-8. Reaction of complexes 5a-d with alpha-imino esters 9a-c in the presence of Ti(OiPr)(4) occurs stepwise to give first the mono(allyl)titanium complexes containing 2a-g as ligands, which react in the presence of ClTi(OiPr)(3) with a second molecule of 9a-c with formation of two molecules of 2a-g. Formation of (S,R,E)-configured homoallylic amines 2a-g entails Si,Re,E processes of alpha-imino esters 9a-c with the (R,R)-configured bis(allyl)titanium complexes (R,R)-5a-d and (R)-configured mono(allyl)titanium complexes (R)-17a-d, both of which are most likely in rapid equilibrium with their (S,S)-diastereomers and (S)-diastereomers, respectively. Interestingly, in the reaction of 5a-d with aldehydes, the (S,S)-configured complexes (S,S)-5a-d are the ones which react faster. Reaction of the N-titanated amino acid derivatives Ti-2a and Ti-2b with N-Ts alpha-imino ester 9a led to the highly diastereoselective formation of imidazolidinones 15a and 15b, respectively. Cleavage of the sulfonamide group of the N-Bus amino acid derivative 2d with CF(3)SO(3)H gave quantitatively the sulfonimidoyl functionalized amino acid H-2d. A Ni-catalyzed cross-coupling reaction of the amino acid derivative 2e with ZnPh(2) led to a substitution of the sulfonimidoyl group by a phenyl group and furnished the enantiomerically pure protected alpha-amino acid Bus-1. Two new N-sulfonyl alpha-imino esters, the SES and the Bus alpha-imino esters 9b and 9c, respectively, have been synthesized from the corresponding sulfonamides by the Kresze method in medium to good yields. The N-SES alpha-imino ester 9b and the N-Bus alpha-imino ester 9c should find many synthetic applications, in particular, in cases where the N-Ts alpha-imino ester 9a had been used before. 相似文献
85.
A highly enantioselective Friedel-Crafts reaction catalyzed by a chiral phosphoric acid was developed. N-Boc-protected ethyl trifluoropyruvate imine was activated by 6 mol % of catalyst and reacted with a wide variety of indole derivatives to afford quaternary α-amino acids in excellent yields (up to 99%) and high enantioselectivities (up to 98:2 er). 相似文献
86.
Andrea Zattoni Diana Cristina Rambaldi Pierluigi Reschiglian Manuela Melucci Silke Krol Ana Maria Coto Garcia Alfredo Sanz-Medel Dierk Roessner Christoph Johann 《Journal of chromatography. A》2009,1216(52):9106-9112
Synthesis and applications of new functional nanoparticles are topics of increasing interest in many fields of nanotechnology. Chemical modifications of inorganic nanoparticles are often necessary to improve their features as spectroscopic tracers or chemical sensors, and to increase water solubility and biocompatibility for applications in nano-biotechnology. Analysis and characterization of structured nanoparticles are then key steps for their synthesis optimization and final quality control. Many properties of structured nanoparticles are size-dependent. Particle size distribution analysis then provides fundamental analytical information. Asymmetrical flow field-flow fractionation (AF4) with multi-angle light scattering (MALS) detection is able to size-separate and to characterize nanosized analytes in dispersion. In this work we focus on the central role of AF4-MALS to analyze and characterize different types of structured nanoparticles that are finding increasing applications in nano-biotechnology and nanomedicine: polymer-coated gold nanoparticles, fluorescent silica nanoparticles, and quantum dots. AF4 not only size-fractionated these nanoparticles and measured their hydrodynamic radius (rh) distribution but it also separated them from the unbound, relatively low-Mr components of the nanoparticle structures which were still present in the sample solution. On-line MALS detection on real-time gave the gyration radius (rg) distribution of the fractionated nanoparticles. Additional information on nanoparticle morphology was then obtained from the rh/rg index. Stability of the nanoparticle dispersions was finally investigated. Aggregation of the fluorescent silica nanoparticles was found to depend on the concentration at which they were dispersed. Partial release of the polymeric coating from water-soluble QDs was found when shear stress was induced by increasing flowrates during fractionation. 相似文献
87.
Ines Raabe Dr. Katrin Wagner Kristin Guttsche Mingkui Wang Dr. Michael Grätzel Prof. Dr. Gustavo Santiso‐Quiñones Dr. Ingo Krossing Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(8):1966-1976
Weak and robust ? Tetraalkylammonium salts of weakly coordinating fluorinated alkoxyaluminates are easily accessible, chemically robust materials that show interesting physico‐chemical properties like low melting points, high electrochemical stability and electric conductivity in weakly polar solvents such as CH2Cl2, Ph‐F and toluene.
88.
Deniz Zengel Pirmin Koch Bentolhoda Torkashvand Jan‐Dierk Grunwaldt Maria Casapu Olaf Deutschmann 《Angewandte Chemie (International ed. in English)》2020,59(34):14423-14428
Reducing greenhouse gas and pollutant emissions is one of the most stringent priorities of our society to minimize their dramatic effects on health and environment. Natural gas (NG) engines, in particular at lean conditions, emit less CO2 in comparison to combustion engines operated with liquid fuels but NG engines still require emission control devices for NOx removal. Using state‐of‐the‐art technologies for selective catalytic reduction (SCR) of NOx with NH3, we evaluated the interplay of the reducing agent NH3 and formaldehyde, which is always present in the exhaust of NG engines. Our results show that a significant amount of highly toxic hydrogen cyanide (HCN) is formed. All catalysts tested partially convert formaldehyde to HCOOH and CO. Additionally, they form secondary emissions of HCN due to catalytic reactions of formaldehyde and its oxidation intermediates with NH3. With the present components of the exhaust gas aftertreatment system the HCN emissions are not efficiently converted to non‐polluting gases. The development of more advanced catalyst formulations with improved oxidation activity is mandatory to solve this novel critical issue. 相似文献
89.
A. Carel N. Kwamen Marcel Schlottmann Dr. David Van Craen Dr. Elisabeth Isaak Julia Baums Li Shen Ali Massomi Dr. Christoph Räuber Benjamin P. Joseph Prof. Dr. Gerhard Raabe Dr. Christian Göb Prof. Dr. Iris M. Oppel Dr. Rakesh Puttreddy Dr. Jas S. Ward Prof. Dr. Kari Rissanen Dr. Roland Fröhlich Prof. Dr. Markus Albrecht 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1396-1405
The dissociation of hierarchically formed dimeric triple lithium bridged triscatecholate titanium(IV) helicates with hydrocarbyl esters as side groups is systematically investigated in DMSO. Primary alkyl, alkenyl, alkynyl as well as benzyl esters are studied in order to minimize steric effects close to the helicate core. The 1H NMR dimerization constants for the monomer–dimer equilibrium show some solvent dependent influence of the side chains on the dimer stability. In the dimer, the ability of the hydrocarbyl ester groups to aggregate minimizes their contacts with the solvent molecules. Due to this, most solvophobic alkyl groups show the highest dimerization tendency followed by alkenyls, alkynyls and finally benzyls. Furthermore, trends within the different groups of compounds can be observed. For example, the dimer is destabilized by internal double or triple bonds due to π–π repulsion. A strong indication for solvent supported London dispersion interaction between the ester side groups is found by observation of an even/odd alternation of dimerization constants within the series of n-alkyls, n-Ω-alkenyls or n-Ω-alkynyls. This corresponds to the interaction of the parent hydrocarbons, as documented by an even/odd melting point alternation. 相似文献
90.