全文获取类型
收费全文 | 363篇 |
免费 | 30篇 |
国内免费 | 1篇 |
专业分类
化学 | 338篇 |
晶体学 | 2篇 |
力学 | 5篇 |
数学 | 24篇 |
物理学 | 25篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 5篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 12篇 |
2018年 | 5篇 |
2017年 | 7篇 |
2016年 | 16篇 |
2015年 | 13篇 |
2014年 | 17篇 |
2013年 | 27篇 |
2012年 | 36篇 |
2011年 | 31篇 |
2010年 | 20篇 |
2009年 | 14篇 |
2008年 | 32篇 |
2007年 | 26篇 |
2006年 | 24篇 |
2005年 | 17篇 |
2004年 | 32篇 |
2003年 | 20篇 |
2002年 | 14篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1994年 | 1篇 |
1985年 | 1篇 |
排序方式: 共有394条查询结果,搜索用时 0 毫秒
61.
Niel V Milway VA Dawe LN Grove H Tandon SS Abedin TS Kelly TL Spencer EC Howard JA Collins JL Miller DO Thompson LK 《Inorganic chemistry》2008,47(1):176-189
"Tritopic" picolinic dihydrazone ligands with tridentate coordination pockets are designed to produce homoleptic [3 x 3] nonanuclear square grid complexes on reaction with transition-metal salts, and many structurally documented examples have been obtained with Mn(II), Cu(II), and Zn(II) ions. However, other oligomeric complexes with smaller nuclearities have also been discovered and identified structurally in some reactions involving Fe(II), Co(II), Ni(II), and Cu(II), with certain tritopic ligands. This illustrates the dynamic nature of the metal-ligand interaction and the conformationally flexible nature of the ligands and points to the possible involvement of some of these species as intermediates in the [3 x 3] grid formation process. Examples of mononuclear, dinuclear, hexanuclear, heptanuclear, and nonanuclear species involving Fe(II), Co(II), Ni(II), and Cu(II) salts with a series of potentially heptadentate picolinic dihydrazone ligands with pyrazine, pyrimidine, and pyridine end groups are described in the present study. Iron and cobalt complexation reactions are complicated by redox processes, which lead to mixed-oxidation-state Co(II)/Co(III) systems when starting with Co(II) salts, and reduction of Fe(III) to Fe(II) when starting with Fe(III). Magnetic exchange within the polynuclear structural frameworks is discussed and related to the structural features. 相似文献
62.
Van Lokeren L Maheut G Ribot F Escax V Verbruggen I Sanchez C Martins JC Biesemans M Willem R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(24):6957-6966
Diffusion-ordered NMR spectroscopy (DOSY NMR) is presented as a tool for the determination of the diffusion coefficients of organic ligands in suspensions of titanium dioxide nanoparticles. The nanoparticles were prepared by a sol-gel process by hydrolysis and condensation reactions of titanium tetra-n-butoxide in the presence of pentane-2,4-dione (acacH: acetylacetone), as well as para-toluenesulfonic acid (pTsA) and n-butanol (nBuOH). NMR spectroscopic studies were performed in various deuterated solvents, on both dispersed xerosols and diluted sols. The bipolar-pulsed field gradient longitudinal eddy-current delay (LED) pulse sequence was used for data acquisition. The data were processed by inverse Laplace transformation (ILT), by using a maximum entropy algorithm, to afford 2D DOSY spectra. Different diffusion regimes for organic ligands in the bound and unbound states were successfully discriminated, more particularly in [D3]acetonitrile, thus allowing assessment of their interactions with the nanoparticles. 相似文献
63.
Alain Valla Zo Andriamialisoa Michel Giraud Virginie Prat Alain Laurent Pierre Potier 《Tetrahedron letters》1999,40(52):1261-9237
A stereoselective synthesis of 13Z retinoic acids via β-methylenealdehydes is described. In methylene-de-oxo-bisubstitution reactions (Knoevenagel, Stobbe, etc.), these new synthons produce stereoselectively E olefins. Hence, a synthesis of 13Z retinoic acids is described, via a stereospecific monodecarboxylation of carboxy-14-retinoic acids. 相似文献
64.
65.
Gorteau V Bollot G Mareda J Perez-Velasco A Matile S 《Journal of the American Chemical Society》2006,128(46):14788-14789
We report the design, synthesis, and evaluation of rigid oligonaphthalenediimide (O-NDI) rods that are expected to act as transmembrane anion-pi slides. Studies in fluorogenic large unilamellar egg yolk phosphatidylcholine vesicles reveal that rigid O-NDI rods mediate anion-selective transport with a rare halide VI selectivity sequence (Cl- > F- > Br- > I-). This and decreasing activity, selectivity, and halide sequence with increasing positive charge of the rod termini support the occurrence of anion-pi interactions. A strong anomalous mole fraction effect in Cl-/I- mixtures is in agreement with the existence of multiple active sites along the anion-pi slide and multi-anion hopping as a mechanism of transport. The strong inverted NDI quadruple moment found by DFT calculations is in excellent agreement with these results. 相似文献
66.
Photocyclization of N-methyldiphenylamine to N-methylcarbazole is achieved within the microenvironment provided by site I of serum albumins. Quantum yield determinations, combined with transient absorption spectroscopic detection of the dihydrocarbazole intermediate, demonstrate that protein encapsulation provides a subtle control of the kinetic parameters, leading to optimized efficiencies. 相似文献
67.
68.
Montaignac B Praveen C Vitale MR Michelet V Ratovelomanana-Vidal V 《Chemical communications (Cambridge, England)》2012,48(52):6559-6561
Enantioselective metallo-organocatalyzed carbocyclizations of formyl-alkynes have been developed. The cooperation between aminocatalysis and a chiral copper(I) complex granted access to enantio-enriched cyclopentanes through the challenging formation of all-carbon quaternary stereocenters. 相似文献
69.
Efficient Csp(3)-Csp(3) Suzuki couplings have been developed with both potassium cyclopropyl- and alkoxymethyltrifluoroborates. Moderate to good yields have been achieved in the cross-coupling of potassium cyclopropyltrifluoroborate with benzyl chlorides possessing electron-donating or electron-withdrawing substituents. Benzyl chloride was also successfully cross-coupled to potassium alkoxymethyltrifluoroborates derived from primary, secondary, and tertiary alcohols. 相似文献
70.
Harrak Y Blaszykowski C Bernard M Cariou K Mainetti E Mouriès V Dhimane AL Fensterbank L Malacria M 《Journal of the American Chemical Society》2004,126(28):8656-8657
5-En-1-yn-3-ol substrates bearing a free hydroxyl group or an acyl group are highly versatile partners for PtCl2-catalyzed cycloisomerizations. Electrophilic activation of the alkyne moiety triggers at wish a hydride or an O-acyl migration yielding at the end to regioisomeric keto derivatives. The efficient preparation of Sabina ketone, an important monoterpene precursor, has been worked out. 相似文献