全文获取类型
收费全文 | 2997篇 |
免费 | 158篇 |
国内免费 | 13篇 |
专业分类
化学 | 2247篇 |
晶体学 | 11篇 |
力学 | 126篇 |
数学 | 344篇 |
物理学 | 440篇 |
出版年
2023年 | 32篇 |
2022年 | 45篇 |
2021年 | 58篇 |
2020年 | 70篇 |
2019年 | 66篇 |
2018年 | 43篇 |
2017年 | 36篇 |
2016年 | 90篇 |
2015年 | 87篇 |
2014年 | 95篇 |
2013年 | 151篇 |
2012年 | 222篇 |
2011年 | 261篇 |
2010年 | 130篇 |
2009年 | 147篇 |
2008年 | 230篇 |
2007年 | 206篇 |
2006年 | 213篇 |
2005年 | 202篇 |
2004年 | 172篇 |
2003年 | 137篇 |
2002年 | 121篇 |
2001年 | 61篇 |
2000年 | 37篇 |
1999年 | 26篇 |
1998年 | 24篇 |
1997年 | 23篇 |
1996年 | 30篇 |
1995年 | 8篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 19篇 |
1991年 | 9篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 11篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1978年 | 7篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1971年 | 2篇 |
排序方式: 共有3168条查询结果,搜索用时 15 毫秒
71.
Iron-catalyzed homo-coupling of simple and functionalized arylmagnesium reagents is described. The reaction is highly chemoselective (CN, COOEt and NO(2) groups are tolerated). The procedure was used to perform intramolecular couplings. This cyclization reaction is the key step of the total synthesis of the N-methylcrinasiadine. 相似文献
72.
F. Schaller W. Schwarz H.-D. Hausen K. W. Klinkhammer J. Weidlein 《无机化学与普通化学杂志》1997,623(9):1455-1466
Base-free Tris(trimethylsilyl)methyl Derivatives of Lithium, Aluminium, Gallium, and Indium Base-free LiR* (R*=-C(SiMe3)3) has been prepared from R*Cl and Li-metal in toluene at 85?90°C and used to synthesize the metallanes R*MMe2 with M = Al, Ga and In, respectively. The NMR (1H, 13C, 29Si) and the vibrational spectra of these trisyl compounds have been discussed. AlCl3 and LiR*(ratio 1 : 1) forms the metallate metallate Li[R*AlCl3]. The triclinic unit cell (space group P1 ) consists of a centrosymmetric assoziate, formed by four Li[R*AlCl3]- units with Al? Cl…?Li bridges, two pairs of Li-atoms differing in their chlorine-coordination and two disordered toluene molecules, inserted in the crystal lattice (R1wR2 =0,0444/0,1072). The reaction of GaCl3 with LiR* (I :1) gives the unusual sesquichloride (R*Ga(Cl1,33)Me0,67)3 in moderate yield. The X-ray structure determination shows a Ga3Cl3-skeleton with chairconformation and disordered, terminal gallium ligands (R1/wR2= 0,0646/0,2270). 相似文献
73.
H. Budzikiewicz U. Schaller H. Korth G. Pulverer 《Monatshefte für Chemie / Chemical Monthly》1979,110(4):947-953
Alkyl and alkenyl quinolines (so-called Pyo-substances) and theirN-oxides were isolated fromPseudomonas aeruginosa. Structures proposed earlier could be confirmed; a new representative (Pyo V) is described.
IV. Mitt.:A. Römer, H. Budzikiewicz, H. Korth undG. Pulverer, Tetrahedron Letters1979, 509. 相似文献
74.
Düggeli M Goujon-Ginglinger C Ducotterd SR Mauron D Bonte C von Zelewsky A Stoeckli-Evans H Neels A 《Organic & biomolecular chemistry》2003,1(11):1894-1899
A series of new tetradentate ligands containing two bipyridine groups or two pyridine moieties carrying amine substituents has been synthesised either from 5'- and 6'-substituted chiral bipyridines, or from chiral pyridine derivatives. These precursors have been prepared from (-)-alpha-pinene or (-)-myrtenal, respectively. The structures of three tetradentate-, and of five chiral bipyridine ligands have been determined by X-ray diffraction. 相似文献
75.
The use of 4.2 nm gold nanoparticles wrapped in an adsorbates shell and embedded in a TiO2 metal oxide matrix gives the opportunity to investigate ultrafast electron-electron scattering dynamics in combination with electronic surface phenomena via the surface plasmon lifetimes. These gold nanoparticles (NPs) exhibit a large nonclassical broadening of the surface plasmon band, which is attributed to a chemical interface damping. The acceleration of the loss of surface plasmon phase coherence indicates that the energy and the momentum of the collective electrons can be dissipated into electronic affinity levels of adsorbates. As a result of the preparation process, gold NPs are wrapped in a shell of sulfate compounds that gives rise to a large density of interfacial molecules confined between Au and TiO2, as revealed by Fourier-transform-infrared spectroscopy. A detailed analysis of the transient absorption spectra obtained by broadband femtosecond transient absorption spectroscopy allows separating electron-electron and electron-phonon interaction. Internal thermalization times (electron-electron scattering) are determined by probing the decay of nascent nonthermal electrons (NNEs) and the build-up of the Fermi-Dirac electron distribution, giving time constants of 540 to 760 fs at 0.42 and 0.34 eV from the Fermi level, respectively. Comparison with literature data reveals that lifetimes of NNEs measured for these small gold NPs are more than four times longer than for silver NPs with similar sizes. The surprisingly long internal thermalization time is attributed to an additional decay mechanism (besides the classical e-e scattering) for the energy loss of NNEs, identified as the ultrafast chemical interface scattering process. NNEs experience an inelastic resonant scattering process into unoccupied electronic states of adsorbates, that directly act as an efficient heat bath, via the excitation of molecular vibrational modes. The two-temperature model is no longer valid for this system because of (i) the temporal overlap between the internal and external thermalization process is very important; (ii) a part of the photonic energy is directly transferred toward the adsorbates (not among "cold" conduction band electrons). These findings have important consequence for femtochemistry on metal surfaces since they show that reactions can be initiated by nascent nonthermal electrons (as photoexcited, out of a Fermi-Dirac distribution) besides of the hot electron gas. 相似文献
76.
Michel F Thomas F Hamman S Saint-Aman E Bucher C Pierre JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(17):4115-4125
Galactose oxidase (GO) is an enzyme that catalyzes two-electron oxidations. Its active site contains a copper atom coordinated to a tyrosyl radical, the biogenesis of which requires copper and dioxygen. We have recently studied the properties of electrochemically generated mononuclear Cu(II)-phenoxyl radical systems as model compounds of GO. We present here the solution chemistry of these ligands under various copper and dioxygen statuses: N(3)O ligands first chelate Cu(II), leading, in the presence of base, to [Cu(II)(ligand)(CH(3)CN)](+) complexes (ortho-tert-butylated ligands) or [(Cu(II))(2)(ligand)(2)](2+) complexes (ortho-methoxylated ligands). Excess copper(II) then oxidizes the complex to the corresponding mononuclear Cu(II)-phenoxyl radical species. N(2)O(2) tripodal ligands, in the presence of copper(II), afford directly a copper(II)-phenoxyl radical species. Addition of more than two molar equivalents of copper(II) affords a Cu(II)-bis(phenoxyl) diradical species. The donor set of the ligand directs the reaction towards comproportionation for ligands possessing an N(3)O donor set, while disproportionation is observed for ligands possessing an N(2)O(2) donor set. These results are discussed in the light of recent results concerning the self-processing of GO. A path involving copper(II) disproportionation is proposed for oxidation of the cross-linked tyrosinate of GO, supporting the fact that both copper(I) and copper(II) activate the enzyme. 相似文献
77.
Benturquia N Couderc F Sauvinet V Orset C Parrot S Bayle C Renaud B Denoroy L 《Electrophoresis》2005,26(6):1071-1079
Serotonin or 5-hydroxytryptamine (5-HT) is a major neurotransmitter in the central nervous system. In this work, a method for analyzing 5-HT in brain microdialysis samples using a commercially available capillary electrophoresis (CE) system has been developed. A pH-mediated in-capillary preconcentration of samples was performed, and after separation by capillary zone electrophoresis, native fluorescence of 5-HT was detected by a 266 nm solid-state laser. The separation conditions for the analysis of 5-HT in standard solutions and microdialysates have been optimized, and this method has been validated on both pharmacological and analytical bases. Separation of 5-HT was performed using a 80 mmol/L citrate buffer, pH 2.5, containing 20 mmol/L hydroxypropyl-beta-cyclodextrin (HP-beta-CD) and +30 kV voltage. The detection limit was 2.5 x 10(-10) mol/L. This method allows the in vivo brain monitoring of 5-HT using a simple, accurate CE measurement in underivatized microdialysis samples. 相似文献
78.
Amgoune A Thomas CM Roisnel T Carpentier JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(1):169-179
A series of new alkoxy-amino-bis(phenols) (H2L 1-6) has been synthesized by Mannich condensations of substituted phenols, formaldehyde, and amino ethers or diamines. The coordination properties of these dianionic ligands towards yttrium, lanthanum, and neodymium have been studied. The resulting Group 3 metal complexes have been used as initiators for the ring-opening polymerization of rac-lactide to provide poly(lactic acid)s (PLAs). The polymerizations are living, as evidenced by the narrow polydispersities of the isolated polymers, together with the linear natures of number average molecular weight versus conversion plots and monomer-to-catalyst ratios. Complex [Y(L6){N(SiHMe2)2}(THF)] (17) polymerized rac-lactide to heterotactic PLA (Pr = 0.90 at 20 degrees C) and meso-lactide to syndiotactic PLA (Pr = 0.75 at 20 degrees C). The in situ formation of [Y(L6)(OiPr)(THF)] (18) from 17 and 2-propanol resulted in narrower molecular weight distributions (PDI = 1.06). With complex 18, highly heterotactic PLAs with narrow molecular weight distributions were obtained with high activities and productivities at room temperature. The natures of the ligand substituents were shown to have a significant influence on the degree of control of the polymerizations, and in particular on the tacticity of the polymer. 相似文献
79.
Xu X Zhao Z Song P Zhou G Xu J Deng P Bourdet G Chanteloup JC Zou JP Fulop A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(11-12):2444-2447
Infrared (1.2-1.6 microm) luminescence in a ytterbium aluminium garnet (YbAG) crystal, doped with Cr (0.05at.%) ions, was investigated under CW laser diode pumping (lambda=940 nm). The Cr4+ emission band was observed with its peak at 1.34 microm and measured to be about 1.3 times with respect to Yb3+ IR luminescence (lambda=1.03 microm). We demonstrate that for the excitation wavelength of 940 nm Yb3+ ions act as sensitizers of the 3B2(3T2)-3B1(3A2) emission of Cr4+ ions. This crystal is promising as a high-efficient system for tunable laser (1.2-1.6 microm) output. 相似文献
80.
The one-carbon elongation of aldoses to ketoses using iodomethyllithium as the key reagent in the homologation step is exemplified by the preparation of two carbohydrates of chemical and biological interests: d-manno-hept-2-ulose from d-mannose and l-fructose from l-arabinose. 相似文献