全文获取类型
收费全文 | 5062篇 |
免费 | 129篇 |
国内免费 | 6篇 |
专业分类
化学 | 4002篇 |
晶体学 | 7篇 |
力学 | 44篇 |
数学 | 646篇 |
物理学 | 498篇 |
出版年
2019年 | 42篇 |
2018年 | 36篇 |
2017年 | 29篇 |
2016年 | 105篇 |
2015年 | 65篇 |
2014年 | 103篇 |
2013年 | 149篇 |
2012年 | 155篇 |
2011年 | 164篇 |
2010年 | 137篇 |
2009年 | 121篇 |
2008年 | 168篇 |
2007年 | 162篇 |
2006年 | 182篇 |
2005年 | 206篇 |
2004年 | 173篇 |
2003年 | 142篇 |
2002年 | 181篇 |
2001年 | 115篇 |
2000年 | 110篇 |
1999年 | 106篇 |
1998年 | 86篇 |
1997年 | 98篇 |
1996年 | 100篇 |
1995年 | 80篇 |
1994年 | 89篇 |
1993年 | 91篇 |
1992年 | 94篇 |
1991年 | 92篇 |
1990年 | 72篇 |
1989年 | 89篇 |
1988年 | 87篇 |
1987年 | 84篇 |
1986年 | 71篇 |
1985年 | 97篇 |
1984年 | 113篇 |
1983年 | 63篇 |
1982年 | 88篇 |
1981年 | 115篇 |
1980年 | 84篇 |
1979年 | 101篇 |
1978年 | 70篇 |
1977年 | 68篇 |
1976年 | 61篇 |
1975年 | 77篇 |
1974年 | 51篇 |
1973年 | 70篇 |
1972年 | 52篇 |
1971年 | 43篇 |
1970年 | 52篇 |
排序方式: 共有5197条查询结果,搜索用时 46 毫秒
861.
Tyrra W Naumann D Buslei S Kremer S Pantenburg I Scherer H 《Dalton transactions (Cambridge, England : 2003)》2007,(18):1829-1837
[NMe(4)][R(f)Te(SC(S)NR(2))(2)] derivatives are selectively formed by the oxidation of [NMe(4)]TeR(f) (R(f) = CF(3), C(2)F(5)) with [R(2)NC(S)S](2) (NR(2) = NEt(2), NBz(2), N(CH(2))(4)) in almost quantitative yields. An alternative route to obtain the dithiocarbamato complex anions offer reactions of Te[SC(S)NR(2)](2) (NR(2) = NEt(2), NBz(2)) with equimolar amounts of Me(3)SiR(f) and [NMe(4)]F. Some of the derivatives were recrystallized with bulky cations in order to determine the crystal structures. Structural elucidation by diffraction methods exhibit the structural feature of a distorted pentagonal planar environment (resembling "butterflies") around the tellurium centres. The carbamato tellurates can be transferred easily into the neutral derivatives, R(f)TeSC(S)NR(2), upon treatment with Ag[BF(4)]. In solution they equilibrate with Te(2)(R(f))(2) and [R(2)NC(S)S](2) and finally are transformed into Te(R(f))(2), Te[SC(S)NR(2)](2), and Te[SC(S)NR(2)](4), respectively. All compounds are fully characterized by NMR spectroscopic methods ((1)H, (13)C, (19)F, (125)Te). Additionally, synthesis and characterization of the hitherto unknown derivative [NMe(4)]TeC(2)F(5) are described. 相似文献
862.
863.
864.
Natalya V. Kirij Yurii L. Yagupolskii Wieland Tyrra Dr. Ingo Pantenburg Dieter Naumann Prof. Dr. 《无机化学与普通化学杂志》2007,633(7):943-945
represents the first structurally characterized example of a trifluoromethyl main group element compound with more than 8‐N (where N is the main group number) perfluoroalkyl groups and also the first fluoro(triorgano)tellurium derivative. Its polymeric nature is caused by asymmetric bridging fluorine atoms forming infinite chains. 相似文献
865.
The anions [(TeCF3)2X]? (X = Cl, Br, I) resemble the trihalides [I2X]? in the solid state and show similar dynamic behaviour in solution. All three compounds crystallize iso‐structurally in the triclinic space group with Z = 2 and exhibit cell dimensions according to the sizes of the halogen atoms. 相似文献
866.
We report the analysis of human rhinovirus serotype 2 (HRV2) on a commercially available lab-on-a-chip instrument. Due to lack of sufficient native fluorescence, the proteinaceous capsid of HRV2 was labeled with Cy5 for detection by the red laser (lambda ex 630 nm) implemented in the instrument. On the microdevice, electrophoresis of the labeled virus was possible in a BGE without stabilizing detergents, which is in contrast to conventional CE; moreover, analysis times were drastically shortened to the few 10 s range. Resolution of the sample constituents (virions, a contaminant present in all virus preparations, and excess dye) was improved upon adaptation of the separation conditions, mainly by adjusting the SDS concentration of the BGE. Purity of fractions from size-exclusion chromatography after labeling of virus was assessed, and affinity complex formation of the labeled virus with various recombinant very-low-density lipoprotein receptor derivatives differing in the number of concatenated V3 ligand binding repeats was monitored. Virus analysis on microchip devices is of particular interest for experiments with infectious material because of easy containment and disposal of samples. Thus, the employment of microchip devices in routine analysis of viruses appears to be exceptionally attractive. 相似文献
867.
Meinhard D Wegner M Kipiani G Hearley A Reuter P Fischer S Marti O Rieger B 《Journal of the American Chemical Society》2007,129(29):9182-9191
Starting from differently substituted boronic acids as versatile building block, new "ortho-aryl" alpha-diimine ligands a-h were synthesized in an easy, high-yielding route. Reaction of the complex precursor diacetylacetonato-nickel(II) with a trityl salt, like [CPh3] [B(C6F5)4] or [CPh3] [SbCl6], in the presence of the diimine ligands afford the monocationic, square planar complexes 2a-g in almost quantitative yields. Suitable crystals (2d',e,f,g) were submitted for X-ray diffraction analysis. A geometry model was developed to describe the orientation of ligand fragments around the nickel(II) center that influence the polymer microstructure. At elevated reaction temperature and pressure, and in the presence of hydrogen, 2a-e catalyze the homopolymerization of ethylene to give branched PE products ranging from HD- to LLD-PE grades. The polymerization results indicate the possibility of precise microstructure control depending on the particular complex substitution. Preliminary investigations on material density and mechanical behavior by uniaxial stretching until failure point toward new material properties that can result from the simple ethylene monomer by catalyst design. 相似文献
868.
Serra D Bosch A Russo DM Rodríguez ME Zorreguieta A Schmitt J Naumann D Yantorno O 《Analytical and bioanalytical chemistry》2007,387(5):1759-1767
This work describes the application of several analytical techniques to characterize the development of Bordetella pertussis biofilms and to examine, in particular, the contribution of virulence factors in this development. Growth of surface-attached
virulent and avirulent B. pertussis strains was monitored in continuous-flow chambers by techniques such as the crystal violet method, and nondestructive methodologies
like fluorescence microscopy and Fourier transform (FT) IR spectroscopy. Additionally, B. pertussis virulent and avirulent strains expressing green fluorescent protein were grown adhered to the base of a glass chamber of
1-μm thickness. Three-dimensional images of mature biofilms, acquired by confocal laser scanning microscopy, were quantitatively
analysed by means of the computer program COMSTAT. Our results indicate that only the virulent (Bvg+) phase of B. pertussis is able to attach to surfaces and develop a mature biofilm. In the virulent phase these bacteria are capable of producing
a biofilm consisting of microcolonies of approximately 200 μm in diameter and 24 μm in depth. FTIR spectroscopy allowed us
not only to follow the dynamics of biofilm growth through specific biomass and biofilm marker absorption bands, but also to
monitor the maturation of the biofilm by means of the increase of the carbohydrate-to-protein ratio. 相似文献
869.
A method for finding a transition state (TS) between a reactant minimum and a quasi-flat, high dissociation plateau on the potential energy surface is described. The method is based on the search of a growing string (GS) along reaction pathways defined by different Newton trajectories (NT). Searches with the GS-NT method always make it possible to identify the TS region because monotonically increasing NTs cross at the TS or, if not monotonically increasing, possess turning points that are located in the TS region. The GS-NT method is applied to quasi-barrierless and truly barrierless chemical reactions. Examples are the dissociation of methylenecyclopropene to acetylene and vinylidene, for which a small barrier far out in the exit channel is found, and the cycloaddition of singlet methylene and ethene, which is barrierless for a broad reaction channel with Cs-symmetry reminiscent of a mountain cirque formed by a glacier. 相似文献
870.
Absorption, fluorescence, and fluorescence excitation spectra of two substituted [(5-methyl-2-pyridine-2'-yl-1,3-thiazole-4-yl)oxy]acetic acid and its methyl ester (2,2'-pyridylthiazoles) are studied at various pH values in aqueous solution. The acid exhibits pKa(1)=2.10+/-0.07 and pKa(2)=3.45+/-0.03, whereas the ester pKa=1.93+/-0.03. The protonation site is the pyridyl-nitrogen. When protonated, the cisoid conformer is the most stable; however, the transoid conformer is more stable in the deprotonated form. Fluorescence quantum yields close to unity are found. Large Stokes shift values are explained by the shortening of the inter-ring bond in the excited state. These compounds may be useful for metal sensing and as laser dyes. 相似文献