全文获取类型
收费全文 | 844篇 |
免费 | 26篇 |
国内免费 | 2篇 |
专业分类
化学 | 697篇 |
晶体学 | 5篇 |
力学 | 7篇 |
数学 | 68篇 |
物理学 | 95篇 |
出版年
2023年 | 9篇 |
2022年 | 13篇 |
2021年 | 20篇 |
2020年 | 10篇 |
2019年 | 13篇 |
2018年 | 10篇 |
2017年 | 8篇 |
2016年 | 14篇 |
2015年 | 18篇 |
2014年 | 28篇 |
2013年 | 44篇 |
2012年 | 62篇 |
2011年 | 68篇 |
2010年 | 30篇 |
2009年 | 19篇 |
2008年 | 44篇 |
2007年 | 52篇 |
2006年 | 51篇 |
2005年 | 44篇 |
2004年 | 48篇 |
2003年 | 43篇 |
2002年 | 32篇 |
2001年 | 11篇 |
2000年 | 10篇 |
1999年 | 10篇 |
1998年 | 11篇 |
1997年 | 10篇 |
1996年 | 7篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 8篇 |
1989年 | 4篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1982年 | 6篇 |
1981年 | 6篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 5篇 |
1975年 | 4篇 |
1973年 | 4篇 |
1968年 | 3篇 |
1937年 | 3篇 |
1932年 | 7篇 |
1925年 | 4篇 |
1911年 | 4篇 |
1908年 | 3篇 |
排序方式: 共有872条查询结果,搜索用时 109 毫秒
21.
Florence Robaut Alexandre Crisci Madeleine Durand-Charre Danielle Jouanne 《Microscopy and microanalysis》2006,12(4):331-334
The carbon contents in carburized steels were investigated by electron probe microanalysis (EPMA) for a range of carbon levels in the solid solution less than 1 wt%. This article describes the difficulties encountered with the classic analytical procedure using the k ratio of X-ray intensities and the phi(rhoz) model. Here, a suitable calibration curve method is presented with emphasis on the metallographic study of standard specimens and on the carbon decontamination of samples. 相似文献
22.
Peptide-based reversible and irreversible cysteine proteases inhibitors are well reported in the literature. Many of these compounds have an electrophilic carbonyl group as a cysteine trap in the place of a scissile amide moiety of the natural substrate. As a common mechanism strategy, we have designed a probe library of a cysteine trap for rapid optimization of P1-P1' pockets of different cysteine proteases. The synthesis of this library using a straightforward methodology based on polymer-supported reagents and scavengers to avoid tedious purification steps has been achieved. For the selective monobromination of diazo ketones, preparation of a new supported reagent, piperidinoaminomethylpolystyrene hydrobromide, is also described. 相似文献
23.
Alan S.F. BoydGraeme Cooke Florence M.A. DuclairoirVincent M. Rotello 《Tetrahedron letters》2003,44(2):303-306
We have investigated the electrochemically controlled hydrogen bonding interactions between tetrathiafulvalene host 3 and guests 4 or 5. Stabilisation of the 3+ state is dependent upon the nature of the guest species, whereas both guests prevent precipitation of the electrochemically generated 32+ species at the working electrode via hydrogen bonded molecular recognition processes. 相似文献
24.
25.
The enantioselective monoreduction of 2-alkyl 1,3-diketones by dynamic kinetic resolution using optically active ruthenium catalysts allowed the preparation of the C14-C25 fragment of bafilomycin A1. 相似文献
26.
Thallium was determined in natural waters by anodic stripping voltammetry at a hanging mercury drop electrode, in acetate buffer pH 4.6+EDTA, after preconcentration and separation on an anion exhange resin. For Pacific Ocean surface waters a mean value of 13.0±1.4 ng Tl l?1 was found, while for freshwater samples the value was 3.7±1.0 ng Tl l?1. Thermodynamic considerations of thallium speciation predict that both in seawater and freshwater thallium exists primarily in the trivalent state. This was confirmed by experiment. 相似文献
27.
Kinetic studies of cyanide exchange on [M(CN)(4)](2-) square-planar complexes (M = Pt, Pd, and Ni) were performed as a function of pH by (13)C NMR. The [Pt(CN)(4)](2-) complex has a purely second-order rate law, with CN(-) as acting as the nucleophile, with the following kinetic parameters: (k(2)(Pt,CN))(298) = 11 +/- 1 s(-1) mol(-1) kg, DeltaH(2) (Pt,CN) = 25.1 +/- 1 kJ mol(-1), DeltaS(2) (Pt,CN) = -142 +/- 4 J mol(-1) K(-1), and DeltaV(2) (Pt,CN) = -27 +/- 2 cm(3) mol(-1). The Pd(II) metal center has the same behavior down to pH 6. The kinetic parameters are as follows: (k(2)(Pd,CN))(298) = 82 +/- 2 s(-1) mol(-1) kg, DeltaH(2) (Pd,CN) = 23.5 +/- 1 kJ mol(-1), DeltaS(2) (Pd,CN) = -129 +/- 5 J mol(-1) K(-1), and DeltaV(2) (Pd,CN) = -22 +/- 2 cm(3) mol(-1). At low pH, the tetracyanopalladate is protonated (pK(a)(Pd(4,H)) = 3.0 +/- 0.3) to form [Pd(CN)(3)HCN](-). The rate law of the cyanide exchange on the protonated complex is also purely second order, with (k(2)(PdH,CN))(298) = (4.5 +/- 1.3) x 10(3) s(-1) mol(-1) kg. [Ni(CN)(4)](2-) is involved in various equilibrium reactions, such as the formation of [Ni(CN)(5)](3-), [Ni(CN)(3)HCN](-), and [Ni(CN)(2)(HCN)(2)] complexes. Our (13)C NMR measurements have allowed us to determine that the rate constant leading to the formation of [Ni(CN)(5)](3-) is k(2)(Ni(4),CN) = (2.3 +/- 0.1) x 10(6) s(-1) mol(-1) kg when the following activation parameters are used: DeltaH(2)() (Ni,CN) = 21.6 +/- 1 kJ mol(-1), DeltaS(2) (Ni,CN) = -51 +/- 7 J mol(-1) K(-1), and DeltaV(2) (Ni,CN) = -19 +/- 2 cm(3) mol(-1). The rate constant of the back reaction is k(-2)(Ni(4),CN) = 14 x 10(6) s(-1). The rate law pertaining to [Ni(CN)(2)(HCN)(2)] was found to be second order at pH 3.8, and the value of the rate constant is (k(2)(Ni(4,2H),CN))(298) = (63 +/- 15) x10(6) s(-1) mol(-1) kg when DeltaH(2) (Ni(4,2H),CN) = 47.3 +/- 1 kJ mol(-1), DeltaS(2) (Ni(4,2H),CN) = 63 +/- 3 J mol(-1) K(-1), and DeltaV(2) (Ni(4,2H),CN) = - 6 +/- 1 cm(3) mol(-1). The cyanide-exchange rate constant on [M(CN)(4)](2-) for Pt, Pd, and Ni increases in a 1:7:200 000 ratio. This trend is modified at low pH, and the palladium becomes 400 times more reactive than the platinum because of the formation of [Pd(CN)(3)HCN](-). For all cyanide exchanges on tetracyano complexes (A mechanism) and on their protonated forms (I/I(a) mechanisms), we have always observed a pure second-order rate law: first order for the complex and first order for CN(-). The nucleophilic attack by HCN or solvation by H(2)O is at least nine or six orders of magnitude slower, respectively than is nucleophilic attack by CN(-) for Pt(II), Pd(II), and Ni(II), respectively. 相似文献
28.
Weawkamol Leelapornpisit Minh‐Tan Ton‐That Florence Perrin‐Sarazin Kenneth C. Cole Johanne Denault Benoit Simard 《Journal of Polymer Science.Polymer Physics》2005,43(18):2445-2453
The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005 相似文献
29.
Florence Babonneau Christine Toutou Stéphanie Gavériaux 《Journal of Sol-Gel Science and Technology》1997,8(1-3):553-556
17O NMR experiments using enriched water were performed to followthe hydrolysis-condensation process of dimethyldiethoxysilanetetraethoxysilane and a 1/1 mixture of dimethyldiethoxysilane andtetraethoxysilane (H2O/OEt = 0.5; pH = 2). The spectrarecorded over several hours time period were simulated to followquantitatively the variations of residual water, hydroxyl groups(Si–17
H) and oxo bridges (Si–17
–Si). Presence of a resonance signal due oxo bridges between di- andtetrafunctional Si units clearly demonstrates that co-condensationreactions occur to a large extent between the two alkoxides, and that thesebonds are stable during the aging period. 相似文献
30.
Graeme Cooke Hugues A de Cremiers Florence M.A DuclairoirJulie Leonardi Georgina RosairVincent M Rotello 《Tetrahedron》2003,59(18):3341-3347
We describe the electrochemically controlled hydrogen bonding interactions between the isobutyl flavin/2,6-diferrocenylamidopyridine (2·5) and 9,10-phenanthrenequinone/1-ferrocenyl-3-hexylurea (4·6) dyads. Cyclic and square wave voltammetry studies have shown that the binding efficiencies between these moieties can be electrochemically actuated in non-polar (CH2Cl2 for 2·5) or polar (DMF for 4·6) organic solvents between three distinct states. 相似文献