全文获取类型
收费全文 | 474篇 |
免费 | 15篇 |
国内免费 | 1篇 |
专业分类
化学 | 400篇 |
晶体学 | 5篇 |
力学 | 1篇 |
数学 | 32篇 |
物理学 | 52篇 |
出版年
2023年 | 3篇 |
2022年 | 6篇 |
2021年 | 11篇 |
2020年 | 11篇 |
2019年 | 8篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 17篇 |
2015年 | 7篇 |
2014年 | 10篇 |
2013年 | 25篇 |
2012年 | 34篇 |
2011年 | 36篇 |
2010年 | 8篇 |
2009年 | 6篇 |
2008年 | 26篇 |
2007年 | 18篇 |
2006年 | 21篇 |
2005年 | 23篇 |
2004年 | 15篇 |
2003年 | 12篇 |
2002年 | 13篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 7篇 |
1998年 | 4篇 |
1994年 | 6篇 |
1992年 | 7篇 |
1991年 | 3篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 9篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 3篇 |
1979年 | 7篇 |
1978年 | 9篇 |
1977年 | 4篇 |
1976年 | 7篇 |
1975年 | 4篇 |
1974年 | 8篇 |
1973年 | 10篇 |
1970年 | 2篇 |
1968年 | 2篇 |
1963年 | 2篇 |
1961年 | 2篇 |
1959年 | 2篇 |
排序方式: 共有490条查询结果,搜索用时 9 毫秒
21.
Metal-ion-assisted hydrolysis of dipeptides involving a serine residue in a neutral aqueous solution
Yashiro M Sonobe Y Yamamura A Takarada T Komiyama M Fujii Y 《Organic & biomolecular chemistry》2003,1(4):629-632
Dipeptides having a serine residue at the C-terminus, X-Ser, where X is an appropriate amino acid residue, were efficiently hydrolyzed in the presence of ZnCl2 at pH 7.0. The rapid hydrolysis of X-Ser is due to an autocatalysis of the hydroxy group in the serine residue, and is found to be accelerated by a metal ion, in particular by ZnCl2. Roles of the metal ion in the hydrolysis of peptides involving a serine residue, in relation to the recently reported protein cleavages, are discussed. 相似文献
22.
Takuya Adachi Yasuhisa Yamamura Mafumi Hishida Mao Ueda Shunji Ito 《Liquid crystals》2013,40(11):1340-1344
Molecular dynamics in the soft crystal, E phase of 6-octyl-2-phenylazulene was studied by X-ray diffraction, and dielectric and Fourier transform infrared spectroscopies. Clear dielectric dispersion is observed due to the head-to-tail disordering in a kHz range around 400 K. The CH stretching frequencies exhibit more pronounced shifts at the phase transition point from the high-temperature ordered crystal to the E phase than that at the melting from the E phase to the isotropic liquid. The results are discussed in comparison with a typical E series, 4-n-alkyl-4′-isothiocyanatobiphenyl (n being the number of carbon atoms in the alkyl group). 相似文献
23.
Sho Ikeda Ryo Shintani 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(17):5790-5794
A new mode of polymerization, rhodium‐catalyzed stitching polymerization, has been developed for the synthesis of π‐conjugated polymers with bridged repeating units from nonconjugated 1,5‐hexadiynes containing both terminal and internal alkyne moieties as monomers. The polymerization proceeded smoothly with a high degree of stitching efficiency under mild conditions, and 1,5,9‐decatriyne and 1,5,9,13‐tetradecatetrayne monomers could also be employed. The present polymerization strategy would be particularly beneficial for the synthesis of polymers consisting of a repeating unit that is difficult to prepare as a stable monomer because it does not require the use of a preformed bridged π‐conjugated monomer. 相似文献
24.
Bischolic acid derivative 1 linked by m-xylylene dicarbamate at the 3,3'-position was synthesized and the single ion channel properties were examined. Compound 1 showed two clearly distinct conductances, 9.5 (type A) and 25.3 pS (type B), under 500 mM KCl symmetric salt conditions, whereas various conductances, ranging from 5-20 pS, were observed in the tetramethylether analogue reported previously. Results indicate that the replacement of four methylether groups with hydroxyls at the 7, 7', 12, and 12' positions in the bischolic acid framework influences the stability of aggregated (supramolecular) ion channel structures. Ion permeability ratios (potassium/chloride and potassium/sodium) for each type of channel were also determined. 相似文献
25.
Photoswitching of the coordination number of silicon between four and five in allyldifluoro[2-(phenylazo)phenyl]silane, which was confirmed by X-ray analysis and multinuclear NMR spectroscopy, caused multistep reactions to proceed or stop, yielding tetrafluoro[2-(1-allyl-2-phenylhydrazino)phenyl]silicate without altering other reaction conditions. 相似文献
26.
Fujimori A Taguchi M Hakozaki S Kamishima K Ochiai B 《Langmuir : the ACS journal of surfaces and colloids》2012,28(29):10830-10837
Surface complexing (i.e., metal-bridged polymerization in this study) of a three-armed amphiphilic compound with metal-scavenging properties has been investigated using the surface pressure-area (π-A) isotherms of a Langmuir monolayer from the subphase. Inductively coupled plasma mass spectrometry (ICP-MS) was also carried out on eluted solutions from corresponding multilayers of the solid. Furthermore, the molecular arrangement and surface morphology of organized molecular films of the resultant comb polymer were estimated by in-plane and out-of-plane X-ray diffraction (XRD) and by atomic force microscopy. From an analysis of the wide-angle X-ray diffraction of the corresponding monomer in the bulk, the long hydrocarbon chains are observed to pack hexagonally in the solid state. Compared to their monolayer on distilled water as the subphase, a polymerized monolayer on a buffer solution containing Cd(2+) ions is remarkably expanded at 15 °C. From ICP-MS and IR measurements, it is found that this monolayer stoichiometrically contains Cd(2+) ions on the -SH group. It is found by XRD that highly ordered layer structures and regular 2D lattices are constructed in the organized molecular films of the Cd-bridged comb polymer. Furthermore, the surface morphology of Langmuir-Blodgett films fabricated from the monolayers on a buffer solution containing Cd(2+) and Pd(2+) shows flat and smooth domains upon metal scavenging and polymerization. 相似文献
27.
Nobutaka Yamaoka Kohei Sumida Itsuki Itani Hiroko Kubo Yusuke Ohnishi Sho Sekiguchi Dr. Toshifumi Dohi Prof. Dr. Yasuyuki Kita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):15004-15011
Metal‐free oxidative C? C coupling by using polyalkoxybenzene‐derived diaryliodonium(III) salts as both the oxidant and aryl source has been developed. These salts can induce single‐electron‐transfer (SET) oxidation to yield electron‐rich arenes and subsequently transfer the polyalkoxyphenyl group into in situ generated aromatic radical cations to produce biaryl products. The reaction is promoted by a Lewis acid that activates the iodonium salts. It has been revealed that the reactivity of the salts under acidic conditions is quite different to their known behavior under basic conditions. The reactivity preference of a series of iodonium salts in the SET oxidation and their ligand transfer abilities have been systematically investigated and the results are summarized in this report. 相似文献
28.
Fujiwara Masahide Hirosawa Koki Nonose Naoko Nishida Sho Furuta Naoki 《Accreditation and quality assurance》2019,24(5):329-339
Accreditation and Quality Assurance - The goal of this study was to evaluate the uncertainty of elemental analytical methods that use laser ablation in liquid (LAL) as a pretreatment. After LAL... 相似文献
29.
Maruyama T Yamamura H Kotani T Kamiya N Goto M 《Organic & biomolecular chemistry》2004,2(8):1239-1244
Lipase-catalyzed alcoholysis between vinyl acetate and 2-phenyl-1-propanol was investigated in dialkylimidazolium-based ionic liquids. Although native lipase powder exhibited very low activity in an ionic liquid, forming a poly(ethylene glycol)(PEG)-lipase complex improved the lipase activity in the ionic liquid. The activity of the PEG-lipase complex was higher in ionic liquids than in common organic solvents (n-hexane, isooctane and dimethylsulfoxide). Fluorescence measurements using 4-aminophthalimide revealed that the ionic liquids were more hydrophilic than the organic solvents used for non-aqueous enzymology. A kinetic study of lipase-catalyzed alcoholysis in an ionic liquid ([Bmim][PF6]) revealed that the Michaelis constant (Km) for 2-phenyl-1-propanol in the ionic liquid was half that in n-hexane, suggesting that the ionic liquid stabilized the enzyme-substrate complex. Finally, we carried out enantioselective alcoholysis of 1-phenylethanol in ionic liquids employing the PEG-lipase complex, and obtained high enantioselectivity, comparable to that in n-hexane. 相似文献
30.
A ring-closing metathesis reaction of allenynes occurred at room temperature in the presence of a molybdenum alkylidene complex to give ring-closed vinylallenes. The vinylallene skeletons were constructed by a metathesis-type reaction between the alkyne moiety and the proximal carbon-carbon double bond of the allene moiety. [reaction: see text] 相似文献