全文获取类型
收费全文 | 614篇 |
免费 | 36篇 |
国内免费 | 2篇 |
专业分类
化学 | 510篇 |
晶体学 | 9篇 |
力学 | 8篇 |
数学 | 16篇 |
物理学 | 109篇 |
出版年
2023年 | 12篇 |
2022年 | 16篇 |
2021年 | 20篇 |
2020年 | 18篇 |
2019年 | 15篇 |
2018年 | 16篇 |
2017年 | 14篇 |
2016年 | 21篇 |
2015年 | 17篇 |
2014年 | 19篇 |
2013年 | 47篇 |
2012年 | 39篇 |
2011年 | 46篇 |
2010年 | 26篇 |
2009年 | 17篇 |
2008年 | 36篇 |
2007年 | 29篇 |
2006年 | 26篇 |
2005年 | 29篇 |
2004年 | 21篇 |
2003年 | 16篇 |
2002年 | 17篇 |
2001年 | 9篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1998年 | 7篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 3篇 |
1992年 | 10篇 |
1991年 | 3篇 |
1990年 | 7篇 |
1989年 | 8篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 8篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1971年 | 2篇 |
1968年 | 4篇 |
1966年 | 2篇 |
排序方式: 共有652条查询结果,搜索用时 15 毫秒
1.
Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Yuya Domoto Dr. Eric Busseron Prof. Dr. Mounir Maaloum Dr. Emilie Moulin Prof. Dr. Nicolas Giuseppone 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(5):1938-1948
We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by 1H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases. 相似文献
2.
Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis
Yuya Nakatsuji Yusuke Kobayashi Yoshiji Takemoto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(40):14253-14257
The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity. 相似文献
3.
Selective oxidation of an AlInAs layer was investigated for enhancement of magneto-optic effect in an optical isolator. Twelve times nonreciprocal phase shift enhancement was estimated from a measured AlInAs-oxide refractive index. 相似文献
4.
Makoto Kume Yuya Maki Bungo Ochiai Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2006,44(24):7040-7053
Spiro orthocarbonate (SOC) monomers having either an exomethylene group {3,3‐dimethyl‐9‐methylene‐1,5,7,11‐tetraoxaspiro[5.5]undecane (ExoSOC)} or an allyl group {9‐allyl‐3,3‐dimethyl‐1,5,7,11‐tetraoxaspiro[5.5]undecane (AllylSOC)} were radically copolymerized with vinyl monomers at several feed ratios to obtain the corresponding copolymers having SOC moieties in the side chain. The obtained copolymers were crosslinked via the double ring‐opening polymerization of the SOC moieties by a treatment with boron trifluoride etherate. The volume changes during the crosslinking of the copolymers were evaluated by density measurements with a gas pycnometer. As the SOC moiety composition increased, the volume shrinkage during the crosslinking was suppressed, and that finally changed into volume expansion. The volume changes during the crosslinking of the copolymers from AllylSOC were slightly larger than those of the copolymers from ExoSOC. The higher volume expansions in the crosslinking of AllylSOC‐based copolymers were ascribable to the lower steric hindrance around the SOC moieties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 7040–7053, 2006 相似文献
5.
6.
Okada T Komatsu K Kawamoto T Yamanaka T Kagi H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(10):2423-2427
In situ Raman spectroscopic measurements of water in the region of OH vibration were conducted up to 0.4 GPa at 23 and 52 degrees C. The frequencies of the decomposed OH stretching bands initially decreased with increasing pressure, reached a minimum at 0.15 GPa and increased up to 0.3 GPa and then decreased, which corresponds to the variations of the strength of hydrogen bonding. This variation was observed at 23 degrees C, but not at 52 degrees C, which suggests a change in pressure dependence on the hydrogen bond interaction between these two temperatures. Based on the equilibration model between hydrogen-bonded and nonhydrogen-bonded molecules, the present experimental results indicate that the pressure variation of the viscosity depends on the ratio of hydrogen-bonded molecules, rather than the strength of hydrogen bonding between molecules. 相似文献
7.
The mechanism of ion-exchange of cobalt(II) and nickel(II) on a resin loaded with 5-sulpho-8-quinolinol has been studied, and the chelate-forming reaction in the resin matrix shown to be rate-determining. The observed rate seems to be related to the rate of water-exchange with the metal ion in the aqueous phase, suggesting that complexation in the resin matrix may proceed according to the Eigen mechanism. 相似文献
8.
9.
Masahiro Murayama Ryoji Kanno Michihiko IrieShinya Ito Takayuki HataNoriyuki Sonoyama Yoji Kawamoto 《Journal of solid state chemistry》2002,168(1):140-148
The new lithium ionic conductors, thio-LISICON (LIthium SuperIonic CONductor), were found in the ternary Li2S-SiS2-Al2S3 and Li2S-SiS2-P2S5 systems. Their structures of new materials, Li4+xSi1−xAlxS4 and Li4−xSi1−xPxS4 were determined by X-ray Rietveld analysis, and the electric and electrochemical properties were studied by electronic conductivity, ac conductivity and cyclic voltammogram measurements. The structure of the host material, Li4SiS4 is related to the γ-Li3PO4-type structure, and when the Li+ interstitials or Li+ vacancies were created by the partial substitutions of Al3+ or P5+ for Si4+, large increases in conductivity occur. The solid solution member x=0.6 in Li4−xSi1−xPxS4 showed high conductivity of 6.4×10-4 S cm−1 at 27°C with negligible electronic conductivity. The new solid solution, Li4−xSi1−xPxS4, also has high electrochemical stability up to ∼5 V vs Li at room temperature. All-solid-state lithium cells were investigated using the Li3.4Si0.4P0.6S4 electrolyte, LiCoO2 cathode and In anode. 相似文献
10.
Changes in the structure of water deduced from the pressure dependence of the Raman OH frequency 总被引:3,自引:0,他引:3
We report on the Raman spectra of water under high temperature and pressure conditions and show a discontinuity in the pressure dependence of the OH stretching frequency. As pressure increases, the strength of hydrogen bonding increases rapidly in the pressure ranges up to 0.4+/-0.1 GPa at 25 degrees C, 1.0+/-0.1 GPa at 100 degrees C, and 1.3+/-0.1 GPa at 300 degrees C and slowly above these pressures. This finding clearly demonstrates the existence of discontinuities in the pressure response of the hydrogen bonds of water, which suggests a possible structural change under these conditions. 相似文献