全文获取类型
收费全文 | 405篇 |
免费 | 11篇 |
国内免费 | 1篇 |
专业分类
化学 | 282篇 |
晶体学 | 3篇 |
力学 | 24篇 |
数学 | 37篇 |
物理学 | 71篇 |
出版年
2024年 | 1篇 |
2022年 | 6篇 |
2021年 | 9篇 |
2020年 | 5篇 |
2019年 | 6篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 5篇 |
2013年 | 22篇 |
2012年 | 28篇 |
2011年 | 23篇 |
2010年 | 13篇 |
2009年 | 18篇 |
2008年 | 29篇 |
2007年 | 23篇 |
2006年 | 13篇 |
2005年 | 20篇 |
2004年 | 13篇 |
2003年 | 13篇 |
2002年 | 18篇 |
2001年 | 13篇 |
2000年 | 10篇 |
1999年 | 3篇 |
1998年 | 8篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 6篇 |
1990年 | 11篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 13篇 |
1983年 | 1篇 |
1982年 | 5篇 |
1981年 | 1篇 |
1978年 | 4篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1972年 | 3篇 |
排序方式: 共有417条查询结果,搜索用时 0 毫秒
1.
Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (CT = 10, 25, or 40%) and with SSS mole fractions covering a broad range (fSSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed CT. The dependence of swelling on μ shows both polyelectrolyte (fSSS beyond the minimum) and antipolyelectrolyte behaviors (in the low fSSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with fSSS for any CT. Moreover, in the low fSSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007 相似文献
2.
Joaquin Barbera Anne-Marie Levelut Mercedes Marcos Pilar Romero Jose Luis Serrano 《Liquid crystals》1991,10(1):119-126
We present a comparative study of various metallomesogenic complexes, using X-ray diffraction methods. For a given ligand linked to different metal atoms (Cu, Ni, VO), the nature of this central atom influences mainly the magnetic susceptibilities of the mesophases. With different ligands, which keep the close neighbourhood of the metal atom unchanged, the apparent length of the mesogenic unit is longer for short ligands than for longer ones. This unexpected behaviour is qualitatively well explained by taking into account the global shape of the different complexes. 相似文献
3.
K. C. Nicolaou Dionisios Vourloumis Tianhu Li Joaquin Pastor Nicolas Winssinger Yun He Sacha Ninkovic Francisco Sarabia Hans Vallberg Frank Roschangar N. Paul King M. Ray V. Finlay Pareskevi Giannakakou Pascal Verdier-Pinard Ernest Hamel 《Angewandte Chemie (International ed. in English)》1997,36(19):2097-2103
4.
Isac-García J Hernández-Mateo F Calvo-Flores FG Santoyo-González F 《The Journal of organic chemistry》2004,69(1):202-205
The reactivity of 2-deoxy-2-iodoglycosyl isothiocyanates toward O- and S-nucleophiles gives an easy access to 2-deoxy-2-iodoglycopyranosyl thiocarbamates and dithiocarbamates. Internal nucleophilic displacement of the iodine by the sulfur atom in these compounds allows the preparation of glycopyranoso[1,2-d]-1,3-thiazoles and glycopyranoso[1,2-d]-1,3-thiazolidin-2-one or -2-thione. Reaction with amines or polyamines as N-nucleophiles led directly to 2-aminoglycopyranoso[1,2-d]-1,3-thiazoles without isolation of the intermediate thioureas. Methyl 2-deoxy-2-iodoglycopyranosyl thiocarbamates also allow the synthesis of 2-deoxyglycopyranosyl thiocarbamates or 2-deoxy-2-iodoglycopyranosyl carbamates. 相似文献
5.
A method is described for the determination by solid phase spectrophotometry (SPS) of trace amounts of vanadium in natural water and crude petroleum samples. The procedure is based on fixation on a dextran-type anion exchanger of the complex V(IV)-Eriochrome Cyanine R. The absorbance of the gel, at 563 and 750 nm, packed in a 1 mm cell, is measured directly. Vanadium can be determined in the 0.6-25.0 mug l(-1) range with a relative standard deviation of 2.2%. The comparison of the SPS method and the gallic acid persulphate method shows that the linearity, analytical sensitivity and precision were better for the SPS method, and that the latter method has lower detection and quantification limits than the gallic acid persulphate method. 相似文献
6.
Castro C Karney WL Valencia MA Vu CM Pemberton RP 《Journal of the American Chemical Society》2005,127(27):9704-9705
Density functional and coupled cluster calculations show that facile thermal configuration change in [12]annulene occurs via a twist-coupled bond-shifting mechanism. The transition state for this process is highly aromatic with M?bius topology. At the CCSD(T)/cc-pVDZ//BH&HLYP/6-311+G** level, the isomerization of tri-trans-[12]annulene 1a (CTCTCT) to its di-trans isomer 2 (CCCTCT) via such a mechanism has a barrier of 18.0 kcal/mol, in good agreement with earlier experiments. Two other aromatic M?bius bond-shifting transition states were located that result in configuration change for other [12]annulene conformers. This mechanism contrasts sharply with diradical configuration change for acyclic polyenes and with planar bond-shifting mechanisms generally assumed for annulenes. This constitutes evidence that neutral M?bius aromatic annulenes play a role in the dynamic processes of neutral [4n]annulenes. 相似文献
7.
8.
9.
Odn Arjona Roberto Fernndez de la Pradilla Angel Martin-Domenech Joaquin Plumet 《Tetrahedron》1990,46(24):8187-8198
The nucleophilic Sn2' bridge opening of 7-oxabicyclo[2.2.1] hept-5-en-2-ols with organolithium reagents occurs in a regio- and stereospecific fashion to produce 6-substituted-cyclohex-4-en-1,3-diols, regardless of the stereochemistry at C-2. A free alcohol functionality is necessary to attain complete regiocontrol of the process. The methodology is utilized to prepare an optically pure cyclohexene derivative, (+)-(1S,3S,6R)-6-n-butyl-3-methyl-cyclohex-4-en-1,3-diol (5b), as a model system. 相似文献
10.
This work presents the carrying out of boiling-point distributions by simulated distillation with direct-column heating rather than oven-column heating. Column-heating rates of 300 degrees C/min are obtained yielding retention times of 73 s for n-tetratetracontane. The calibration curves of the retention time versus the boiling point, in the range of n-pentane to n-tetratetracontane, are identical to those obtained by slower oven-heating rates. The boiling-point distribution of the reference gas oil is compared with that obtained with column oven heating at rates of 15 to 40 degrees C/min. The results show boiling-point distribution values nearly the same (1-2 degrees F) as those obtained with oven column heating from the initial boiling point to 80% distilled off. Slightly higher differences are obtained (3-4 degrees F) for the 80% distillation to final boiling-point interval. Nonetheless, allowed consensus differences are never exceeded. Precision of the boiling-point distributions (expressed as standard deviations) are 0.1-0.3% for the data obtained in the direct column-heating mode. 相似文献