全文获取类型
收费全文 | 3357篇 |
免费 | 439篇 |
国内免费 | 240篇 |
专业分类
化学 | 3411篇 |
晶体学 | 33篇 |
力学 | 22篇 |
综合类 | 17篇 |
数学 | 218篇 |
物理学 | 335篇 |
出版年
2024年 | 5篇 |
2023年 | 33篇 |
2022年 | 206篇 |
2021年 | 220篇 |
2020年 | 207篇 |
2019年 | 149篇 |
2018年 | 91篇 |
2017年 | 109篇 |
2016年 | 176篇 |
2015年 | 175篇 |
2014年 | 222篇 |
2013年 | 296篇 |
2012年 | 186篇 |
2011年 | 181篇 |
2010年 | 162篇 |
2009年 | 176篇 |
2008年 | 157篇 |
2007年 | 154篇 |
2006年 | 160篇 |
2005年 | 158篇 |
2004年 | 138篇 |
2003年 | 125篇 |
2002年 | 88篇 |
2001年 | 46篇 |
2000年 | 57篇 |
1999年 | 51篇 |
1998年 | 51篇 |
1997年 | 31篇 |
1996年 | 46篇 |
1995年 | 30篇 |
1994年 | 46篇 |
1993年 | 22篇 |
1992年 | 17篇 |
1991年 | 11篇 |
1990年 | 4篇 |
1989年 | 10篇 |
1988年 | 9篇 |
1987年 | 12篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1978年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有4036条查询结果,搜索用时 15 毫秒
51.
The preparation of concentrated sols and transparent stiff gels of II-VI semiconductors nanocrystals is reported. A two-step process for the production of cadmium sulfide is reported. Sol stabilization and gelation control are achieved through successive passivation and depassivation of the surface of the nanocrystals which are complexed with thiols. The mechanisms driving the aggregation and the gelation are explained on the basis of NMR and SAXS experiments. Thin films as well as monoliths can be produced. The general principles of the method presented are not restricted to chalcogenide systems and thus enlarge the domain of application of the inorganic sol-gel process. 相似文献
52.
53.
Carlo Bonini Lucia Chiummiento Maria Funicello Gerardina Suanno Pietro Campaner 《Tetrahedron》2005,61(27):6580-6589
An efficient method has been developed for the synthesis of a versatile intermediate bearing azido, hydroxyl and ester functions, a useful precursor for peptidomimetic compounds. The two main features for this synthesis were the use of the Sharpless asymmetric dihydroxylation on thiophene acrylate and the subsequent regioselective ring opening by sodium azide of the cyclic sulfite. Highly chemoselective reduction of the azido alcohol led to a key compound which was utilized for the synthesis of two analogues of commercial anti HIV PR such as nelfinavir and saquinavir. The biological activity and molecular modelling study on these two new potential drugs have been evaluated. 相似文献
54.
Andrew M. Piggott 《Tetrahedron letters》2007,48(42):7452-7455
Sulfinamides are important in enantioselective synthesis, as rare post-translational modifications of proteins and as isosteres of the amide bond. Little is known about the rates of hydrolysis for aliphatic sulfinamides or the mechanism of hydrolysis. In this Letter, we show that sulfinamides hydrolyse by predominantly a non-specific acid/base catalysis with phosphate buffer but by varying the buffer concentration, it was possible to determine the hydrolysis rates of a range of sulfinamides with water through non-linear least squares regression. 相似文献
55.
S.?K.?MehtaEmail author K.?K.?Bhasin Neena?Mehta Shilpee?Dham 《Colloid and polymer science》2005,283(5):532-538
The behavior of rifampicin (D) with -cyclodextrin (-CyD) in aqueous media (W) has been examined by means of UV-vis spectroscopy and conductivity measurements over the temperature range 15–30 °C. The UV-vis study has been used to characterize the systems. The estimated molar absorption coefficient for D/CyD/W system was 10757±280 M–1 cm–1 in comparison to the value of 6133±99 M–1 cm–1 for D/W system. The conductivity was measured (i) as a function of [D] for binary D/W systems, (ii) as a function of [CyD], keeping the concentration of drug constant, for D/CyD/W system, and (iii) as a function of [D] in the presence of a constant cyclodextrin concentration. Two transition points were observed for D/CyD/W system at constant [CyD], which were assigned as cac-1 and cac-2. The stoichiometry of the association was estimated from the conductivity data. This was obtained from [drug] value at which the change in slope of occurs. The standard free energy change,
of aggregation was also calculated from the critical concentration data. An attempt has also been made to estimate the stoichiometry of -cyclodextrin:rifampicin association. 相似文献
56.
Yoichiro Iwase Koichi Kondo Kenji Kamada Koji Ohta 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3534-3541
1,4‐Bis(4‐benzylpyridinium)butadiyne triflate was aggregated in dimethylformamide and spontaneously converted into the 1,4‐addition type of polydiacetylene. The polymerization took place in a dipolar aprotic solvent with a large dielectric constant that could enhance the aggregation of the ionic diacetylene salt through the electrostatic interaction. The molecular weight of the diacetylene was leveled off after 30 h at 80 °C to reach 1.5 × 104 (number‐average molecular weight) that consisted of the 1,4‐addition type of polydiacetylene similar to polydiacetylenes obtained in the conventional solid‐state polymerization. Electron spin resonance spectra revealed that diradicals were generated at the earlier state aggregation to give rise to a solution polymerization. The UV spectra also suggested the presence of the activated aggregation associated with the polymerization as well as the eximer emission spectra. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3534–3541, 2002 相似文献
57.
Minoru Isobe Prof. Dr. Masakuni Kurono Dr. Katsunori Tsuboi Dr. Akira Takai Prof. Dr. 《化学:亚洲杂志》2007,2(3):377-385
We have accomplished the synthesis of 13C‐labeled tautomycin at the C18, C19, C21, and C22 positions starting from 100 % [13C]triethylphosphonoacetate for the purpose of elucidating the dynamics and conformation of the C17–C26 moiety. NMR spectroscopy of 13C‐labeled tautomycin revealed strong binding with protein phosphatase type 1 and new features in the 13C NMR spectrum, such as the very small three‐bond coupling constants (2J). 相似文献
58.
The efficiency of the operation of a porous electrode with an immobilized enzyme is defined, in particular, by a lucky structure of its active layer, which can contain nanosized particles of the support. The composites of such a kind are prepared with the aid of methods of colloidal chemistry. The aim of this particular investigation is to perform a computer simulation of processes of coagulation of particles of the support and their possible heterocoagulation with molecules of the enzyme. Algorithms of the formation of nanocomposite structures in solution are suggested. Calculations show that the concentration of the enzyme molecules in the nanocomposite structures cannot exceed a certain critical value. On the other hand, at a fixed value of the concentration of the enzyme molecules, the concentration of the support particles must not fall below a certain threshold quantity, which provides for the passing of current through the active layer. In order for all the enzyme molecules, rather than for a fraction of these, in the composite to take part in the process of bioelectrocatalysis, the concentration of support particles must be increased even higher, to an optimum value.__________Translated from Elektrokhimiya, Vol. 41, No. 6, 2005, pp. 738–747.Original Russian Text Copyright © 2005 by Chirkov, Rostokin. 相似文献
59.
Hansen PH Malmsten M Bergenståhl B Bergström L 《Journal of colloid and interface science》1999,220(2):269-280
Orthokinetic aggregation of colloids trapped at the air–liquid interface was studied by direct imaging in a couette cell. This method allowed us to follow the temporal evolution of both the cluster-mass distribution and the cluster structure at a shear rate where Brownian aggregation is suppressed. The interactions between the monodisperse latex particles floating at the air–liquid interface were controlled either by varying the electrolyte concentration or by creating a bidisperse system through the addition of small particles. The results show that the clusters in all of the systems are characterized by a high fractal dimension, indicating that the clusters are rearranged and densified by the shear. Kinetic analysis suggests that aggregation of monodisperse systems mainly proceeds through homogeneous aggregation, i.e., large clusters sticking to other large clusters. The bidisperse system, finally, with a size ratio around 10, favored a more heterogeneous aggregation among small and large clusters throughout the aggregation process; a slightly lower fractal dimension was observed compared to the strongly aggregated monodisperse system. 相似文献
60.
Cyanex301的纯化及其特性 总被引:7,自引:0,他引:7
研究了用Cyanex301[TM]铵盐在苯中重结晶以纯化Cyanex301的方法,该法收率62.4%,产品纯度>99%。测定了经纯化后产品的红外光谱,研究了纯化产品在-水正庚烷体系中的分配平衡及其在正庚烷中的缔合,浓度在0.2~1.0mo1/L范围,Cyanex301主要以二聚形式存在。 相似文献