全文获取类型
收费全文 | 3136篇 |
免费 | 411篇 |
国内免费 | 238篇 |
专业分类
化学 | 2153篇 |
晶体学 | 43篇 |
力学 | 113篇 |
综合类 | 11篇 |
数学 | 420篇 |
物理学 | 1045篇 |
出版年
2024年 | 3篇 |
2023年 | 39篇 |
2022年 | 58篇 |
2021年 | 83篇 |
2020年 | 116篇 |
2019年 | 109篇 |
2018年 | 92篇 |
2017年 | 87篇 |
2016年 | 134篇 |
2015年 | 157篇 |
2014年 | 143篇 |
2013年 | 261篇 |
2012年 | 283篇 |
2011年 | 290篇 |
2010年 | 179篇 |
2009年 | 160篇 |
2008年 | 203篇 |
2007年 | 190篇 |
2006年 | 149篇 |
2005年 | 144篇 |
2004年 | 97篇 |
2003年 | 111篇 |
2002年 | 79篇 |
2001年 | 78篇 |
2000年 | 62篇 |
1999年 | 51篇 |
1998年 | 52篇 |
1997年 | 39篇 |
1996年 | 49篇 |
1995年 | 31篇 |
1994年 | 38篇 |
1993年 | 38篇 |
1992年 | 25篇 |
1991年 | 24篇 |
1990年 | 12篇 |
1989年 | 28篇 |
1988年 | 15篇 |
1987年 | 9篇 |
1986年 | 20篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1979年 | 2篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1973年 | 3篇 |
1940年 | 1篇 |
1938年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有3785条查询结果,搜索用时 15 毫秒
81.
Treatment of halides 5 with electrophilic alkenes 2 afforded the corresponding dihydrofurans 3 and 4 in the presence of 1, 4-diazabicyclo[2.2.2]octane (DABCO) with good to excellent yields and in a stereoselective manner in most cases. Moreover, the stereoisomers 3 and 4 could be easily transformed each other in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). 相似文献
82.
R. Mu?oz Olivas Philippe Quevauviller O. F. X. Donard 《Fresenius' Journal of Analytical Chemistry》1998,360(5):512-519
Long term stability of organic selenium compounds (selenocystine, selenomethionine, trimethylselenonium ion) has been studied
over a one year period for 2 analyte concentrations: 25 and 150 μg/L Se, at pH 4.5 in the dark, under different storage conditions:
temperature of –20°C, 4°C, 20°C, 40°C; in Pyrex, Teflon, or polyethylene containers; in an aqueous matrix or in the presence
of a chromatographic counter ion (pentyl sulfonate at 10–4 mol/L concentration). Light effects have also been tested. The stability of the selenium species was monitored by HPLC-ICP/MS.
Storage conditions can drastically alter the stability of organic selenium species. Organoselenium compounds were shown to
be stable in the dark over a one year period in an aqueous matrix at pH 4.5 in Pyrex containers at both 4°C and 20°C. Pyrex
vials exposed to natural sunlight at room temperature resulted in a steady decrease of the selenoamino acid concentration.
Teflon containers caused losses of less than 25% at both 4° C and 20° C in the dark. However, polyethylene vials presented,
at all temperatures tested, a rapid decrease of the TMSe+ concentration. The stability of the Se species studied did not show significant differences between 4° C and 20° C in any
container material used. Storage of solutions at 40° C led to slight differences between the Pyrex and Teflon containers.
However, polyethylene presented a drastic decrease of the three species over time at this higher temperature. Solutions frozen
at –20° C in polyethylene vials did not stabilize the TMSe+ signal. Finally, concentrations and matrices of the samples did not significantly affect the stability of the species.
Received: 15 July 1996 / Revised: 14 July 1997 / Accepted: 18 July 1997 相似文献
83.
Bolm C Hildebrand JP Muñiz K Hermanns N 《Angewandte Chemie (International ed. in English)》2001,40(18):3284-3308
Addition and substitution reactions with carbon nucleophiles are fundamental processes in organic synthesis, and the development of general catalytic asymmetric variants thereof is still a major challenge today. In contrast to enantioselective alkyl transfer reactions, the corresponding arylations have not yet reached a high level of maturity. The existing protocols are either of no general applicability or are limited in terms of selectivity. This article summarizes established routes for catalytic asymmetric aryl transfer together with the latest developments in this area. The scope and limitations of this reaction are discussed. 相似文献
84.
Maria Zaharescu Maria Crisan I. MuŠeviČ 《Journal of Sol-Gel Science and Technology》1998,13(1-3):769-773
Atomic Force Microscopy (AFM) was used to study the influence of thermal treatments on the structural and textural properties of the sol-gel TiO2 films obtained from Ti(OC3H7i)4. X-ray diffraction (XRD), ellipsometric and porosity measurements have also been made.The TiO2 sol-gel films were homogeneous, transparent and amorphous. Heat treatments in the 400–600°C range indicate that the films have a strong tendency to crystallization. The high initial homogeneity of the TiO2 films was preserved during the crystallization process. AFM shows that the thermally treated films exhibit uniform, monodispersed crystals. 相似文献
85.
Muñoz-Muriedas J Perspicace S Bech N Guccione S Orozco M Luque FJ 《Journal of computer-aided molecular design》2005,19(6):401-419
Summary The use of a recently proposed hydrophobic similarity index for the alignment of molecules and the prediction of their differences
in biological activity is described. The hydrophobic similarity index exploits atomic contributions to the octanol/water transfer
free energy, which are evaluated by means of the fractional partitioning scheme developed within the framework of the Miertus-Scrocco-Tomasi
continuum model. Those contributions are used to define global and local measures of hydrophobic similarity. The suitability of this computational strategy is examined for two series of compounds
(ACAT inhibitors and 5-HT3 receptor agonists), which are aligned to maximize the global hydrophobic similarity using a Monte Carlo-simulated protocol.
Indeed, the concept of local hydrophobic similarity is used to explore structure–activity relationships in a series of COX-2 inhibitors. Inspection of
the 3D distribution of hydrophobic/hydrophilic contributions in the aligned molecules is valuable to identify regions of very
similar hydrophobicity, which can define pharmacophoric recognition patterns. Moreover, low similar regions permit to identify
structural elements that modulate the differences in activity between molecules. Finally, the quantitative relationships found
between the pharmacological activity and the hydrophobic similarity index points out that not only the global hydrophobicity,
but its 3D distribution, is important to gain insight into the activity of molecules.
J.M.M. and S.P. have contributed equally to this study. 相似文献
86.
ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE 总被引:1,自引:0,他引:1
The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here. 相似文献
87.
掺杂阴离子对电化学合成的聚邻甲苯胺性质的影响 总被引:3,自引:0,他引:3
邻甲苯胺在酸性介质中的聚合速率与酸的种类有关,聚合速率影响了各种掺杂阴离子聚合物膜的形态,聚合物的电导率、循环伏安曲线形状受掺杂阴离子的影响,其电容量与掺杂阴离子的种类及形态有关,阴离子的种类对电极电位和紫外-可见光谱无影响。 相似文献
88.
Mounir Maafi Belkacem Laassis Jean-Jacques Aaron M. Carmen Mahedero Arsenio Muñoz De La Peña Francisco Salinas 《Journal of inclusion phenomena and macrocyclic chemistry》1995,22(3):235-247
The photooxidation of Azure A and fluorescence properties of Azure A and its photoproduct have been investigated in aqueous media and in the presence of-cyclodextrin (-CD). The fluorescence intensity of the complex formed between the photoproduct and -CD was found to be three times higher than that of the uncomplexed Azure A photoproduct. A complex formation constant of 110±40 M–1 was calculated using the Benesi-Hildebrand treatment of the fluorescence emission data. Although the stoichiometry of the Azure A photoproduct: -CD complex was found to be 1: 1, it seems that the Azure A structure is only partially included. Calibration graphs were plotted for the free Azure A photoproduct and the photogenerated product included in -CD. The analytical parameters and quantification limits were determined. 相似文献
89.
离子液体的酸性测定及其催化的二苯醚/十二烯烷基化反应 总被引:20,自引:0,他引:20
采用乙腈探针红外光谱法测定了[bmim]Cl/AlCl3类离子液体的酸性.结果表明,乙腈可以区分离子液体的酸类型(Bronsted酸或Lewis酸),同时可以指示离子液体的Lewis酸强度.使用[bmim]Cl/AlCl3类离子液体催化二苯醚与十二烯的烷基化反应,研究了离子液体的酸强度、反应温度和醚烯比对反应的影响,并与AlCl3催化体系进行对比.结果发现,该离子液体对二苯醚与十二烯烷基化反应的催化活性明显高于AlCl3.使用离子液体作催化剂显著提高了烷基化反应的产率,简化了产物的分离与提纯,且对环境友好.当控制反应温度为80℃,原料醚烯摩尔比为7,并采用酸强度适中的离子液体时,目标产物单十二烷基二苯醚的产率接近90%. 相似文献
90.