全文获取类型
收费全文 | 1537篇 |
免费 | 48篇 |
国内免费 | 5篇 |
专业分类
化学 | 1011篇 |
晶体学 | 1篇 |
力学 | 42篇 |
数学 | 330篇 |
物理学 | 206篇 |
出版年
2022年 | 9篇 |
2021年 | 14篇 |
2020年 | 9篇 |
2019年 | 21篇 |
2018年 | 16篇 |
2017年 | 16篇 |
2016年 | 35篇 |
2015年 | 46篇 |
2014年 | 39篇 |
2013年 | 104篇 |
2012年 | 97篇 |
2011年 | 124篇 |
2010年 | 69篇 |
2009年 | 71篇 |
2008年 | 124篇 |
2007年 | 90篇 |
2006年 | 82篇 |
2005年 | 80篇 |
2004年 | 87篇 |
2003年 | 44篇 |
2002年 | 53篇 |
2001年 | 15篇 |
2000年 | 22篇 |
1999年 | 20篇 |
1998年 | 18篇 |
1997年 | 13篇 |
1996年 | 14篇 |
1995年 | 13篇 |
1994年 | 18篇 |
1993年 | 15篇 |
1992年 | 9篇 |
1991年 | 14篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 7篇 |
1986年 | 5篇 |
1985年 | 10篇 |
1984年 | 12篇 |
1982年 | 7篇 |
1981年 | 10篇 |
1980年 | 10篇 |
1979年 | 10篇 |
1978年 | 18篇 |
1977年 | 4篇 |
1976年 | 7篇 |
1975年 | 8篇 |
1974年 | 6篇 |
1973年 | 8篇 |
1971年 | 4篇 |
1936年 | 6篇 |
排序方式: 共有1590条查询结果,搜索用时 15 毫秒
41.
The esterfication of ethylene glycol (EG) with benzoic acid (BA) is an acid-catalyzed reaction which leads, as a first intermediate, to ethylene glycol monobenzoate (EGMB). This compound has an ? OH group which is more active towards carboxylic groups than the first ? OH group of EG. Moreover, it is a key intermediate in the formation of sideproducts containing diethylene glycol (DEG) moieties. The condensation reaction of EGMB was particularly studied in the presence of carboxylic acids or metal derivatives as catalysts. Titanium is the most active. Sb, which is widely used in the industrial synthesis of PET, needs to be present at a high level of concentration to show an activity. The presence of carboxylic groups in the reaction medium does not affect its activity, but it is necessary to remove the ethylene glycol as soon as it is formed in order to keep it active during the condensation reaction. 相似文献
42.
Abstract— Quantum chemical calculations have been performed on the retinylidene Schiff base assumed to be protonated or hydrogen bonded at the nitrogen and perturbed by a carboxylate ion at its β-ionone end. The results indicate that weak charge transfer type bands might exist due to electron transfer from the carboxylate ion to the Schiff base and that the intense (π, π*) band in the visible spectrum might acquire a significant degree of charge transfer character. 相似文献
43.
Robert J. Houben Hans-Gerd M. Janssen Piet A. Leclercq Jacques A. Rijks Carel A. Cramers 《Journal of separation science》1990,13(10):669-673
A simple and versatile system is described for the on-line coupling of SFE to capillary GC. The interfacing consists of a programmed temperature vaporizer (PTV) injector. With this injector it is possible to combine solute trapping, elimination of a high flow of extraction fluid, and quantitative transfer of solutes to the seperation column. The problems caused by impurities in the extraction fluid in on-line SFE-GC are discussed. Simple methods are described for the purification of commercially available carbon dioxide. The trapping efficiency of the PTV injector is studied. Applications of the SFE-PTV-GC system are given for the analysis of polymer anti-degradants, polar compounds, and samples with environmental relevance. 相似文献
44.
QIU Ping NI Yong-nian KOKOT Serge 《高等学校化学研究》2007,23(1):14-17
IntroductionOrganophosphorus pesticides( OPPs) are widelyused in agriculture as insecticides, but they are foundto contaminate agricultural products such as fruits andvegetables to variable extents. Because of their toxicproperties[1,2]and the potential r… 相似文献
45.
[structures: see text] A versatile (S)-3-(hydroxymethyl)butane-1,2,4-triol building block has been synthesized starting from D-isoascorbic acid, a common food preservative. The key transformation in this approach was the introduction of branching through a high yield and fully regioselective epoxide opening. This flexible synthon has been elaborated to a new class of (dihydro-)N-homo(phyto)ceramides. 相似文献
46.
[reaction: see text] The phosphoramidite 11 was prepared in three steps from methyl 2-mercaptoacetate and demonstrated efficiency in the synthesis of conventional 5'-/3'-phosphate/thiophosphate monoester derivatives of 2'-deoxyribonucleosides and DNA oligonucleotides. Moreover, the use of 11 has enabled the preparation of the dinucleoside phosphorothioate analogue 26 in high yields (>95%) with minimal cleavage (<2%) of the thermolytic thiophosphate protecting group. 相似文献
47.
Boudjahem AG Monteverdi S Mercy M Bettahar MM 《Langmuir : the ACS journal of surfaces and colloids》2004,20(1):208-213
We have studied the effect of silica of quartz-type on the reducibility of nickel acetate in aqueous hydrazine (80 degrees C, pH = 10-12) and metal particle formation. The obtained materials were characterized by X-ray diffraction, transmission electron microscopy, and thermodesorption experiments. With nickel acetate alone, the reduction was partial (45%) and a metal film at the liquid-gas interface or a powdered metal precipitate with an average particle size of 120 nm was obtained. In the presence of silica as the surfactant, the reduction of nickel acetate was total and the nickel phase deposited as a film on the support with an average particle size of 25 nm. Supported nickel acetate was also totally reduced. Crystallites of a mean particle size of about 3 nm were obtained. Decreasing the nickel content or increasing the hydrazine/nickel ratio decreased the metal particle size. Whiskers were formed for low nickel loadings. Hydrogen thermal treatment of the reduced phase showed that the organic acetate fragment, belonging to the precursor salt, still remained strongly attached to the nickel phase. The amount of the retained organic matrix depended on the metal particle size. Surface defects are suggested as active sites, which enhanced nickel ion reduction in the presence of silica as the surfactant or support. Metal-support interactions and the nucleation/ growth rate were the main factors determining the size and morphology of the supported metal particles formed. The organic matrix covered the reduced nickel phase. 相似文献
48.
H. A. Claessens M. J. J. Hetem P. A. Leclercq C. A. Cramers 《Journal of separation science》1988,11(2):176-180
In comparison with conventionally packed HPLC columns, from a theoretical point of view, open capillary liquid chromatography (OTLC) systems offer a number of advantages like high plate numbers and short analysis times. On the other hand, drastic changes have to be made to the instrumentation. In particular, the contribution to band broadening by the chromatographic equipment must be considerably reduced. In the present study an OTLC system was developed and evaluated, which yields satisfactory results for 26 μm i. d. columns. The determination of the contribution of the chromatographic equipment to the total band broadening is discussed. 相似文献
49.
Carbery DR Reignier S Miller ND Adams H Harrity JP 《The Journal of organic chemistry》2003,68(11):4392-4399
A stereocontrolled approach to alpha-alkyl beta-alkynyl cyclohexanones is reported through a Lewis acid mediated rearrangement reaction of enol ethers bearing an Co-alkyne moiety. The reaction proceeds with high levels of stereoselectivity in the presence of Ti- and B-Lewis acids to provide a range of alpha,beta-disubstituted cyclohexanones in high yield although the products are prone to epimerization at the alpha-position in the presence of the B-promoter system. The potential for an enantioselective variant of this process is outlined, and a rationale for the observed stereochemical trends and detailed structural analyses of the ketone products are described. 相似文献
50.
The main principles of solid-phase extraction techniques are reviewed in this paper. Various solid sorbents can be used as a suitable trap for direct accumulation of organic compounds from aqueous solutions. The trapped analytes can be desorbed by elution with suitably chosen liquid phases. These preconcentration procedures can be considered as low performance liquid chromatography and the efficiency of the procedure can thus be related to the retention characteristics of the preconcentration column. The main sorbents used for trace enrichment purposes are also reviewed. Besides, the concise methodology, sample storage, and automation are discussed. The advantages of solid phase extraction as compared to liquid-liquid extraction are given as well as some drawbacks of this method. 相似文献