全文获取类型
收费全文 | 1747篇 |
免费 | 28篇 |
专业分类
化学 | 960篇 |
晶体学 | 33篇 |
力学 | 12篇 |
数学 | 317篇 |
物理学 | 453篇 |
出版年
2023年 | 7篇 |
2021年 | 18篇 |
2020年 | 11篇 |
2019年 | 25篇 |
2018年 | 51篇 |
2017年 | 41篇 |
2016年 | 71篇 |
2015年 | 54篇 |
2014年 | 65篇 |
2013年 | 161篇 |
2012年 | 62篇 |
2011年 | 91篇 |
2010年 | 64篇 |
2009年 | 72篇 |
2008年 | 83篇 |
2007年 | 68篇 |
2006年 | 64篇 |
2005年 | 55篇 |
2004年 | 54篇 |
2003年 | 59篇 |
2002年 | 42篇 |
2001年 | 46篇 |
2000年 | 28篇 |
1999年 | 26篇 |
1998年 | 30篇 |
1997年 | 24篇 |
1996年 | 17篇 |
1995年 | 21篇 |
1994年 | 18篇 |
1993年 | 17篇 |
1992年 | 20篇 |
1991年 | 12篇 |
1990年 | 18篇 |
1989年 | 15篇 |
1988年 | 13篇 |
1987年 | 24篇 |
1986年 | 12篇 |
1985年 | 13篇 |
1984年 | 18篇 |
1982年 | 19篇 |
1981年 | 17篇 |
1980年 | 17篇 |
1979年 | 17篇 |
1978年 | 10篇 |
1977年 | 11篇 |
1976年 | 6篇 |
1975年 | 8篇 |
1973年 | 7篇 |
1939年 | 7篇 |
1929年 | 6篇 |
排序方式: 共有1775条查询结果,搜索用时 15 毫秒
31.
Krystyna Cieśla H. Rahier Grażyna Zakrzewska-Trznadel 《Journal of Thermal Analysis and Calorimetry》2004,77(1):279-293
One to three endothermal peaks atributted to melting of bulk and interfacial water were observed by DSC in the regenerated
cellulose — water system. The profiles of thermal effects depend on water content, time of conditioning, film pretreatment
and the conditions applied during the preceding freezing-thawing cycles. The occurrence might be deduced of melting-crystallisation
processes. A large amount of non-freezable strongly bounded water was also detected.
Although cellulose absorbs water quickly after immersion, the structural changes consisting on ordering of polymer fraction
occur during further conditioning due to increase in strength of water binding. Using the membranes in the separation module
at 90°C causes weakening of these bonds. Differences between interaction of particular cellulose films with water can be detected
during the first, the second and the third heating.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
32.
Given a finite setX of vectors from the unit ball of the max norm in the twodimensional space whose sum is zero, it is always possible to writeX = {x1, , xn} in such a way that the first coordinates of each partial sum
lie in [–1, 1] and the second coordinates lie in [–C, C] whereC is a universal constant. 相似文献
33.
Z. Gyrgydek K. E. Kvr I. Miskolczi A. Zkny F. Rantal R Luger M. Katona Strumpel 《Journal of heterocyclic chemistry》1996,33(4):1099-1105
The reaction of (4S)-5,5-dimethyl-4-thiazolidine-carboxylic acid 1 with alkyl and aryl isothiocyanates 2 gave bicyclic thiohydantoins 3 . The (2R,4S)- and (2S,4S)-mixtures of 2-substituted 5,5-dimethyl-4-thiazolidine-carboxylic acids 4 and 8 containing two centers of chirality in the analogous reaction afforded thiohydantoins 7 and 10 , respectively, with (1R)-configuration. In some cases we managed to isolate the thioureido acid intermediates 6 and 9 or their triethylamine salts which afforded the corresponding bicycles 7 and 10 under thermal cyclization or acidification. The stereochemistry has been elucidated by high resolution ram studies, optical rotation measurements and X-ray crystallography. 相似文献
34.
Preparation and investigation of structural and photocatalytic properties of phosphate modified titanium dioxide 总被引:2,自引:0,他引:2
Lszl Krsi Imre Dkny 《Colloids and surfaces. A, Physicochemical and engineering aspects》2006,280(1-3):146-154
A series of high surface area titanium dioxide samples (P-TiO2) with varying phosphate content have been prepared by the sol–gel technique. The structural characterization of the samples included X-ray powder diffraction, diffuse reflectance infrared and UV–vis spectroscopy (DRIFT and UV–vis–DR), and nitrogen adsorption measurements. The structural properties of the P-TiO2 samples significantly changed with the phosphate content and calcination temperature. According to XRD data the presence of phosphate shifts the anatase rutile phase transition to higher temperatures, revealing that phosphate improves the thermal stability of the samples. The specific surface area and the semiconductor band gap energy increase with the phosphate content.
The photocatalytic activity of TiO2 and P-TiO2 was studied by phenol degradation in liquid phase. A small amount of phosphate of the catalysts increases the photocatalytic activity, but further increase of the P/Ti molar ratio (above 0.01), leads to a considerable loss in activity. The optimal calcination temperature of P-TiO2 was 300–500 °C. The phenol conversion rate is highest with catalysts calcined at 700 °C, but phenol does not degrade to carbon dioxide. 相似文献
35.
J. Maślińska-Solich 《European Polymer Journal》1975,11(1):43-46
The copolymerization of 2-furyl-5,5-dimethyl-1,3-dioxane with maleic anhydride in the presence of a radical catalyst yields equimolar, alternating copolymers in which the furyl units have 2,5-linkage. It has been shown that 2-furyl-5,5-dimethyl-1,3-dioxane forms a charge transfer complex with maleic anhydride. The equilibrium constant for the complex was determined by NMR spectroscopy. 相似文献
36.
[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
37.
Summary A new method of collection of representative air samples for the determination of TC and TOC from volatile air pollutants has been developed. The organic substances undergo combustion and only the carbon dioxide produced is concentrated on molecular sieve 5 A at ambient temperature. The CO2 is subsequently liberated by thermal desorption at ca. 380°C in a stream of purified gas. Atmospheric CO2 must be removed first and this can be done (at the sample flow rate of 700 ml/min) by a layer of Ascarite heated at 90° C. Organic compounds passing through the layer are then combusted by a dynamic method utilizing Körbl catalyst and the CO2 formed is concentrated on a molecular sieve 5 A, followed by thermal desorption and final determination. Organic acids are also retained by the first CO2 absorber. A diffusion cell for preparation of the mixtures of purified air with vapours of organic compounds is described.
Zusammenfassung Eine neue Anreicherungsmethode zur Gewinnung representativer Luftproben zur Bestimmung des Gesamtkohlenstoffgehaltes und des Gehaltes an organischem Kohlenstoff (TOC) aus flüchtigen Luftverunreinigungen wurde entwickelt. Während der Probenahme werden die flüchtigen Verunreinigungen verbrannt und nur das entstandene Kohlendioxid bei Zimmertemperatur am Molekularsieb 5A angereichert. Anschließend wird CO2 bei ca. 380° C im gereinigten Gasstrom thermisch desorbiert. Bei der TOC-Bestimmung muß atmosphärisches CO2 vorangehend aus dem Luftstrom entfernt werden und wird an einer auf 90° C erwärmten Ascariteschicht gebunden. Die durchfließenden organischen Verbindungen werden dann im dynamischen System am Körblkatalysator oxydiert, das entstandene CO2 am Molekularsieb 5A angereichert, thermisch desorbiert und einer Endbestimmung zugeführt. Organische Säuren werden gleichfalls durch den ersten CO2-Absorber gebunden. Eine Diffusionszelle zur Herstellung von Gemischen gereinigter Luft mit Dämpfen organischer Verbindungen wurde beschrieben.相似文献
38.
Adsorptive stripping voltammetric (AdSV) methods are presented for the determination of titanium and iron in quartz and silica glass samples obtained after pressure decomposition. Mandelic acid and catechol were used as complexing agents for titanium and iron, respectively. The method for titanium determination is based on the catalytic effect of chlorate ions. An insoluble residue remaining after decomposition of quartz and silica glass samples in HF+H2SO4 mixture was checked by energy-dispersive X-ray analyses. ET-AAS was applied as a reference method to AdSV measurements. 相似文献
39.
The intercalation process ofn-butylamine was investigated. The adsorption ofn-butylamine in interlamellar space had stepwise character in case of both crystalline forms of zirconium phosphate. The intercalatedn-butylamine existed at low concentration as bilayered complex. The reaction heat was determined by a microcalorimetric method. It was found that about 90% of it refers to the neutralization ofn-butylamine and only about 10% is related with surface adsorption (ion exchange). The steps of adsorption are 6.0 J/g and 1.0 J/g reaction heat values, respectively. The enthalpy balance of total process in dilute solution system (c
0=3.0 vol%) is 14.67 kJ/mol. The calculated value for ion adsorption (exchange) was 1.37 kJ/mol. 相似文献
40.
Propargyl ethers treated with dimsyl anion in DMSO at 80-100°C undergo terminal methylenation to afford corresponding (E) 1-alkoxy-1,3-butadienes. The reaction proceeds via an alkoxy-allene. 相似文献