全文获取类型
收费全文 | 911篇 |
免费 | 65篇 |
国内免费 | 1篇 |
专业分类
化学 | 711篇 |
晶体学 | 2篇 |
力学 | 30篇 |
数学 | 100篇 |
物理学 | 134篇 |
出版年
2023年 | 12篇 |
2022年 | 5篇 |
2021年 | 16篇 |
2020年 | 23篇 |
2019年 | 23篇 |
2018年 | 11篇 |
2017年 | 11篇 |
2016年 | 39篇 |
2015年 | 27篇 |
2014年 | 36篇 |
2013年 | 47篇 |
2012年 | 79篇 |
2011年 | 66篇 |
2010年 | 41篇 |
2009年 | 43篇 |
2008年 | 67篇 |
2007年 | 54篇 |
2006年 | 66篇 |
2005年 | 55篇 |
2004年 | 40篇 |
2003年 | 31篇 |
2002年 | 37篇 |
2001年 | 9篇 |
2000年 | 10篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 5篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1974年 | 4篇 |
1972年 | 3篇 |
1970年 | 3篇 |
1969年 | 4篇 |
1962年 | 3篇 |
1932年 | 2篇 |
1931年 | 2篇 |
1930年 | 2篇 |
1929年 | 2篇 |
排序方式: 共有977条查询结果,搜索用时 611 毫秒
11.
This paper describes a new extraction tool for the determination of polycyclic aromatic hydrocarbons (PAHs) in soil and sediment samples, using dynamic microwave-assisted extraction combined with solid-phase extraction (DMAE-SPE). The critical variables for DMAE-SPE are investigated and optimized in an experimental design. The technique proved to be fast, accurate and able to yield quantitative extraction of PAHs from naturally contaminated sediment and soil samples. The set-up is fully automated and features monitored extraction, which facilitates rapid optimization of the method. In addition, only small quantities of solvent and sample are required. 相似文献
12.
Córdova A Ibrahem I Casas J Sundén H Engqvist M Reyes E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4772-4784
Hexose sugars play a fundamental role in vital biochemical processes and their biosynthesis is achieved through enzyme-catalyzed pathways. Herein we disclose the ability of amino acids to catalyze the asymmetric neogenesis of carbohydrates by sequential cross-aldol reactions. The amino acids mediate the asymmetric de novo synthesis of natural L- and D-hexoses and their analogues with excellent stereoselectivity in organic solvents. In some cases, the four new stereocenters are assembled with almost absolute stereocontrol. The unique feature of these results is that, when an amino acid is employed as the catalyst, a single reaction sequence can convert a protected glycol aldehyde into a hexose in one step. For example, proline and its derivatives catalyze the asymmetric neogenesis of allose with >99 % ee in one chemical manipulation. Furthermore, all amino acids tested catalyzed the asymmetric formation of natural sugars under prebiotic conditions, with alanine being the smallest catalyst. The inherent simplicity of this catalytic process suggests that a catalytic prebiotic "gluconeogenesis" may occur, in which amino acids transfer their stereochemical information to sugars. In addition, the amino acid catalyzed stereoselective sequential cross-aldol reactions were performed as a two-step procedure with different aldehydes as acceptors and nucleophiles. The employment of two different amino acids as catalysts for the iterative direct aldol reactions enabled the asymmetric synthesis of deoxysugars with >99 % ee. In addition, the direct amino acid catalyzed C(2)+C(2)+C(2) methodology is a new entry for the short, highly enantioselective de novo synthesis of carbohydrate derivatives, isotope-labeled sugars, and polyketide natural products. The one-pot asymmetric de novo syntheses of deoxy and polyketide carbohydrates involved a novel dynamic kinetic asymmetric transformation (DYKAT) mediated by an amino acid. 相似文献
13.
Ulf Berg Marcia Berglund Nina Bladh Anette Svensson Magnus Stödeman 《Journal of inclusion phenomena and macrocyclic chemistry》1996,25(1-3):73-76
The properties of inclusion complexes of 1,4-di-R-bicyclo[2.2.2]octaves (R = H (1), Me (2), Cl (3), Br (4), and OH (5)) with cyclodextrins have been studied by NMR, microcalorimetry, and force-field computations. The compounds2 and3 (but not the other compounds) give dynamically stable 1:2 guest-host complexes with -cyclodextrin. Microcalorimetry of5 in water indicates a moderately strong 1:1 complex with - but weak complexes with - or -cyclodextrin. The behaviour depends on the subtle interplay size, polarity, hydrophobicity and type of solvent. 相似文献
14.
An on-line method for the determination of airborne organophosphate esters based on dynamic sonication-assisted solvent extraction and large-volume injection (LVI) gas chromatography with nitrogen-phosphorous detection is introduced. The LVI is performed with a programmed-temperature vaporizer. The entire extracted fraction of 800 microl (hexane-methyl-tert.-butyl ether, 7:3, v/v) is introduced directly into the GC system without any clean-up step following extraction. The extraction and analysis step were completed in less than 15 min. The limit of detection of the investigated organophosphate esters was established to be in the range of 5-32 pg/filter. The correlation coefficients (r2) were investigated in the linear range study of the entire system and established to be approximately 0.9900 for all the investigated organophosphates esters. Applications of the method was demonstrated with the extraction of air samples collected onto glass fiber filters from different indoor environments. Six organophosphate esters were found at the levels 0.4-138 ng/m3. 相似文献
15.
Hisanobu Wakita Georg Johansson Magnus Sandström Peter L. Goggin Hitoshi Ohtaki 《Journal of solution chemistry》1991,20(7):643-668
Structures of the complexes formed in aqueous solutions between zinc(II) and iodide ions have been determined from large-angle X-ray scattering, Raman and far-IR measurements. The coordination in the hydrated Zn2+ hexaaqua ion and the first iodide complex, [ZnI]+, is octahedral, but is changed into tetrahedral in the higher complexes, [ZnI2(H2O)2], [ZnI3(H2O)]– and [ZnI4]2–. The Zn-I bond length is 2.635(4)Å in the [ZnI4]2– ion and slightly shorter, 2.592(6)Å, in the two lower tetrahedral complexes. In the octahedral [ZnI(H2O)5]+ complex the Zn-I bond length is 2.90(1)Å. The Zn-O bonding distances in the complexes are approximately the same as that in the hydrated Zn2+ ion, 2.10(1)Å. 相似文献
16.
Adams LA Aggarwal VK Bonnert RV Bressel B Cox RJ Shepherd J de Vicente J Walter M Whittingham WG Winn CL 《The Journal of organic chemistry》2003,68(24):9433-9440
A simple and high-yielding method for the preparation of cyclopropane amino acids is described. The novel method involves the one-pot cyclopropanation of readily available dehydroamino acids using aryl and unsaturated diazo compounds generated in situ from the corresponding tosylhydrazone salts. It was found that thermal 1,3-dipolar cycloaddition followed by nitrogen extrusion gave the cyclopropane amino acid derivatives with good E selectivity, while reactions in the presence of meso-tetraphenylporphyrin iron chloride gave predominantly the corresponding Z isomers. The synthetic utility of this process was demonstrated in the synthesis of (+/-)-(Z)-2,3-methanophenylalanine [(+/-)-(Z)-1], the anti-Parkinson (+/-)-(E)-2,3-methano-m-tyrosine [(+/-)-(E)-2], and the natural product (+/-)-coronamic acid [(+/-)-3]. 相似文献
17.
Tyrode E Johnson CM Kumpulainen A Rutland MW Claesson PM 《Journal of the American Chemical Society》2005,127(48):16848-16859
The OH stretching region of water molecules in the vicinity of nonionic surfactant monolayers has been investigated using vibrational sum frequency spectroscopy (VSFS) under the polarization combinations ssp, ppp, and sps. The surface sensitivity of the VSFS technique has allowed targeting the few water molecules present at the surface with a net orientation and, in particular, the hydration shell around alcohol, sugar, and poly(ethylene oxide) headgroups. Dramatic differences in the hydration shell of the uncharged headgroups were observed, both in comparison to each another and in comparison to the pure water surface. The water molecules around the rigid glucoside and maltoside sugar rings were found to form strong hydrogen bonds, similar to those observed in tetrahedrally coordinated water in ice. In the case of the poly(ethylene oxide) surfactant monolayer a significant ordering of both strongly and weakly hydrogen bonded water was observed. Moreover, a band common to all the surfactants studied, clearly detected at relatively high frequencies in the polarization combinations ppp and sps, was assigned to water species located in proximity to the surfactant hydrocarbon tail phase, with both hydrogen atoms free from hydrogen bonds. An orientational analysis provided additional information on the water species responsible for this band. 相似文献
18.
Samskog J Bergström SK Jönsson M Klett O Wetterhall M Markides KE 《Electrophoresis》2003,24(11):1723-1729
A method for coupling an electrophoretic driven separation to a liquid flow, using conventional fused-silica capillaries and a soft polymeric interface is presented. A novel design of the electrode providing high voltage to the electrophoretic separation was also developed. The electrode consisted of a conductive polyimide/graphite imbedded coating immobilized onto the capillary electrophoresis (CE) column inlet. This integrated electrode gave the same separation performance as a commonly used platinum electrode. The on-column electrode also showed good electrochemical stability in chronoamperometric experiments. In addition, with this electrode design, the electrode position relative to the inlet end of the CE column will always be constant and well defined. The on-line flow injection analysis (FIA)-CE system was used with electrospray ionization (ESI)-time of flight (TOF)-mass spectrometry detection. The preparation of the PDMS (poly(dimethylsiloxane)) interface for FIA-CE is described in detail and used for initial tests of the on-column polymer-imbedded graphite inlet electrode. In this interface, a pressure-driven liquid flow, a make up CE electrolyte and a CE column inlet meet in a two-level cross (95 microm ID) in the PDMS structure, enabling independent flow characterization. 相似文献
19.
The total synthesis of tetrahydroisoquinoline alkaloids (+/-)-renieramycin G (4) and a lemonomycinone analogue (7) is described. A general strategy to synthesize both the mono- and bistetrahydroisoquinoline alkaloids from a common advanced intermediate, 17, is presented. 相似文献
20.
Earlier studies of electric field assisted LC (EF-LC) have shown that the effect on charged analytes of the application of an electric field over a capillary LC column is relatively small. Charged analytes can only be affected by the electric field while present in the mobile phase, which makes the effective time for influence of the electric field t(0) independent of retention time. Because the charged analytes only can be affected for a short time the electric field strength ought to be high in order to increase the impact of the electric field on the separation. We have, however, found that only a relatively low electric field strength can be used in EF-LC when pressure is used as main driving force. The useful field strength was limited by a dramatic increase in the current. This increase in current was found to origin from an increased concentration of buffer ions that have an electrophoretic mobility towards the pumped flow. 相似文献