全文获取类型
收费全文 | 3252篇 |
免费 | 15篇 |
国内免费 | 234篇 |
专业分类
化学 | 2741篇 |
力学 | 13篇 |
数学 | 13篇 |
物理学 | 428篇 |
综合类 | 306篇 |
出版年
2023年 | 4篇 |
2022年 | 4篇 |
2021年 | 3篇 |
2020年 | 4篇 |
2019年 | 6篇 |
2018年 | 3篇 |
2017年 | 15篇 |
2016年 | 18篇 |
2015年 | 16篇 |
2014年 | 8篇 |
2013年 | 9篇 |
2012年 | 267篇 |
2011年 | 336篇 |
2010年 | 57篇 |
2009年 | 150篇 |
2008年 | 452篇 |
2007年 | 314篇 |
2006年 | 378篇 |
2005年 | 377篇 |
2004年 | 262篇 |
2003年 | 204篇 |
2002年 | 151篇 |
2001年 | 107篇 |
2000年 | 122篇 |
1999年 | 39篇 |
1998年 | 15篇 |
1997年 | 12篇 |
1996年 | 37篇 |
1995年 | 20篇 |
1994年 | 20篇 |
1993年 | 46篇 |
1992年 | 26篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1986年 | 4篇 |
1979年 | 1篇 |
排序方式: 共有3501条查询结果,搜索用时 15 毫秒
131.
Bond AD Doyle EL García F Kowenicki RA McPartlin M Riera L Wright DS 《Chemical communications (Cambridge, England)》2003,(24):2990-2991
The in situ reaction of the phosphazane dimer [CIP(mu-N-2-NC5H4)]2 (2) with CuCl in the presence of CsH5N/H2O gives the title complex [(P(mu-N-2-NC5H4))2(mu-O)]2(CuCl x (C5H5N)2)4 (1), containing a tricyclic [(P(mu-N-2-NC5H4))2(mu-O)]2 ligand which is isoelectronic with species of the type [(P(mu-NR))2NR]2. 相似文献
132.
Doyle EL García F Humphrey SM Kowenicki RA Riera L Woods AD Wright DS 《Dalton transactions (Cambridge, England : 2003)》2004,(5):807-812
The reaction of [ClP(mu-NtBu)]2 (1) with H2O (1 : 2 equivalents) in the presence of excess Et3N gives the new chain compound [(mu-O)[P(mu-NtBu)2P(H)=O]2] (3), consisting of two P2N2 rings linked by a mu-O atom and terminating in P(V)(H)=O groups. A similar chain species is obtained from the reaction of the lithiate of [(tBuNH)P(mu-NtBu)2P(H)=O] (5) with [ClP(mu-NtBu)2P(NHtBu)] (2), the product being [(mu-O)[P(mu-NtBu)2P(NHtBu)]2] (6). Compounds 3 and 6 are the first examples of O-bridged chain phosphazanes and potential precursors to new phosphorus-nitrogen macrocycles. The syntheses and X-ray structures of 3, 5 and 6 are reported. 相似文献
133.
Martínez-Galera M López-López T Gil-García MD Martínez-Vidal JL Picón-Zamora D Cuadros-Rodríguez L 《Analytical and bioanalytical chemistry》2003,375(5):653-660
A comparative study of two mathematical approaches was performed in order to correct systematic errors due to the presence of the unexpected interferences which appear when the quantitation of the analyte in real samples is carried out with calibration curves built using standards in pure solvent. These methods consisted in the establishment of different mathematical expressions which transform the concentration (Cs) obtained using calibration graphs built using pure solvent into the corrected concentration (C(M)) that should be obtained if the quantitation is carried out with calibration curves built using standards dissolved in blank matrix extracts. In the two approaches the correction is performed from the results of an intermediate precision study which was carried out using both calibration graphs (prepared using pure solvent and blank matrix extract). By using ANCOVA to compare the slope of both solvent-based and matrix-matched calibration graphs, matrix effect was found in the determination of deltamethrin in tomato and acrinathrin in tomato and pepper. In these cases, both approaches led to good results. 相似文献
134.
WANG Shu-Pinga GAO Dong-Zhaoa LIAO Dai-Zhenga JIANG Zong-Huia② YAN Shi-Pinga LI Li-Cuna b a 《结构化学》2006,(2)
1 INTRODUCTION Pyridyl-substituted nitroxide radicals have at- tracted considerable attention in recent years due to the ability to coordinate with metal ions and act as magnetic couplers, giving rise to new functional ma- terials with particular magnetic and optical prope- rties as well as a variety of structural topologies[1~3]. Considerable efforts have been made in designing and preparing multi-dimensional materials with app- ropriate bridges, such as pseudohalide, dicyanide, dicyanoa… 相似文献
135.
Dodds F García F Kowenicki RA McPartlin M Steiner A Wright DS 《Chemical communications (Cambridge, England)》2005,(29):3733-3735
The reaction of [ClP(mu-NtBu)]2 with 1,5-diamino-naphthalene [1,5-(NH2)2C10H6] in Et3N-thf gives the trimeric macrocycle [{P(mu-NtBu)}2{1,5-(NH)2C10H6}]3(1); the X-ray structure of the toluene solvate 1.3toluene reveals a cone-shaped (calixarene-like) arrangement in which toluene guest molecules are trapped within the cavity. 相似文献
136.
Román-Bravo P López-Cardoso M y García PG Höpfl H Cea-Olivares R 《Chemical communications (Cambridge, England)》2004,(17):1940-1941
The molecular structures of two lipophilic polyion aggregates derived from tetraphenyl imidodiphosphinate are described: [Na(crown ether)][MNa(2)[Ph(2)P(O)NP(O)Ph(2)](4)] with crown ether = 15-crown-5 for 1and benzo-15-crown-5 for (M = Na(+) for 1 and Na(H(2)O)(+) for 2). 相似文献
137.
Carabias-Martínez R Rodríguez-Gonzalo E Domínguez-Alvarez J García Pinto C Hernández-Méndez J 《Journal of chromatography. A》2003,1005(1-2):23-34
A preconcentration study based on the cloud point phenomenon was carried out for a set of triazine herbicides, three of them chloro-substituted and three of them methylthio-substituted. Concentration factors and recoveries were calculated as function of the percentage of the non-ionic surfactant Triton X-114 employed. From these values, obtained from a cloud point extraction (CPE) procedure, the distribution coefficient between the Triton X-114 micelles and water, Kc, prior to CPE was calculated for each triazine and related to the corresponding octanol-water partition coefficient, Kow. In order to confirm the results obtained with the triazine herbicides, two sets of data from chemically different organic pollutants--organophosporous and chlorophenols--obtained from the literature were assessed, concluding that they display a similar behaviour to that of the triazine herbicides. This can be used to predict the CPE behaviour of other organic pollutants from their octanol-water partition coefficients. The Kc values were compared with the analyte concentration ratio in the surfactant-rich phase and aqueous phase (Ksa) with a view to obtaining a link between the analyte behaviour prior to and after cloud point extraction procedures. 相似文献
138.
Zucolotto V Faceto AD Santos FR Mendonça CR Guimarães FE Oliveira ON 《The journal of physical chemistry. B》2005,109(15):7063-7066
The fabrication of varied molecular architectures in layer-by-layer (LbL) films is exploited to control the photoluminescence (PL) of poly(p-phenylene vinylene) (PPV) in an unprecedented way. This was achieved by controlling the F?rster energy transfer between PPV layers (donors) and layers of a commercial azodye, Brilliant Yellow (BY) (acceptors). Energy transfer was controlled by inserting spacer layers of inert polymers between PPV and BY layers and by photoaligning the BY molecules via trans-cis-trans isomerization. The PPV/BY LbL films displayed polarized PL whose intensity could be varied almost continuously by changing the time of photoalignment, which was carried out by impinging a linearly polarized laser light simultaneously to the PL experiments. For PPV/BY films with no spacer layers, PL was completely quenched, but its intensity increased with the number of spacing layers. Further increase in PL was obtained by photoaligning the BY molecules perpendicularly to the PPV molecules. This minimizes energy transfer, since F?rster processes are directional, dipole-dependent resonant transfers. Energy transfer is also controlled by imparting a preferential orientation of the PPV chains on PPV/BY LbL films deposited onto flexible Teflon substrates that may be stretched. 相似文献
139.
European Legislation establishes that the sum of the migration levels of bisphenol A diglycidyl ether (BADGE), its hydrolysis (BADGE.H2O and BADGE.2H2O) and chlorohydroxy (BADGE.HCl, BADGE.2HCl and BADGE.H2O.HCl) derivatives shall not exceed the limit of 1 mg/kg in foodstuffs or food simulants. A reversed-phase high-performance liquid chromatographic (RP-HPLC) method combined with mass spectrometry detection using atmospheric pressure chemical ionisation (APCI) is developed for the separation, quantification and identification of the interesting compounds. Quantification of the analytes was carried out in the single ion recording mode, once their characteristic masses were selected from their full spectra, by using an external calibration. The optimised method was suitable for the migration evaluation of these compounds in different samples. 相似文献
140.
Carmona AT Fuentes J Robina I García ER Demange R Vogel P Winters AL 《The Journal of organic chemistry》2003,68(10):3874-3883
A new route for the preparation of four new indolizidines, (1R,2S,6S,7S,8aS)- and (1R,2S,6R,7R,8aS)-1,2,6,7-tetrahydroxyindolizidine (30 and 32) and (1S,2R,7S,8S,8aR)- and (1S,2R,7R,8R,8aR)-1,2,7,8-tetrahydroxyindolizidine (44 and 46), is reported. The synthesis is based on Knoevenagel homologation of the readily available enantiomerically pure pyrrolidin-carbaldehydes 13 and 37followed by asymmetric dihydroxylation of the subsequent alkenyl pyrrolidines and cyclization of the corresponding imino-octitols. The new indolizidines and their precursors (imino-octitols 20, 25, 26) and indolizidinones 28a and 28b have been tested for inhibitory activities toward 26 glycosidases. The enzymatic inhibition of trans-7-hydroxy-d-(-)-swainsonine (44) toward alpha-mannosidases is similar to that described for trans-7-hydroxy-l-(+)-swainsonine (11b) toward naringinase (alpha-l-rhamnosidase from Penicillium decumbens). 相似文献