全文获取类型
收费全文 | 266篇 |
免费 | 13篇 |
专业分类
化学 | 171篇 |
晶体学 | 2篇 |
力学 | 3篇 |
数学 | 36篇 |
物理学 | 67篇 |
出版年
2023年 | 2篇 |
2022年 | 7篇 |
2021年 | 4篇 |
2020年 | 13篇 |
2019年 | 9篇 |
2018年 | 10篇 |
2017年 | 13篇 |
2016年 | 14篇 |
2015年 | 10篇 |
2014年 | 5篇 |
2013年 | 17篇 |
2012年 | 14篇 |
2011年 | 22篇 |
2010年 | 20篇 |
2009年 | 14篇 |
2008年 | 20篇 |
2007年 | 19篇 |
2006年 | 13篇 |
2005年 | 8篇 |
2004年 | 5篇 |
2003年 | 6篇 |
2002年 | 5篇 |
2001年 | 5篇 |
2000年 | 6篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1986年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有279条查询结果,搜索用时 15 毫秒
51.
Serap Seyhan Bozkurt Deniz Erdogan Mine Antep Nalan Tuzmen Melek Merdivan 《液相色谱法及相关技术杂志》2016,39(1):21-29
The possibility of using ionic liquid based chitosan sorbent for the separation and preconcentration of fluoroquinolone antibiotics (marbofloxacin, enoxacin, ofloxacin, ciprofloxacin, and enrofloxacin) has been studied. For this reason, different ionic liquids were prepared and coated on the chitosan sorbent. The conditions of the preconcentration of fluoroquinolones on a microcolumn have been optimized and the extraction efficiencies of the prepared sorbents have been compared. The compounds were eluted with 5 mL of 20% NH3 (v/v, MeOH) solution and determined by HPLC with diode array and fluorescence detector. The limits of detection were found as 4.23 µ g L?1 for marbofloxacin, and 1.09 µg L?1 for enoxacin; 3.23 × 10?3 µg L?1 for ofloxacin; 8.39 × 10?3 µg L?1 for ciprofloxacin; and 19.50 × 10?3 µg L?1 for enrofloxacin. The developed method was applied for the analysis of fluoroquinolone in milk, egg, fish, bovine, and chicken samples and the recoveries were obtained in the range 70–100%. 相似文献
52.
Deprotonation of a cyclotriphosphazene with a tert-butylamino group in the side chain results in ring expansion to a very stable, planar cyclohexaphosphazene derivative that still contains eight P-Cl bonds suitable for forming macromolecular structures. 相似文献
53.
Gülay Bayramoğlu Nilhan Kayaman‐Apohan Memet Vezir Kahraman Sabriye Karadenizli Serap Erdem Kuruca Atilla Güngör 《先进技术聚合物》2012,23(10):1403-1413
A branched methacrylated poly(caprolactone‐co‐lactic acid) and methacrylated poly(tetramethylene ether glycol) (PTMG‐IEM) resins were synthesized. 1H‐NMR spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR) spectroscopy, and gel permeation chromatography confirmed the chemical structures of copolymers. The photoinitiated polymerization of formulation composed of various amounts of methacrylated poly(caprolactone‐co‐lactic acid), PTMG‐IEM, poly(ethylene glycol) diacrylate, water, and photoinitiator were performed. The curing reactions were followed by photo‐DSC (Differential scanning calorimetry). Gel fraction was calculated from the insoluble part and found as ≥93%. Swelling and contact angles were measured, and all increased with the increasing amount of PTMG‐IEM in network formulations. In vitro degradation studies were performed at 37 °C in phosphate‐buffered saline (pH 7.4). Collagen‐modified polymers were also prepared and introduced as a bioactive moiety to modify the polymer to enhance cell affinity. To compare the cell adhesion affinity to the polymer with and without collagen, cell growth experiments were performed. The results showed that collagen improves the cell adhesion onto the polymer surface. With the increasing amount of collagen, cell viability increases 86% (ECV304, p < 0.05) and 83% (3 T3, p < 0.05). Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
54.
Hu C Barabanschikov A Ellison MK Zhao J Alp EE Sturhahn W Zgierski MZ Sage JT Scheidt WR 《Inorganic chemistry》2012,51(3):1359-1370
Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate, or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200-300 cm(-1). Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with density functional theory (DFT) calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe-N(Im) vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape). 相似文献
55.
56.
The novel (E,E)-dioxime 5,6:13,14-dibenzo-9,10-benzo(15-crown-5)-2,3-bis(hydroxyimino)-7,12-dioxo-1,4,8,11-tetraazacyclotetradecane (H2L) has been synthesized by the reaction of 4′,5′-diaminobenzo(15-crown-5) with N,N′-bis(2-carbomethoxyphenyl)diaminoglyoxime (1). Only mononuclear CoIII and RuII complexes with a metal/ligand ratio of 1:2 have been isolated. The cobalt(III) complex bridged with BF2+ is achieved with H-bonded cobalt(III) complex and borontrifluoride ethyl ether complex. The reaction of BF2 bridged cobalt(III) complex with bis(benzonitril)palladium(II) chloride gives a trinuclear complex. The structures of dioxime and its complexes are proposed according to elemental analyses, 1H and 13C-NMR, IR and mass spectral data. 相似文献
57.
Murat Çelik Cemalettin Alp M. Serdar Gültekin Metin Balci 《Tetrahedron letters》2006,47(22):3659-3663
1,2- and 1,3-Bis(trifluoroacetoxy) alcohols are easily obtained from the one-pot reaction of alkenes with phenyliodine(III) bis(trifluoroacetate) (PIFA) in the absence of any additive or catalyst. The products were converted into the corresponding diols by ammonolysis. The use of bicyclic alkenes has shown that rearranged 1,3-diacetoxy alcohols are mostly formed as the major products. 相似文献
58.
Roemeria refracta DC. (Papaveraceae) of Turkish origin yielded two novel epimeric N-oxides, (?)-(5R, 11S,14R)-reframidine N-oxide ( = (?)-(5R, 11S,14R)-11,12-dihydro-14-methyl-11,5-(iminomethano)-5H -cyclohepta[1, 2-f: 4, 5-f′]bis[1,3]benzodioxole 14-oxide; 1 ) and (?)-(5R, 11S, 14S)-reframidine N-oxide ( = (?)-(5R, 11S, 14S)-11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxole 14-oxide; 2 ). The isolated (?)-roelactamine ( = (?)-11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxol-15-one, 4 ) is the first natural isopavinoid incorporating a lactam group. The epimeric (?)-15-(2-oxopropyl)reframidines ( = (?)-1-[11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxol-15-y1]propan-2-ones; 5/6 ) and the epimeric (?)-ethyl (reframidin-15-yl)acetates ( = (?)-ethyl [11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxol-15-y1]acetates; 7/8 ) are probably artifacts. (±)-Coclaurine ( 9 ), (±)-N-methylcoclaurine ( 10 ), (?)-roemeridine ( 11 ), and N-feruloyltyramine ( 12 ) are also isolated from R. refracta together with the previously reported bases. Specific 13C-NMR assignments are reported for the first time for the isopavines. 相似文献
59.
Dipl.-Phys. Lena Scherthan Rouven F. Pfleger Dr. Hendrik Auerbach Dipl.-Phys. Tim Hochdörffer Dr. Juliusz A. Wolny Dr. Wenli Bi Dr. Jiyong Zhao Dr. Michael Y. Hu Dr. E. Ercan Alp Dr. Christopher E. Anson Prof. Rolf Diller Prof. Annie K. Powell Prof. Volker Schünemann 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):8902-8907
60.
Alexey Kirilin Serap Sahin Päivi Mäki‐Arvela Johan Wärnå Tapio Salmi Dmitry Yu. Murzin 《国际化学动力学杂志》2010,42(10):629-639
The kinetics of the acylation of (R,S)‐1‐phenylethanol was investigated using lipase as a catalyst. The main parameters were temperature, reaction atmosphere, different acyl donors, and different amounts of acyl donor as well as the presence of some additives in the reaction mixture. The initial reaction rate increased with increasing temperature and with a decreasing amount of an acyl donor. The activated esters, such as isopropenyl‐ and vinyl acetate, exhibited very high acylation rates for R‐1‐phenylethanol, whereas low rates were obtained with ethyl acetate and 2‐methoxyethyl acetate. The addition of water and acetophenone decreased the acylation rate. A kinetic model was developed based on a sequential step mechanism, in which enzyme was reacting in the first step with an acyl donor followed by the reaction of a modified enzyme complex with the reactant, R‐1‐phenylethanol. Comparison with experimental data obtained at different temperatures allowed simplification of this model, leading to a kinetic equation with just one apparent parameter. The influence of the amount of acyl donor, ethyl acetate, could be quantitatively described by taking into account the competitive inhibition of the ethanol produced. The rate constants and apparent activation energy for experiments performed under different temperatures and the amounts of acylation agent were determined. The apparent activation energy was 24.5 kJ/mol. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 629–639, 2010 相似文献