全文获取类型
收费全文 | 1639篇 |
免费 | 65篇 |
国内免费 | 18篇 |
专业分类
化学 | 1026篇 |
晶体学 | 27篇 |
力学 | 58篇 |
数学 | 261篇 |
物理学 | 350篇 |
出版年
2023年 | 10篇 |
2022年 | 31篇 |
2021年 | 47篇 |
2020年 | 49篇 |
2019年 | 62篇 |
2018年 | 58篇 |
2017年 | 57篇 |
2016年 | 76篇 |
2015年 | 56篇 |
2014年 | 69篇 |
2013年 | 159篇 |
2012年 | 103篇 |
2011年 | 140篇 |
2010年 | 84篇 |
2009年 | 91篇 |
2008年 | 108篇 |
2007年 | 105篇 |
2006年 | 71篇 |
2005年 | 61篇 |
2004年 | 49篇 |
2003年 | 48篇 |
2002年 | 36篇 |
2001年 | 11篇 |
2000年 | 12篇 |
1999年 | 8篇 |
1998年 | 8篇 |
1997年 | 7篇 |
1996年 | 12篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 9篇 |
1992年 | 10篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 10篇 |
1983年 | 4篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1977年 | 2篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1967年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有1722条查询结果,搜索用时 31 毫秒
41.
A CZE method was developed and validated for the analysis of Olmesartan medoxomil (OLMD) in tablets. The influences of pH, buffer concentration, applied voltage and capillary temperature on the migration time of OLMD were investigated. About 50 mM pH 6.5 phosphate buffer were used as background electrolyte. The optimum instrument parameters were found to be 30 °C temperature with 30 kV applied voltage and diode array detection was carried out at 210 nm. OLMD was hydrodynamically injected (P inj = 50 mbar, t inj = 3 s) and an internal standard, diflunisal (IS), was used to improve the precision and repeatability. Under these conditions, the migration time of OLMD was 2.32 min and the total analysis time was shorter than 5 min. Linearity range for the developed method was found to be 2.0–50.0 μg mL?1 and the limit of detection was 0.5 μg mL?1. The developed method was applied for the analysis of OLMD in pharmaceutical tablet formulations. 相似文献
42.
The divalent metal ion sorption (Cu(2+), Cd(2+), Ni(2+), and Pb(2+)) on chromium phosphate (CrPO(4)) was studied as a function of pH, temperature, and concentration of metal ions. The sorption of metal ions is observed to increase with the increase in pH, temperature, and concentration of metal ions in solution. The mechanism of sorption is found to be the exchange of the hydrolyzed metal cations with the protons from solid at high temperature. The sorption at low temperature is found to be accompanied by the precipitation of the corresponding metal phosphates such as Pb(3)(PO(4))(2). 相似文献
43.
Mustafa R. Ibrahim Zacharia A. Fataftah Paul von Ragu Schleyer Peter D. Stout 《Journal of computational chemistry》1987,8(8):1131-1138
Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases. 相似文献
44.
Arzu
zek idem Albayrak Mustafa Odabaolu Orhan Büyükgüngr 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(3):o177-o180
The title compounds, (E)‐2‐[(2‐bromophenyl)iminomethyl]‐4‐methoxyphenol, C14H12BrNO2, (I), (E)‐2‐[(3‐bromophenyl)iminomethyl]‐4‐methoxyphenol, C14H12BrNO2, (II), and (E)‐2‐[(4‐bromophenyl)iminomethyl]‐4‐methoxyphenol, C14H12BrNO2, (III), adopt the phenol–imine tautomeric form. In all three structures, there are strong intramolecular O—H⋯N hydrogen bonds. Compound (I) has strong intermolecular hydrogen bonds, while compound (III) has weak intermolecular hydrogen bonds. In addition to these intermolecular interactions, C—H⋯π interactions in (I) and (III), and π–π interactions in (I), play roles in the crystal packing. The dihedral angles between the aromatic rings are 15.34 (12), 6.1 (3) and 39.2 (14)° for (I), (II) and (III), respectively. 相似文献
45.
A simple solid phase extraction procedure for speciation of selenium(IV) and selenium(VI) in environmental samples has been proposed prior to graphite furnace atomic absorption spectrometry. The method is based on the solid phase extraction of the selenium(IV)-ammonium pyrrolidine dithiocarbamate (APDC) chelate on the Diaion HP-2MG. After reduction of Se(VI) by heating the samples in the microwave oven with 4 mol l−1 HCl, the system was applied to the total selenium. Se(VI) was calculated as the difference between the total selenium content and Se(IV) content. The experimental parameters, pH, amounts of reagents, eluent type and sample volume were optimized. The recoveries of analytes were found greater than 95%. No appreciable matrix effects were observed. The adsorption capacity of sorbent was 5.20 mg g−1 Se (IV). The detection limit of Se (IV) (3sigma, n = 11) is 0.010 μg l−1. The preconcentration factor for the presented system was 100. The proposed method was applied to the speciation of selenium(IV), selenium(VI) and determination of total selenium in natural waters and microwave digested soil, garlic, onion, rice, wheat and hazelnut samples harvested various locations in Turkey with satisfactory results. In order to verify the accuracy of the method, certified reference materials (NIST SRM 2711 Montana Soil, NIST SRM 1568a Rice Flour and NIST SRM 8418 Wheat Gluten) were analyzed and the results obtained were in good agreement with the certified values. The relative errors and relative standard deviations were below 6 and 10%, respectively. 相似文献
46.
A squarate-based synthesis of 2-ferrocenylidene-4-cyclopentene-1,3-diones is described. When refluxed in dioxane at 100 °C, heated with silica gel as a solvent free grinded solid mixture at 125 °C or stirred with silica gel in ethyl acetate at room temperature, 4-ferrocenylethynyl-4-hydroxy-2-cyclobutenones, prepared from ethynylferrocene and 3-cyclobutene-1,2-diones, afforded 2-ferrocenylidene-4-cyclopentene-1,3-diones as the major or single product of the reaction. In some cases, ferrocenyl quinones also resulted from these reactions as the minor products. The major or exclusive formation of 2-ferrocenylidene-4-cyclopentene-1,3-diones is attributed to the radical-stabilizing ability of the ferrocenyl group. 相似文献
47.
Ali irpan Selmiye Alkan Levent Toppare Yeim Hepuzer Yusuf Yaci 《Journal of polymer science. Part A, Polymer chemistry》2002,40(23):4131-4140
A thiophene‐functionalized methacrylate monomer (3‐methylthienyl methacrylate) was synthesized via the esterification of 3‐thiophene methanol with methacryloyl chloride. The methacrylate monomer was polymerized by free‐radical polymerization in the presence of azobisisobutyronitrile as the initiator. Graft copolymers of poly(3‐methylthienyl methacrylate) (PMTM2) and polypyrrole and of PMTM2 and polythiophene were synthesized by constant‐potential electrolyses. p‐Toluene sulfonic acid, sodium dodecyl sulfate, and tetrabutylammonium tetrafluoroborate were used as the supporting electrolytes. PMTM2‐coated platinum electrodes were used as anodes in the polymerization of pyrrole and thiophene. Moreover, the oxidative polymerization of poly(3‐methylthienyl methacrylate) (PMTM1) was studied with FeCl3 as the oxidant. The self‐polymerization of PMTM1 was also investigated by galvanostatic electrolysis both in dichloromethane and in propylene carbonate. The structures of PMTM1 and PMTM2 were investigated by several spectroscopic and thermal methods. The grafting process was elucidated with conductivity measurements, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy studies. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4131–4140, 2002 相似文献
48.
Naki Çolak Yılmaz Yıldırır Mustafa Kavutcu Nilhan Nurlu 《Monatshefte für Chemie / Chemical Monthly》2007,138(12):1283-1287
Summary. Methotrexate (MTX) is a folate antagonist used in treatment of several chronic inflammatory and neoplastic conditions. In this study, new MTX-like compounds that may-be potential anticancer agents were synthesized and their structures were determined by IR, UV, GC-MS,
1H NMR, and 13C NMR spectra. Also, in this study, a series structurally related to MTX or folate analogous compounds were evaluated whether they have inhibitory properties on the dihydrofolate reductase activity
(DHFR). 相似文献
49.
Yusuf M. Al-Hiari Ali M. Qaisi Mustafa M. El-Abadelah Wolfgang Voelter 《Monatshefte für Chemie / Chemical Monthly》2006,137(2):243-248
Summary. A synthesis of 3-(4-methoxycarbonyl-2,6-dinitrophenyl)indole, its 2,6-diamino analog, and 3-(2-amino-4-trifluoromethyl-6-nitrophenyl)indole
is described. 4-(Trifluoromethyl)phenyl derivatives exhibit higher antibacterial potency than the former 4-(methoxycarbonyl)phenyl
homologs, while 3-(4-trifluoromethyl-2-nitrophenyl)indole was the most active agent in the series, with MIC ≈ 7 μg/cm3 against E. coli and S. aureus. 相似文献
50.
Nobuo Ishikawa Tomoya Kitazume Kunitake Chino Mohamed El-Said Mustafa 《Journal of fluorine chemistry》1981,18(4):447-457
The reactions of -2-methyl-2-pentene (1) with several - difunctional benzenes afforded eight- and nine-membered benzoheterocyclic compounds carrying perfluoroalkyl groups. Salicylic acid, salicylaldehyde, and their methyl or chloro derivatives reacted in triethylamine-acetonitrile system giving perfluoroalkylated 2H,6H-1,5-benzodioxocin-2,6-dione (8) and 4H,6H-1,5-benzodioxocin (9) compounds respectively, while phthalyl alcohol and o-hydroxyphenethyl alcohol in triethylamine-diethyl ether system gave perfluoroalkylated 1H,3H,7H-2,6- and 4H,6H,7H-1,5-benzodioxonin compounds, (10) and (11). o-Aminobenzyl alcohol and (1) in diethyl ether afforded a perfluoroalkylated benzoxazocinobenzoxazocinone compound (15). 相似文献