全文获取类型
收费全文 | 645篇 |
免费 | 42篇 |
国内免费 | 12篇 |
专业分类
化学 | 556篇 |
晶体学 | 2篇 |
力学 | 15篇 |
数学 | 63篇 |
物理学 | 63篇 |
出版年
2023年 | 10篇 |
2022年 | 7篇 |
2021年 | 25篇 |
2020年 | 49篇 |
2019年 | 28篇 |
2018年 | 54篇 |
2017年 | 30篇 |
2016年 | 43篇 |
2015年 | 41篇 |
2014年 | 46篇 |
2013年 | 69篇 |
2012年 | 27篇 |
2011年 | 49篇 |
2010年 | 38篇 |
2009年 | 31篇 |
2008年 | 34篇 |
2007年 | 26篇 |
2006年 | 25篇 |
2005年 | 18篇 |
2004年 | 12篇 |
2003年 | 10篇 |
2002年 | 7篇 |
1999年 | 3篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 5篇 |
1977年 | 2篇 |
排序方式: 共有699条查询结果,搜索用时 500 毫秒
31.
Issa Yavari Abdolali Alizadeh Hamed Mohebbi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1741-1746
The reactive 1:1 intermediate produced in the addition reaction between trimethyl-phosphite and dibenzoylacetylene was trapped by SH- or NH-acids such as 4-nitroimidazole, 4-methyl-5-nitroimidazole, succinimide, or mercaptoacetic acid to produce 2-substituted 1,4-diphenylbutane-1,4-diones. 相似文献
32.
A simple, rapid, and highly sensitive method for simultaneous analysis of anti‐inflammatory drugs (naproxen, ibuprofen, and mefenamic acid) in diluted human serum was developed using the electrochemically controlled solid‐phase microextraction coupled to ion mobility spectrometry. A conducting molecularly imprinted polymer film based on polypyrrole was synthesized for the selective uptake and release of drugs. The film was prepared by incorporation of a template molecule (naproxen) during the electropolymerization of pyrrole onto a platinum electrode using cyclic voltammetry method. The measured ion mobility spectrometry intensity was related to the concentration of analytes taken up into the films. The calibration graphs (naproxen, ibuprofen, and mefenamic acid) were linear in the range of 0.1–30 ng/mL and detection limits were 0.07–0.37 ng/mL and relative standard deviation was lower than 6%. On the basis of the results obtained in this work, the conducting molecularly imprinted polymer films as absorbent have been applied in the electrochemically controlled solid‐phase microextraction and ion mobility spectrometry system for the selective clean‐up and quantification of trace amounts of anti‐inflammatory drugs in human serum samples. Scanning electron microscopy has confirmed the nano‐structure morphology of the polypyrrole film. 相似文献
33.
Abbas Rahmati Ali Hossein Rezayan Meysam Alizadeh Ali Nikbakht 《Journal of the Iranian Chemical Society》2013,10(3):521-525
A simple and eco-friendly synthesis of the biologically important spirooxindole scaffold was done by the reaction of isatin with activated pyrazolones in the presence of a catalytic amount of p-toluenesulfonic acid in water at room temperature. A variety of symmetrical spirooxindole derivatives were obtained with excellent yields within short reaction time. This method is of great value because of its environmentally benign character, high yield, and easy handling. 相似文献
34.
Concentration effect of silver nanoparticles (AgNPs) on the photophysical properties of ciprofloxacin (Cip) have been investigated using optical absorption and fluorescence techniques. When performed AgNPs solution was added to the Cip solution, metal-enhanced fluorescence intensity and a blue-shift of 20 nm in the maximum emission spectra of Cip has been observed. The enhanced intensity of this system is strongly dependent on the AgNPs concentration and largest at the 6.0 × 10?6 mol L?1. With increase of AgNPs concentration, quenching of fluorescence is observed. Stern–Volmer quenching constants have been calculated at four temperatures. The results show the quenching constants are directly correlated with temperature. It indicates the quenching mechanism is the dynamic quenching in nature rather than static quenching. From which we determined the activation energy for the quenching of Cip-AgNPs to be about 31.1 kJ mol?1. In addition, in the presence of optimum AgNPs concentration, a sensitive fluorimetric method for the determination of ciprofloxacin at the range 5.0 × 10?7–3.0 × 10?5 mol L?1 and the detection limit of 2 × 10?8 mol L?1 in solution is proposed. 相似文献
35.
Abbas Afkhami Farzaneh Soltani-Felehgari Tayyebeh Madrakian Hamed Ghaedi Majid Rezaeivala 《Analytica chimica acta》2013
A new chemically modified carbon paste electrode was constructed and used for rapid, simple, accurate, selective and highly sensitive simultaneous determination of cadmium, copper and mercury using square wave anodic stripping voltammetry (SWASV). The carbon paste electrode was modified by N,N′-bis(3-(2-thenylidenimino)propyl)piperazine coated silica nanoparticles. Compared with carbon paste electrode, the stripping peak currents had a significant increase at the modified electrode. Under the optimized conditions (deposition potential, −1.100 V vs. Ag/AgCl; deposition time, 60 s; resting time, 10 s; SW frequency, 25 Hz; pulse amplitude, 0.15 V; dc voltage step height, 4.4 mV), the detection limit was 0.3, 0.1 and 0.05 ng mL−1 for the determination of Cd2+, Cu2+ and Hg2+, respectively. The complexation reaction of the ligand with several metal cations in methanol was studied and the stability constants of the complexes were obtained. The effects of different cations and anions on the simultaneous determination of metal ions were studied and it was found that the electrode is highly selective for the simultaneous determination of Cd2+, Cu2+ and Hg2+. Furthermore, the present method was applied to the determination of Cd2+, Cu2+ and Hg2+ in water and some foodstuff samples. 相似文献
36.
An efficient approach for the preparation of functionalized 2‐aryl‐2,5‐dihydro‐5‐oxo‐4‐[2‐(phenylmethylidene)hydrazino]‐1H‐pyrroles is described. The four‐component reaction between aldehydes, NH2NH2?H2O, dialkyl acetylenedicarboxylates, and 1‐aryl‐N,N′‐bis(arylmethylidene)methanediamines proceeds in EtOH under reflux in good‐to‐excellent yields (Scheme 1). The structures of 4 were corroborated spectroscopically (IR, 1H‐ and 13C‐NMR, and EI‐MS, and, in the case of 4f , by X‐ray crystallography). A plausible mechanism for this type of reaction is proposed (Scheme 2). 相似文献
37.
Taher Alizadeh 《International journal of environmental analytical chemistry》2013,93(15):1742-1760
Molecularly imprinted polymer nanoparticles (nano-MIP), containing parathion selective sites, were synthesized by using suspension polymerization in silicon oil and then used for carbon paste electrode preparation. The obtained electrode was applied as an electrochemical sensor for parathion determination in different fruit and vegetable samples. Different factors including electrode composition, conditions of parathion extraction in the electrode and electrochemical measurement conditions were evaluated and then optimized by using various techniques of screening and response surface experimental designs. Electrode response to parathion (Res1) and its selectivity for parathion (Res2) were the desired responses. These responses were optimized simultaneously. After optimization, a sensor with high selectivity and picomolar detection limit were obtained. It was shown that the sensor response to parathion concentration was linear in the concentration range of 0.05 to 150?nmol?L?1. The detection limit of designed sensor was calculated equal to 0.02?nmol?L?1. The developed determination method was properly used for ultra-trace level assay of parathion in different fruit and cabbage samples. 相似文献
38.
The synthesis of 3-(4-alkyl-4,5-dihydropyrrolo[1,2-a]quinoxalin-4-yl)-2H-chromen-2-one derivatives by a three-component reaction of salicylaldehyde, β-keto esters, and 1-(2-aminophenyl)pyrrole using piperidine–iodine as a dual system catalyst is reported. Good yields, mild reaction conditions, and ease of handling are the main aspects of the method. The structural assignments are supported by 1H NMR, 13C NMR, and X-ray crystallography data. 相似文献
39.
Solid‐based disperser liquid–liquid microextraction for the preconcentration of phthalate esters and di‐(2‐ethylhexyl) adipate followed by gas chromatography with flame ionization detection or mass spectrometry 下载免费PDF全文
Mir Ali Farajzadeh Parisa Khorram Ali Akbar Alizadeh Nabil 《Journal of separation science》2014,37(9-10):1177-1184
A new approach for the development of a dispersive liquid–liquid microextraction followed by GC with flame ionization detection was proposed for the determination of phthalate esters and di‐(2‐ethylhexyl) adipate in aqueous samples. In the proposed method, solid and liquid phases were used as the disperser and extractant, respectively, providing a simple and fast mode for the extraction of the analytes into a small volume of an organic solvent. In this method, microliter levels of an extraction solvent was added onto a sugar cube and it was transferred into the aqueous phase containing the analytes. By manual shaking, the sugar was dissolved and the extractant was released into the aqueous phase as very tiny droplets to provide a cloudy solution. Under optimized conditions, the proposed method showed good precision (RSD less than 5.2%), high enrichment factors (266–556), and low LODs (0.09–0.25 μg/L). The method was successfully applied for the determination of the target analytes in different samples, and good recoveries (71–103%) were achieved for the spiked samples. No need for a disperser solvent and higher enrichment factors compared with conventional dispersive liquid–liquid microextraction and low cost and short sample preparation time are other advantages of the method. 相似文献
40.
Dr. Zhaowen Dong Dr. Andrzej Sienkiewicz Dr. Abdusalom A. Suleymanov Cesare Berton Dr. Farzaneh Fadaei-Tirani Dr. Rosario Scopelliti Prof. Kay Severin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200893
Dichalcogenolenes are archetypal redox non-innocent ligands with numerous applications. Herein, a diselenolene ligand with fundamentally different electronic properties is described. A mesoionic diselenolene was prepared by selenation of a C2-protected imidazolium salt. This ligand is diamagnetic, which is in contrast to the paramagnetic nature of standard dichalcogenolene monoanions. The new ligand is also redox-active, as demonstrated by isolation of a stable diselenolene radical dianion. The unique electronic properties of the new ligand give rise to unusual coordination chemistry. Thus, preparation of a hexacoordinate aluminum tris(diselenolene) complex and a Lewis acidic aluminate complex with two ligand-centered unpaired electrons was achieved. 相似文献