摘要：
A graphene oxide (GO) film coated glassy carbon electrode (GCE) was fabricated for sensitive determination of 4-nitrophenol (4-NP). The GO-based sensor was characterized by scanning electron microscope, atomic force microscopy and electrochemical impedance spectroscopy. The electrochemical behaviors of 4-NP at the GO-film coated GCE were investigated in detail. In 0.1 M acetate buffer with a pH of 4.8, 4-NP yields a very sensitive and well-defined reduction peak at the GO-modified GCE. It is found that the GO film exhibits obvious electrocatalytic activity toward the reduction of 4-NP since it not only increases the reduction peak current but also lowers the reduction overpotential. Based on this, an electrochemical method was proposed for the direct determination of 4-NP. Various kinetic parameters such as transfer electron number, transfer proton number and standard heterogeneous rate constant were calculated, and various experimental parameters were also optimized. Under the optimal conditions, the reduction peak current varies linearly with the concentration of 4-NP ranging from 0.1 to 120 mu M, and the detection limit is 0.02 mu M at the signal noise ratio of 3. Moreover, the fabricated sensor presented high selectivity and long-term stability. This electrochemical sensor was further applied to determine 4-NP in real water samples, and it showed great promise for simple, sensitive, and quantitative detection of 4-NP. (C) 2011 Elsevier B.V. All rights reserved.
摘要：
We report on a glassy carbon electrode that was modified with a composite made from graphene oxide (GO) and multiwalled carbon nanotubes (MWCNT) that enables highly sensitive determination of L-tyrosine. The sensor was characterized by transmission electron microscopy and electrochemical impedance spectroscopy, and its electrochemical properties by cyclic voltammetry, chronocoulometry and differential pulse voltammetry. The GO/MWCNT hybrid exhibits strong catalytic activity toward the oxidation of L-tyrosine, with a well defined oxidation peak at 761 mV. The respective current serves as the analytical information and is proportional to the L-tyrosine concentration in two ranges of different slope (0.05 to 1.0 μM and 1.0 to 650.0 μM), with limits of detection and quantification as low as 4.4 nM and 14.7 nM, respectively. The method was successfully applied to the analysis of L-tyrosine in human body fluids. The excellent reproducibility, stability, sensitivity and selectivity are believed to be due to the combination of the electrocatalytic properties of both GO and MWCNT. They are making this hybrid electrode a potentially useful electrochemical sensing platform for bioanalysis. Figure A new L-tyrosine electrochemical sensor was fabricated based on graphene oxide and multiwalled carbon nanotube. The prepared sensor exhibits excellent electro-catalysis to the oxidation of L-tyrosine, and can improve determination sensitivity and decrease detection limit. This sensor was successfully applied to detect L-tyrosine in human fluids with satisfactory results.
摘要：
We report on a highly sensitive glucose biosensor that was fabricated from a composite made from mesoporous hydroxyapatite and mesoporous titanium dioxide which then were ultrasonically mixed with multi-walled carbon nanotubes to form a rough nanocomposite film. This film served as a platform to immobilize glucose oxidase onto a glassy carbon electrode. The morphological and electrochemical properties of the film were examined by scanning electron microscopy and electrochemical impedance spectroscopy. Cyclic voltammetry and chronoamperometry were used to characterize the electrochemical performances of the biosensor which exhibited excellent electrocatalytic activity to the oxidation of glucose. At an operating potential of 0.3 V and pH 6.8, the sensor displays a sensitivity of 57.0 μA mM−1 cm−2, a response time of <5 s, a linear dynamic range from 0.01 to 15.2 mM, a correlation coefficient of 0.9985, and a detection limit of 2 μM at an SNR of 3. No interferences are found for uric acid, ascorbic acid, dopamine and most carbohydrates. The sensor is stable and was successfully applied to the determination of glucose in real samples. Mesoporous hydroxyapatite, titanium dioxide and multi-walled carbon nanotubes were ultrasonically mixed to form a rough nanofilm, and a new glucose biosensor was fabricated based on this nanofilm. The biosensor had great bioelectrocatalytic activity to glucose oxidation, and it exhibited a high sensitivity, wide linear dynamic range and high selectivity for glucose determination.
摘要：
The CuI/triethanolamine catalyst system efficiently promotes the direct hydroxylation of aryl iodides and bromides in water to provide the corresponding phenols in good to excellent yields. Moreover, the procedure avoids the use of toxic organic solvents and tolerates many functional groups.
摘要：
A series of five diruthenium diethynyl complexes based on alpha,beta-fused oligothienoacenes in the core of the bridging ligands [{Ru(dppe)Cp*}2(mu-C identical withC-L-C identical withC)] [dppe = 1,2-bis(diphenylphosphino)ethane, Cp* = eta(5)-C5Me5; L = thieno[3,2-b]thiophene (4), thieno[2,3-b]thiophene (5), 3,4-dimethylthieno[2,3-b]thiophene (6), dithieno[3,2-b:2',3'-d]thiophene (7), and thieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophene (8)] have been synthesized and fully characterized electrochemically and spectroscopically. Elongation of the redox noninnocent oligothienoacene bridge core causes a smaller potential difference between the initial two anodic steps, not seen for free dialkyl oligothienoacenes, and increased positive charge delocalization over the conjugated bridge backbone. The highest occupied molecular orbital of the parent complexes resides predominantly on the oligothienoacene core, with strong participation of the ethynyl linkers and slightly smaller contribution from the metallic termini. This bonding character makes the initial one-electron oxidation symmetrical, as revealed by combined voltammetric and spectroscopic (IR, UV-vis-near-IR, and electron paramagnetic resonance) methods as well as density functional theory (DFT) and time-dependent DFT calculations of truncated and selected nontruncated models of the studied series. The remarkable gradual appearance of two C identical withC stretching absorptions in the IR spectra of the monocationic diethynyl complexes is ascribed to increasing vibronic coupling of the IR-forbidden nus(C identical withC) mode of the oxidized -[C identical withC-core-C identical withC](+)- bridge with a low-lying pi-pi*(intrabridge)/metal-to-ligand charge-transfer electronic transition in the near-to-mid-IR spectral region.
摘要：
An efficient protocol for ligand-free Cu-catalyzed N-arylation of heteroarylamines has been developed. With the use of 1% CuI, a wide range of aryl iodides and bromides coupled with heteroarylamines to afford the corresponding products in high yields. Further, this protocol is particularly suitable for reactions of the most hindered aryl iodides with 2-aminopyridines. (C) 2014 Elsevier Ltd. All rights reserved.
摘要：
Eight organotin(IV) complexes (C1-C8) have been synthesized and characterized by elemental analysis, fourier transform infrared spectroscopy (FT-IR), multinuclear nuclear magnetic resonance ((1)H, (13)C and (119)Sn NMR), high resolution mass spectroscopy (HRMS) and single crystal X-ray structural analysis. Crystallographic data show that C1 was a tetranuclear 16-membered macrocycle complex, C2-C4 and C7 were centrosymmetric dimer distannoxane and there was a Sn2O2 four-membered ring in the middle of the molecule, respectively, C5 and C6 are monoorganotin complexes due to the dehydroalkylation effect during the reaction, while C8 forms a one-dimensional chain structure. The cytotoxicity of all complexes were tested by 3-(4,5)-dimethylthiahiazo(-z-y1)-3,5-di-phenytetrazoliumromide (MTT) assays against three human tumor cell lines NCI-H460, MCF-7 and HepG2. The dibutyltin complex C2 has been shown to be more potent antitumor agents than other complexes and carboplatin. Cell apoptosis study of C2 with the high activity on HepG2 and MCF-7 cancer cell lines was investigated by flow cytometry, it was shown that the antitumor activity of C2 was related to apoptosis, but it has different cell cycle arrest characteristics from platinum compounds, and the proliferation was inhibited by blocking cells in S phase. The DNA binding activity of the C2 was studied by UV-visible absorption spectrometry, fluorescence competitive, viscosity measurements and gel electrophoresis, results shown C2 can be well embedded in the double helix of DNA and cleave DNA.
作者机构：
[Zhang, Faxing; Yu, Jiangxi; Zhu, Xiaoming; Kuang, Daizhi; Zhu, XM; Yu, JX] Hengyang Normal Univ, Hunan Prov Univ Key Lab Funct Organomet Mat, Coll Chem & Mat Sci, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Hunan, Peoples R China.;[Zhu, XM; Liang, Yun; Yang, Yuan; Zhu, Xiaoming; Deng, Guobo] Hunan Normal Univ, Key Lab Assembly & Applicat Organ Funct Mol Hunan, Changsha 410081, Hunan, Peoples R China.
通讯机构：
[Zhu, XM; Yu, JX; Liang, Y] H;Hengyang Normal Univ, Hunan Prov Univ Key Lab Funct Organomet Mat, Coll Chem & Mat Sci, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Hunan, Peoples R China.;Hunan Normal Univ, Key Lab Assembly & Applicat Organ Funct Mol Hunan, Changsha 410081, Hunan, Peoples R China.
摘要：
We describe a three-component reaction of o-iodoanilines with K2S and DMSO that provides 2-unsubstituted benzothiazoles in moderate to good isolated yields with good functional group tolerance. Electron-rich aromatic amines and o-phenylenediamines instead of o-iodoanilines provided 2-unsubstituted benzothiazoles and 2-unsubstituted benzimidazoles with and without K2S under similar conditions. Notably, DMSO plays three vital roles: carbon source, solvent, and oxidant.
摘要：
A novel and convenient electrochemical method has been developed for sensitive determination of melamine (MEL) using ascorbic acid (AA) as the recognition element. The working electrode employed in this method was modified with the nanocomposite of hydroxyapatite/carbon nanotubes to enhance the current signal of recognition element. The interaction between MEL and AA was investigated by fourier transform infrared spectroscopy and cyclic voltammetry, and the experimental results indicated that hydrogen bonding was formed between MEL and AA. Because of the existing hydrogen bonding and electrostatic interaction, the anodic peak current of AA was decreased obviously while the non-electroactive MEL added in. It illustrated that the MEL acted as an inhibitor to the oxidation of AA and the decreasing signals can be used to detect MEL. Under the optimal conditions, the decrease in anodic peak current of AA was proportional to the MEL concentrations ranging from 10 to 350 nM, with a detection limit of 1.5 nM. Finally this newly-proposed method was successfully employed to detect MEL in infant formula and milk, and good recovery was achieved.
摘要：
The first room-temperature copper-catalyzed arylations of dimethylamine and methylamine in neat water have been developed. Using a combination of CuI and 6,7-dihydroquinolin-8(5H)-one oxime as catalyst, dimethylamine is arylated with various aryl halides to give the corresponding products in good to excellent yields. Further, this catalysis enables the selective arylation of methylamine to afford the high yields of monoarylated methylamines as the sole products.
