纳米金/β-环糊精复合修饰碳糊电极测定亚硝酸盐

本文研究了亚硝酸盐(NO_2~-)在纳米金和β-环糊精复合修饰碳糊电极(AuNPs-β-CD/CPE)上的电化学行为。实验结果表明,与裸CPE相比,AuNPs-β-CD/CPE对NO_2~-的电化学氧化有显著的促进作用,其氧化峰电流显著增加。同时用循环伏安法(CV)、计时电流法(CA)测定了NO_2~-在AuNPs-β-CD/CPE上的电极反应动力学参数,用线性扫描伏安法(LSV)法测得NO_2~-氧化峰电流与其浓度在6.0×10-6~8.0×10-3 mol·L-1范围内呈良好的线性关系,检出限(S/N=3)为5.7×10-7 mol·L-1。将该传感器应用于水样的检测,相对标准偏差在0.15%~1.40%之间,回收率达99.3%~104.0%,检测结果符合定量测定要求。     

Computational Insights into Different Mechanisms for Ag-, Cu-, and Pd-Catalyzed Cyclopropanation of Alkenes and Sulfonyl Hydrazones

The [2+1] cycloaddition reaction of a metal carbene with an alkene can produce important cyclopropane products for synthetic intermediates, materials, and pharmaceutical applications. However, this reaction is often accompanied by side reactions, such as coupling and self-coupling, so that the yield of the cyclopropanation product of non-silver transition-metal carbenes and hindered alkenes is generally lower than 50 %. To solve this problem, the addition of a low concentration of diazo compound (decomposition of sulfonyl hydrazones) to alkenes catalyzed by either CuOAc or PdCl₂ was studied, but side reactions could still not be avoided. Interestingly, however, the yield of cyclopropanation products for such hindered alkenes were as high as 99 % with AgOTf as a catalyst. To explain this unexpected phenomenon, reaction pathways have been computed for four different catalysts by using DFT. By combining the results of these calculations with those obtained experimentally, it can be concluded that the efficiency of the silver catalyst is due to the barrierless concerted cycloaddition step and the kinetic inhibition of side reactions by a high concentration of alkene.     

In beam Mößbauer spectroscopy: 57Fe in semiconductors

Abstract

An overview of results on microscopic properties, implantation features and dynamics of Fe ions implanted into Si, Ge and ZnS as investigated with in beam Mößbauer spectroscopy(IBMS) is given. Potential and limitations of the method are discussed.     

Carbon Paste Composite with Co3O4 as a New Electrochemical Sensor for the Detection of Allura Red by Reduction

The detection of Allura red (AR) by electrochemical reduction using a different electrode from the conventional mercury electrode is presented. A carbon paste with cobalt (II, III) oxide composite electrode (CoO_x/CPE) is reported for the first time for the detection of AR. Moreover, others dyes such as tartrazine (TZ), sunset yellow (SY), amaranth (AM), Ponceaut 4‐R (P‐4R), and Sudan (SD) as well as pharmaceutical agents such as paracetamol (PMC) that are present in samples that contained AR did not show a reduced signal between 0.0 and ?0.3 V, which is the potential range where AR reduction was observed. The surface electroactivity was studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The presence of CoO_X increased the cathodic peak current for AR by more than 50 % and 65 % via CV and square wave voltammetry (SWV), respectively, compared with an unmodified carbon paste electrode. Under the optimal parameters, (pH=3.0, accumulation time (t_ACC)=60 s and accumulation potential (E_ACC)=0.50 V), the detection limit for AR was 0.05 μmol L^?1. The new sensor was sensitive and stable for the detection of AR. Moreover, it was easily manufactured and very convenient for food samples such as soft and isotonic drinks as well as chili sauce.     

Ru(II)‐based antineoplastic: A “wingtip” N‐heterocyclic carbene facilitates access to a new class of organometallics that are cytotoxic to common cancer cell lines

The syntheses, structures, and chemotherapeutic activities of Ag(I)‐, Au(I)‐, and Ru(II)‐complexes ligated to a novel N‐heterocyclic carbene ligand, 2‐(4‐nitrophenyl)imidazo[1,5‐a]pyridin‐2‐ylidene ( 1 ), are described. The corresponding complexes, [Ag( 1 )₂][PF₆], [Au( 1 )₂][PF₆] ( 3 ), and [Ru( 1 )(p‐cymene)Cl][PF₆] ( 4 ), were prepared using convenient transmetallation chemistry and characterized using a range of spectroscopic and analytical techniques. X‐ray crystallography revealed that complexes 2 and 3 adopted linear structures whereas 4 exhibited a prototypical “piano‐stool”‐like geometry; the structural assignments were further supported by DFT calculations. A series of in vitro studies revealed that while the aforementioned Ag(I), Au(I) and Ru(II) complexes exhibited significant cytotoxicities against the human colon adenocarcinoma (HCT 116), lung cancer (A549), and breast cancer (MCF7) cell lines, the Ru derivative was most prominent.     

Ultrasonic assisted synthesis of nanocrystalline cellulose as support and reducing agent for Ag nanoparticles: green synthesis and novel effective nanocatalyst for degradation of organic dyes

In this study, nanocrystalline cellulose (NCC) prepared from microcrystalline cellulose using high‐intensity ultrasonication as mechanical method without any chemical treatment. The obtained NCC with around 30–50 nm diameters, utilized as support, reducing and stabilizing agent for in‐situ green and eco‐friendly synthesis of silver nanoparticles (Ag NPs). The catalytic activity of composite was examined for degradation of environmental pollutants. The structure of as‐synthesized composite (Ag@NCC) was characterized by ultraviolet–visible spectroscopy (UV–vis), field emission scanning electron microscopy (FE‐SEM); Transmission electron microscopy (TEM); Energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD) and thermogravimetric analysis (TGA). The results of the catalytic reaction experiments showed that spherically shaped silver nanoparticles of around 20 nm distributed on the surface of nanocellulose demonstrated high catalytic efficiency towards the removal of methyl orange (MO) and 4‐nitrophenol (4‐NP).     

CoO–xCo(OH)2 supported silver nanoparticles: electrosynthesis in acetonitrile and catalytic activity

1. Download : Download high-res image (151KB)
2. Download : Download full-size image

     

银纳米晶对铒镱共掺的TeO2-WO3-La2O3微晶玻璃发光性能的影响

通过熔融退火的方法以及热处理技术制备得到含有Er₂WO₆，La₂WO₆晶体的TeO₂-WO₃-La₂O₃-Er₂O₃-Yb₂O₃微晶玻璃，该玻璃具有优异的上转换发光性能。结果表明，在含银纳米晶的碲酸盐微晶玻璃中，银纳米晶和微晶的析出情况与银纳米晶的引入方式和热处理温度有关。经过390℃下15 min的热处理后，AgCl和AgNO₃共掺的碲酸盐微晶玻璃比单掺AgCl或AgNO₃的碲酸盐微晶玻璃具有更高的发光强度。银纳米晶与微晶的引入可协同提高碲酸盐玻璃的上转换发光性。     

Green synthesis and antibacterial effects of aqueous colloidal solutions of silver nanoparticles using clove eugenol

Silver nanoparticles were synthesized using clove extract (CE). Scanning transmission electron microscopy (STEM) revealed the morphology of the metallic Ag nanoparticles obtained via the clove extract synthesis (Ag NPs‐CE), which had a uniform distribution and average sizes varying from 10 nm to 100 nm. Fourier transform infra‐red (FTIR) spectroscopy showed that clove eugenol acts as a capping and reducing agent being adsorbed on the surface of Ag NPs‐CE, enabling their reduction from Ag⁺ and preventing their agglomeration. Formation of the Ag⁰ structure is also confirmed in the FTIR spectrum by the presence in the Ag NPs‐CE sample of the –C=O and –C=C vibrations at wavenumbers 1600 and 2915 cm^‐1, respectively. Antibacterial and antifungal tests using three strains of bacteria and one fungi strain showed that the Ag NPs‐CE performed better compared to pure clove extract (CE) sample.     

Voltammetric Study and Rapid Quantification of Resorcinol in Hair Dye and Biological Samples Using Ultrasensitive Maghemite/MWCNT Modified Carbon Paste Electrode

Increased concern over the risk resorcinol (RS) pose to ecology and humans, led to its position in European Union Category 1 list of endocrine disruptors. Legal measures restricted RS utilization and hence crucial to monitor its levels in the environment. Herein we report development of highly efficient and economically viable electrochemical sensor for quantitative determination of RS based on 77Maghemite/MultiWall Carbon Nanotube (M/MWCNT) modified carbon paste electrode. M/MWCNT was synthesized via strategic IR irradiation for the first time, a promising approach to overcome other complicated chemical routes. Powder X‐ray diffraction (PXRD), Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM) and Energy dispersive X‐ray (EDX) were used for characterization. Using Differential Pulse Voltammetry (DPV), we report the lowest detection limit at 0.02 μM. The potential application of the sensor was accomplished as a result of excellent recoveries made from real samples fortified with RS. Results indicated the proficiency of the sensor reliable for rapid, onsite monitoring of RS water contamination and in biological matrices.