Characterization and Use of Copper Solid Amalgam Electrode for Electroanalytical Determination of Triazines‐Based Herbicides

This paper reports the construction, characterization and use of copper solid amalgam electrode in the study of the electrochemical behavior of atrazine and ametryne herbicides by square‐wave voltammetry. This study was used as basis for the development of sensitive analytical methods for the determination of these herbicides in natural water, avoiding the use of mercury, by means of a solid electrode that presents high sensitivity and minimizes any environment contamination with mercury residues. The experimental and voltammetric conditions were evaluated and the results showed a reduction peak for atrazine at ?0.98 and at ?1.1 V vs. Ag/AgCl 3.0 mol L^?1 for ametryne, both with characteristic of an irreversible electrode reaction in an electrochemical diffusion controlled process, involving two electrons for each herbicide reduction. Based on voltammetric studies, it has been demonstrated that the most possible mechanism for the reduction of herbicides involved reduction of bond carbon‐chloride for atrazine and the reduction of bond carbon–SCH₃ for ametryne. The detection limit of herbicides obtained in pure water (laboratory samples) was shown to be lower than the maximum limit of residue established for natural water by the Brazilian Environmental Agency, demonstrating that this methodology is very suitable for determining any contamination by atrazine and ametryne residues in different samples, proving a good substitute for mercury electrodes.     

Chiral separation of halogenated amino acids by ligand-exchange capillary electrophoresis

The chiral separation of halogenated amino acids by ligand-exchange CE is described. Halogenated amino acids attracted increasing interest in recent years because of their physiological activities. Different chiral selectors, as there are L-4-hydroxyproline, L-histidine, and N-alkyl derivatives of L-4-hydroxyproline in form of their copper(II) complexes, are compared for their chiral recognition ability for halogenated amino acids. The influence of various parameters, such as selector concentration, pH, organic modifier, and field strength, on the resolution was investigated. All halogenated amino acids investigated were baseline-separated under optimized conditions.     

Study of the Electrochemical Behavior of Disperse Blue 1‐Modified Graphite Electrodes. Application to the Flow Determination of NADH

The preparation and the electrochemical study of Disperse Blue 1‐chemically modified electrodes (DB1‐CME), as well as their efficiency for the electrocatalytic oxidation of NADH is described. The proposed mediator was immobilized by physical adsorption onto graphite electrodes. The electrochemical behavior of DB1‐CME was studied with cyclic voltammetry. The electrochemical redox reaction of DB1 was found to be reversible, revealing two well‐shaped pair of peaks with formal potentials 152 and ?42 mV, respectively, (vs. Ag/AgCl/3M KCl) at pH 6.5. The current I_p has a linear relationship with the scan rate up to 800 mV s^?1, which is indicative for a fast electron transfer kinetics. The dissociation constants of the immobilized DB1 redox couple were calculated pK₁=4 and pK₂=5. The electrochemical rate constants of the immobilized DB1 were calculated k₁°=18 s^?1 and k₂°=23 s^?1 (Γ=2.36 nmol cm^?2). The modified electrodes were mounted in a flow injection manifold, poised at +150 mV (vs. Ag/AgCl/3M KCl) and a catalytic current due to the oxidation of NADH was measured. The reproducibility was 1.4% RSD (n=11 for 30 μM NADH) The behavior of the sensor towards different reducing compounds was investigated. The sensor exhibited good operational and storage stability.     

Highly Sensitive Amperometric Glucose Biosensor Based on Glassy Carbon Electrode with Copper/Palladium Coating

A highly sensitive amperometric glucose biosensor based on immobilizing glucose oxidase in electropolymerized poly(o‐phenylenediamine) film on glassy carbon electrode coated sequentially with copper and palladium layers has been developed. The steady‐state amperometric response to glucose was determined by means of the oxidation of hydrogen peroxide generated by the enzymatic reaction at a potential of either +0.70 or +0.40 V (vs. Ag|AgCl reference). The deposited copper/palladium layer showed great enhancement in the performance of the enzyme electrode, possibly due to its better electrocatalytic activity for hydrogen peroxide oxidation and large surface area. Effects of the relative loading of palladium, enzyme and polymer on the electrode performance were examined in detail. Sensitivity and detection limit for glucose determinations at +0.70 V were about 7.3 μA/mM and 0.1 μM, respectively. A wide linear range up to 6.0 mM glucose could be achieved. Electrode performance was superior to similar works reported in the literature. The response time was less than 2 s and its lifetime was longer than three months. The permeable polyphenylenediamine film also offered good anti‐interference ability to ascorbic acid, uric acid and acetaminophen, especially when a detection potential of +0.40 V was employed.     

Syntheses and Crystal Structures of Two Metal Succinates Modified by Bipyridines

Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C₄H₄O₄)·1/4H₂O ( 1 ) and Cu(2, 2′‐bpy)(C₄H₄O₄)_0.5(NO₃)(H₂O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) ų, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) ų, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the Cu^II atom adopts a distorted octahedral in which the Cu^II atoms are bridged by two H₂O molecules into an infinite zigzag chain, [Cu₂(H₂O)₂(C₄H₄O₄)]_n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure.     

基于快速扫描光学延迟线谐振扫描的相位调制方法

提出利用快速扫描光学延迟线(Rapid Scanning Optical Delay Line,RSOD)作为光学相干层析成像(Optical Coherence Tomography,OCT)系统的相位调制器,并采用正弦驱动方式(谐振扫描)来提高扫描频率,进而实现高频相位调制的方法.介绍了基于RSOD相位调制器的干涉信号包络解调方法,分析了大振镜低频率线性驱动、小振镜高频线性驱动和大振镜高速正弦驱动三种实施方案对OCT性能的影响,并针对谐振扫描方案中轴向扫描的非线性提出了图像畸变定量校正的方法.结果表明:RSOD大振镜谐振扫描的模式能够兼顾系统成像速度、成像范围以及系统信噪比的要求,是一种行之有效的相位调制方法.     

Cornelian Cherry (Cornus mas L.) Extracts Exert Cytotoxicity in Two Selected Melanoma Cell Lines—A Factorial Analysis of Time-Dependent Alterations in Values Obtained with SRB and MTT Assays

Despite the fact that phytochemicals of Cornaceae species have long been discussed as possible auxiliary agents in contemporary treatment, the insights on their properties remain relatively scarce. This study focuses on Cornus mas L. (Cornelian cherry), the extracts of which are reported to exert a pleiotropic effect shown in both in vivo and in vitro studies. This study aimed to explore the cytotoxic effect of extracts from fruits of red (Cornus mas L. ‘Podolski’) and yellow (Cornus mas L. ‘Yantarnyi’ and ‘Flava’) Cornelian cherries on two melanoma cell lines (A375 and MeWo). The extracts were characterized in the context of the concentration of bioactive compounds of antioxidative properties. Cytotoxicity was investigated with the use of the following two assays: SRB and MTT. An additional, alternative protocol for the SRB assay was used in this study so as to account for possible bias. Cytotoxicity was assessed as a difference in the whole time series of cell viability, instead of analyzing differences in raw values (often found in the literature). Both extracts from Cornus mas L. induced cytotoxicity in both A375 and MeWo cell lines, although the response of these cells was different. Moreover, based on this study, there is no evidence for claiming a different magnitude of cytotoxicity between these two extracts.     

基于金纳米棒-壳聚糖复合膜的葡萄糖生物传感器

本文采用金纳米棒-壳聚糖复合膜固定葡萄糖氧化酶构建电流型葡萄糖生物传感器.通过电化学交流阻抗法和循环伏安法对酶膜状态进行了表征,得到了相应的等效电路和动力学参数.实验结果表明,金纳米棒-壳聚糖复合膜可以辅助电子传递,提高电极的电流响应,并使生物传感器的使用温度范围有很大的扩展.此传感器表现出对葡萄糖溶液浓度的优良响应,线性范围在2.78×10^-5mol/L—2.22×10^-3mol/L,响应灵敏度约为7.819μA·cm^-2(mmol/L)^-1,表观米氏常数为10mmol/L.本工作还研究了温度和溶液pH值对电极电流响应的影响.     

类氢氖在高温高密度等离子体中的光谱漂移

 采用离子球模型,通过自洽求解Poisson方程和Dirac方程,得到氖的类氢离子低能级组态的能级能量随等离子体电子温度和电子密度的变化关系,进一步研究了等离子体电子温度和电子密度对光谱漂移的影响。结果表明：光谱漂移随着等离子体电子密度的增大而增大,随着电子温度的升高而减小;谱线精细结构分裂随着电子密度的增大而减小,随着电子温度的升高而增大。等离子体对束缚电子的屏蔽是决定光谱漂移的主要原因。这些变化规律不仅对等离子体光谱模拟结果产生影响,而且使实验上观测光谱的相对或绝对漂移成为可能,从而为高密度等离子体诊断的新方法提供了理论依据。