钴-锌试剂络合吸附伏安法测定中草药中钴

研究了测定痕量钴的一种灵敏的吸附伏安法 ,利用钴和锌试剂络合物在悬汞电极上的吸附性 ,有效地提高了分析的灵敏度。在 0 .0 0 5mol·L-1NH3 和 0 .0 6mol·L-1NH4Cl及 2 .5× 1 0 -6mol·L-1锌试剂底液条件下 ,该体系 1 .5 ,2 .5阶微分吸附伏安法测定钴的线性范围为 1× 1 0 -10 ～ 1× 1 0 -7mol·L-1,用 2 .5阶微分吸附伏安法 ,富集 3min的检出限为 5× 1 0 -11mol·L-1。用此法直接测定了中草药中痕量钴     

苯巴比妥的二次微分简易示波伏安法测定

利用苯巴比妥的示波特性 ,分别建立了在0.2mol/LKOH和1.0×10-4mol/LCd2 +-0.1mol/L硼砂底液中直接和间接测定苯巴比妥的二次微分简易示波伏安法 ;直接测定和间接测定的线性范围分别为1.0×10 -5mol/L～1.0×10 -4mol/L和4.0×10 -6mol/L～8.0×10 -5mol/L ;检出限分别为8×10 -6mol/L和2×10 -6mol/L;在直接测定中 ,对6.000×10 -5mol/L苯巴比妥进行10次测定的RSD为4.5 % ;间接测定中 ,对2.000×10 -5mol/L苯巴比妥进行10次测定的RSD为2.6 % ;这一研究表明对于一些在示波分析中灵敏度不高或本身没有示波活性的药物 ,可以利用其与金属离子生成沉淀的方法间接测定 ,从而提高药物测定的灵敏度、拓宽示波分析应用领域     

Simultaneous Determination of Platinum and Rhodium with Hydroxylamine and Acetone Oxime by Catalytic Adsorptive Stripping Voltammetry (CAdSV)

This paper describes a very sensitive catalytic adsorptive stripping voltammetry (CAdSV) procedure for the simultaneous determination of traces of platinum and rhodium in new supporting electrolyte containing hydroxylamine or acetone oxime and formaldehyde in sulfuric acid medium. Platinum and rhodium were pre‐accumulated simultaneously and after 120 s of accumulation time at 0.0 V, the achieved detection limits were equal 0.1 ng L^?1 and 0.2 ng L^?1 for platinum and rhodium respectively in the presence of acetone oxime and 0.6 ng L^?1 and 0.2 ng L^?1 for platinum and rhodium respectively in the presence of hydroxylamine. Described reagents were successfully applied to the determination of platinum and rhodium in plant material. Inductively coupled plasma mass spectrometry (ICP MS) was used as a reference method to the CAdSV measurements.     

碳糊电极阳极吸附伏安法测定大黄酸

在pH4.2的HAc-NaAc底液中,大黄酸在碳糊电极(CPE)上有一灵敏的吸附氧化峰,峰电位为1.14V(vs.SCE)。该氧化峰的二阶导数峰电流与大黄酸的浓度在8.0×10-9~8.0×10-7mol/L(富集120s)范围内呈良好的线性关系(r=0.998),检出限为2×10-9mol/L(S/N=3,富集180s)。探讨了大黄酸在CPE上的伏安性质和电极反应机理,并将本法应用于中药大黄中的大黄酸的测定,结果良好。     

Some chemical transformations of the neo-clerodane diterpene teubotrin

Starting from the natural neo-clerodane diterpenoid teubotrin (1) several neo-clerodane derivatives (3-7,9-11) have been obtained. The naturally occurring diterpenoid teuscordinon (12) has also been synthesized from teubotrin (1), showing thereby how some of these transformations can be useful for the synthesis of other natural neo-clerodane diterpenes. The latter are of interest due to their activity as insect antifeedants and other important biological properties.     

Integrated Microanalytical System Coupling Permeation Liquid Membrane and Voltammetry for Trace Metal Speciation. Technical Description and Optimization

A new minicell coupling the liquid‐liquid extraction technique called permeation liquid membrane (PLM) with an integrated Ir‐based Hg‐plated microelectrode array for voltammetric detection has been developed for the speciation of heavy metals in natural waters. Lead and cadmium have been used as model compounds. The PLM consists of a carrier (0.1 M 22DD+0.1 M lauric acid) dissolved in 1 : 1 mixture of toluene/phenylhexane held in the small pores (30 nm) of a hydrophobic polypropylene membrane (Celgard 2500). One side of this membrane is in contact with a flowing source solution, containing the metal ions of interest. An acceptor or strip solution (pyrophosphate) is placed on the other side of the PLM with the microelectrode array placed at 480 μm of the PLM. The analyte is transported by the carrier from the source solution to the strip solution. The originality of the new minicell is that accumulation in the strip solution is voltammetrically followed by the integrated microelectrode array in real time, and at low concentration level, using square‐wave anodic stripping voltammetry (SWASV). In order to protect the Hg microelectrodes from the adsorption of the hydrophobic carrier, the microelectrodes are embedded in a thin gel layer (280 μm) of 1.5% LGL agarose gel containing 10% of hydrophobic silica particles C18. The choice of optimum conditions is discussed in details in this article. Due to the very small effective strip volume of the new cell (less than 1 μL), high enrichment factor can be obtained (e.g., 330 for Pb) after 2 hours of accumulation. No deaeration of the solutions is required for SWASV measurements. Detection limits under these conditions are 2 pM and 75 pM for Pb and Cd, respectively, using a voltammetric deposition time of 5 min. In addition, no fouling effects were observed with natural water samples.     

Oxidation of theexo- andendo-phenylcyclohexadienyl iron complexes Fe(η5-6-PhC6H6) (η5- C5H5)

The roe of oxidatively induced homolyhc scission a the C(sp³)-H bonds in the iron phenykychhexadienyl complexes Fe(⁵-6-PhC₆H₆)(⁵-C₅H₅) (1) depends on the spatial orientation of the Ph substitutent. In the case of the (1 _endo ⁺) radical cation this process, resulting in the cationic biphenyl complex (Fe(⁶ -C₆H₅C₆H₅)(⁵-C₅H₅)]⁺ (2 ⁺), is fast and proceeds for several minutes. In the case of the more stable radical cation (1 _exo ⁺) the formation of 2⁺ is slow and takes tens minutes to complete.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1698–1700, July, 1996.     

Study on the anodic reaction of Ni in an alkaline solution by transient pH detection based on scanning electrochemical microscopy (SECM)

The anodic reaction of Ni in an alkaline solution was studied by the tip–substrate voltammetry mode of scanning electrochemical microscopy (SECM) and cyclic voltammetry (CV). A platinum microdisc electrode was selected as the tip electrode, which functioned as a pH sensor with transient response capability. The pH value of the solution near the Ni electrode surface varied while the Ni substrate oxidation reaction occurred, and the pH variation could be detected by the tip faradic current. The cyclic voltammogram results showed that two types of hydroxides: i.e. α‐Ni(OH)₂ and β‐Ni(OH)₂ were formed during Ni oxidation in the lower potential region. In the proceedings of α‐Ni(OH)₂ → γ‐NiOOH and β‐Ni(OH)₂ → β‐NiOOH, the process of OH^? concentration decrease in the solution was ahead and behind of electron transfer in the solid phase, respectively. These results indicate that the OH^? adsorption process occurs as an elementary step in the former reaction and the H⁺ diffusion process from the inner to the outer layer of the solid phase occurs as a subsequent step in the latter reaction. The results also revealed that the oxide film on the Ni surface has a two‐layer structure. The real potential of the oxygen evolution reaction (OER) on the Ni surface with different cycles is also analyzed in the paper. Copyright © 2007 John Wiley & Sons, Ltd.     

Studies on the Electrochemical Characteristics of K2FeO4 Electrode

Discharge performance of K2FeO4 electrode under different conditions was studied by the constant electric current discharge method. The electrochemical characteristics of K2FeO4 electrode were investigated for the first time by means of cyclic voltammetry. The results show that the K2FeO4 electrode made at moderate pressure (20MPa) and discharged at lower current has better discharge performance. It is also found that K2FeO4 electrode is significantly rechargeable.     

PAMAM Dendrimers as Anchors for the Preparation of Electrocatalytically Active Ultrathin Metallic Films

This paper describes the formation of catalytically active thin films of Pt, Pt/Au, and Pt/Ru on gold substrates stabilized by amine‐terminated polyamidoamine (PAMAM) dendrimers. A monolayer of dendrimer is initially self‐assembled on the gold substrate, which serves as a template for the growth of catalytically active thin films. As dendrimers contain tens to hundreds of functional groups at the periphery, the aggregate strength of the multidentate interactions with the gold substrate leads to the formation of robust films. The films were found to exhibit high catalytic activity for the oxidation of small hydrocarbons such as methanol. Such films offer versatility and scope for the design of effective electrocatalysts, especially in the context of microfuel cells and “dendrichips”; hence, they could find applications in the fields of sensors, fuel cells, and waste‐water treatment.