Determination of carbaryl by flow injection with luminol chemiluminescence inhibition detection

A flow-injection procedure is described for the determination of carbaryl based on its inhibition effect on luminol-cobalt(II) chemiluminescence reaction in alkaline medium in the presence of hydrogen peroxide. The calibration data over the range 5.0?×?10^?7 to 20?×?10^?6?M give a correlation coefficient (r ²) of 0.9972 with relative standard deviations (RSD; n?=?4) in the range of 1.0–2.1% with a limit of detection (3?×?blank noise) of 2.37?×?10^?7?M for carbaryl. The sample throughput was 120?h^?1. The effects of some carbamates, anions, and cations were studied on luminol CL system for carbaryl determination. The proposed method has been applied to determine carbaryl in natural waters.     

A stable chemiluminophore,adamantylideneadamantane 1,2-dioxetane: from fundamental properties to utilities in mechanochemistry and soft crystal science

Chemiluminescence (CL) is a luminescence phenomenon originated by a “chemical reaction.” CL provides a basis for real-time imaging technology in materials science. In fact, a CL reaction is easily triggered in general and makes it possible to track its progress in a target material by highly sensitive photon detection. Recently, real-time CL imagings became breakthrough techniques for analyzing the molecular mechanisms of failures of polymeric materials and of reactions and phase transitions in soft crystals. In the CL imaging techniques, adamantylideneadamantane 1,2-dioxetane (Adox) has been adopted as a stable core structure of chemiluminophores. That is, Adox is an essential seed compound to design a chemiluminophore with a desired molecular function. To support developments of real-time CL imaging techniques, we review the chemistry of Adox as a representative stable chemiluminophore including scientific history and utilities of Adox and its derivatives.     

Native vs photoinduced chemiluminescence in dimethoate determination

The determination of dimethoate using either its native chemiluminescent (CL) properties or its photoinduced chemiluminescence obtained by irradiation with a 15 W low-pressure mercury lamp was studied. Thereby, two flow injection systems (FIA) with and without irradiation were exhaustively optimized and their analytical characteristics studied. Better sensitivity and selectivity was found in absence of irradiation, due to the enhancing effect of hexadecylpyridinium chloride (HPC), which acted as a sensitizer. In the developed FIA-CL system, the alkaline hydrolysis of dimethoate with NaOH was performed on-line in presence of HPC. The oxidation of the product of hydrolysis with Ce(IV) in hydrochloric medium induced chemiluminescence. The method provided a limit of detection of only 0.05 ng mL⁻¹ without any pre-treatment. However, the combination with solid phase extraction allowed the removal of some potential interferents as well as the preconcentration of the pesticide. Finally, the developed method was successfully applied to natural waters with recoveries between 95 and 108%.     

Nylon and nylon blend nanotubes and nanorods

Nylon nanorods and nanotubes (200 nm diameter) were fabricated by the membrane wetting technique (solvent and melt wetting) from a range of nylons (6; 6,6; 6,9; 6,10; 6,12; 11; 12, 6(3)T) and nylon blended with different dyes (Nylon Cast Blue, Nylon 6/6 Black) or with molybdenum disulfide (Nylon cast MDS). The 65-μm long nylon nanotubes and nanorods were characterized by scanning electron microscopy. The nanoscale nylon 6,6 served as an effective high surface area alternative to a nylon membrane as a solid support in a chemiluminescent assay for nylon-bound biotinylated nucleic acids based on streptavidin- alkaline phosphatase and chemiluminescent detection of the bound alkaline phosphatase label with the dioxetane substrate, CDP-Star. Layer-by-layer deposition of the cationic polymer (Sapphire-II™; Tropix) onto the nylon 6,6 nanostructures prior to UV-cross-linking with biotinylated DNA resulted in further enhancement of binding and detection of biotinylated DNA.     

Chemiluminescence determination of antibacterial drug trimethoprim by automated sequential injection technique with permanganate and hexametaphosphate as reagents

Antibacterial drug trimethoprim [2,4-diamino-5-(3,4,5-trimethoxybenzyl)-pyrimidine] (I) was determined in pharmaceutical formulations by using a lab-made PC-controlled SIA analyser linked to conventional HPLC fluorimetric detector equipped with a chemiluminescence module. The chemical principle is the oxidation of I by KMnO(4) in acid medium; the reaction is accompanied by the emission of chemiluminescence, which is enhanced in the presence of hexametaphosphate (HMP). The optimum sequence and the flow parameters and concentrations and volumes of reagents aspirated optimised by a computer-aided simplex method were, 100 mul of 5 mM HMP, 40 mul of a test solution of I, 2 mul of 0.5 M H(2)SO(4) and 20 mul of 1 mM KMnO(4); the luminescing zone was pushed into the detector at a flow rate of 49 mul s(-1). The calibration graph relating the intensity of luminescence to concentration of I was parabolic (r=0.9994) in the range 0.5-100 mug ml(-1) of I with rectilinear part (r=0.9999) in the range 20-100 mug ml(-1) of I; the limit of detection was 0.1 mug ml(-1) of I. The method was used for the assay of Triprim(R) tablets (with nominal content 100 or 200 mg of I) for the active substance as well as for content uniformity tests; the R.S.D. values did not exceed 1% (n=5). The SIA results did not show statistical difference from those obtained by pharmacopoeial acidimetric titration in non-aqueous medium; the excipients such as microcrystalline cellulose, maze starch, povidone, talc, magnesium stearate and gelatin did not interfere.     

Chemiluminescence detection of superoxide anion release and superoxide dismutase activity: modulation effect of<Emphasis Type="Italic"> Pulsatilla chinensis</Emphasis>

A novel flow-injection chemiluminescence-based method has been developed for determination of superoxide dismutase (SOD) activity. An in-vitro superoxide anion generation xanthine/xanthine oxidase stable source was established on line with FIA/CL-detection apparatus, for measuring SOD activity. This method can detect SOD in the linear range of 0.002–2.00 U mL^–1 with a detection limit of 0.001 U mL^–1. Another method for detection of superoxide anion is based on the luminol–FeCl₃ chemiluminescence (CL) reaction. This method was used to evaluate superoxide release and SOD activity in rats treated with the traditional Chinese herb Pulsatilla chinensis, which resulted in high clearance of hepatitis B virus (HBV) after treatment of a hepatitis B patient. Interestingly, we found that treatment with Pulsatilla chinensis can specifically increase superoxide release by liver tissues and, at the same time, slightly increase extracellular SOD (ECSOD) activity in plasma; in particular it can markedly increase MnSOD activity in mitochondria in liver tissue. This work revealed a possible mechanism whereby Pulsatilla chinensis prevents possible infection (for example HBV) by specifically increasing superoxide release in the liver and increasing MnSOD activity to minimize superoxide-mediated toxicity.     

Chemiluminescence microfluidic system sensor on a chip for determination of glucose in human serum with immobilized reagents

A chemiluminescence (CL) biosensor on a chip coupled to microfluidic system is described in this paper. The CL biosensor measured 25×45×5 mm in dimension, was readily produced in analytical laboratory. Glucose oxidase (GOD) was immobilized onto controlled-pore glass (CPG) via glutaraldehyde activation and packed into a reservoir. The analytical reagents, including luminol and ferricyanide, were electrostatically co-immobilized on an anion-exchange resin. The most characteristic of the biosensor was to introduce the air as the carrier flow in stead of the common solution carrier for the first. The glucose was sensed by the CL reaction between hydrogen peroxide produced from the enzymatic reaction and CL reagents, which were released from the anion-exchange resin. The proposed method has been successfully applied to the determination of glucose in human serum. The linear range of the glucose concentration was 1.1-110 mM and the detection limit was 0.1 mM (3σ).     

Dialysis membrane sampler for on-line flow injection analysis/chemiluminescence-detection of peroxynitrite in biological samples

Peroxynitrite, as a derivative of nitric oxide, is a potent oxidant. It reacts with several biological molecules, makes cellular and tissue damages, and is related with many diseases; therefore, it is of major concern in current medical research works. In this work, a special perm-selective cellulose acetate membrane sampler is used to implement flow injection analysis (FIA)/chemiluminscence (CL)-detection method for the detection of peroxynitrite with Luminol CL-reagent. Optimum detection conditions were established, and the permeability of peroxynitrite through cellulose acetate (CA) membrane, as well as the interference from matrix constituents were studied. The proposed method has the high sensitivity of the CL-detection and the selectivity of perm-selective membrane sampler. The obtained detection limit of 1×10⁻¹¹ M (without dialysis membrane) and 1×10⁻¹⁰ M (with dialysis membrane), makes it possible to monitor the elusive peroxynitrite in biological samples. The mechanism of luminol CL-emission generated during oxidation by peroxynitrite and the kinetics of peroxynitrite decomposition were also studied using FIA/CL-detection set-up.     

三唑磷-鲁米诺-H2O2发光体系的研究与应用

研究了碱性介质中三唑磷-鲁米诺-H2O2体系的化学发光特征,建立了三唑磷流动注射化学发光分析方法,并对反应机理进行了探讨.研究了三唑磷-鲁米诺-H2O2体系的化学发光反应动力学,考察了pH、流速、鲁米诺-H2O2配比等因素对化学发光的影响.在最佳条件下,过氧化氢HOO-负离子可能与三唑磷的磷原子反应生成磷的过氧化合自由基,与鲁米诺作用使得体系化学发光得到增强,3s内达到了最大值;应用于三唑磷的测定,在1.0×10-8-1.0×10-5g/mL范围内呈良好的线性关系,检出限(S/N=3)为6.7×10-9g/mL;测定蔬菜样品,三唑磷浓度分别为1.0-5.0μg/mL时,测定回收率为82.3%-108.6%,测定偏差为1.6%-4.7%.     

光泽精与钨（Ⅲ）的流动注射－胶束增敏化学发光反应

采用了Jones柱在线还原钨（Ⅵ）为钨（Ⅲ），详细研究了钨（Ⅲ）与光泽精的化学发光反应，加入乳化剂OP能明显提高发光的信噪比，基于此建立了痕量钨的流动注射化学发光分析法。该法线性范围为1×10－6～1×10－2 g·L－1, 检出限为5×10－7 g·L－1 , 相对标准偏差为2.0％（5×10－5 g·L－1, n=11）。文中还探讨了反应机理。