Electrochemiluminescent detection based on solid-phase extraction at tris(2,2 '-bipyridyl)ruthenium(II)-modified ceramic carbon electrode

A sensitive electrochemiluminescent detection scheme by solid-phase extraction at Ru(bpy)(3)(2+)-modified ceramic carbon electrodes (CCEs) was developed. The as-prepared Ru(bpy)(3)(2+)-modified CCEs show much better long-term stability than other Nafion-based Ru(bpy)(3)(2+)-modified electrodes and enjoy the inherent advantages of CCEs. The log-log calibration plot for dioxopromethazine is linear from 1.0 x 10(-9) to 1.0 x 10(-4) mol L-1 using the new detection scheme. The detection limit is 6.6 x 10(-10) mol L-1 at a signal-to-noise ratio of 3. The new scheme improves the sensitivity by similar to 3 orders of magnitude, which is the most sensitive Ru(bpy)(3)(2+) ECL method. The scheme allows the detection of dioxopromethazine in a urine sample within 3 min. Since Ru(bpy)(3)(2+) ECL is a powerful technique for determination of numerous amine-containing substances, the new detection scheme holds great promise in measurement of free concentrations, investigation of protein-drug interactions and DNA-drug interactions, pharmaceutical analysis, and so on.

Analysis of nephroloxic and carcinogenic aristolochic acids in Aristolochia plants by capillary electrophoresis with electrochemical detection at a carbon fiber microdisk electrode

Aristolochic acids (AAs) are the main bioactive ingredients in the most of Aristolochia plants, which are used to make dietary supplements, slimming pills and Traditional Chinese Medicines (TCMs). Excessive ingestion of AAs can lead to serious nephropathy. Therefore, quantitative analysis and quality control for the plants containing AAs is of great importance. In this paper, capillary electrophoresis (CE) with electrochemical detection (ED) at a 33 mu m carbon fiber microdisk electrode (CFE) has been applied to detect AA-I and AA-II in Aristolochia plants. Under the optimum conditions: detection potential at 1.20 V, 2.0 x 10(-2) mol L-1 phosphate buffer solution (PBS) (pH 10.0), injection time 25 s at a height of 17 cm and separation voltage at 12.5 kV, the AA-I and AA-II were baseline separated within 5 min. Low detection limits for AA-I and AA-II were 4.0 x 10(-8) mol L-1 and 1.0 x 10(-7) mol L-1, respectively. Wide linear ranges were from 4.0 x 10(-8) mol L-1 to 1.9 x 10(-5) mol L-1 and 1.0 X 10(-7) mol L-1 to 5.0 x 10(-5) mol L-1 for AA-I and AA-II, respectively. The proposed method has been successfully applied to analyze AAs contents in plant extracts. The results indicated that the contents of AAs in each part of Aristolochia debilis Sieb. Et Zucc.

Synthesis and characterization of the biodegradable polycaprolactone-graft-chitosan amphiphilic copolymers

A novel synthetic approach to biodegradable amphiphilic copolymers based on poly (epsilon-caprolactone) (PCL) and chitosan was presented, and the prepared copolymers were used to prepare nanoparticles successfully. The PCL-graft-chitosan copolymers were synthesized by coupling the hydroxyl end-groups on preformed PCL chains and the amino groups present on 6-O-triphenylmethyl chitosan and by removing the protective 6-O-triphenylmethyl groups in acidic aqueous solution. The PCL content in the copolymers can be controlled in the range of 10-90 wt %. The graft copolymers were thoroughly characterized by H-1 NAM, C-13 NMR, FT-IR and DSC. The nanoparticles made from the graft copolymers were investigated by H-1 NMR, DLS, AFM and SEM measurements. It was found that the copolymers could form spherical or elliptic nanoparticles it? water. The amount of available primary amines on the surface of the prepared nanoparticles was evaluated by ninhydrin assail, and it can be controlled by the grafting degree of PCL.

Efficient synthesis of aryl hydroxylactams by reducing imides with activated zinc dust

A series of aryl hydroxylactams (2a, 2b, 2d-2g, 2i-2k, 2m, and 2n) was synthesized by partially reducing aryl cyclic imides in moderate to excellent yields with activated zinc dust alone in acetic acid. This method was regiospecific and can be employed as an alternative for reported methods to partially reduce aryl cyclic imides.

Characterization of Full-Biodegradable Starch-PVA-Polyester Film

IntroductionConventional polymers such as polyethyleneand polypropylene persistfor many years after landdisposal.Furthermore,plastics are often soiled byfood and other biological substances,making phys-ical recycling of those materials impractical andgenerally undesirable. In contrast,biodegradablepolymers disposed in bioactive environment are de-graded by the enzymatic action of microorganismssuch as bacteria,fungi,and algae.The worldwideconsumption of biodegradable polymers increasedfrom1.4×107kg in ...

Direct tris(2,2 '-bipyridyl)ruthenium(II) electrochemiluminescence detection of polyamines separated by capillary electrophoresis

Capillary electrophoresis (CE) with tris(2,2'-bipyridyl) ruthenium (II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) detection technique was developed for the analysis of four polyamines (putrescine (Put), cadaverine (Cad), spermidine (Spd), and spermine (Spm)) analysis. The four polyamines contain different amine groups, which have different ECL activity. There are several parameters which influence the resolution and ECL peak intensities, including the buffer pH and concentrations, separation voltage, sample injection, electrode materials, and Ru(bpy)(3)(2+) concentrations. Polyamines are separated by capillary zone electrophoresis in an uncoated fused-silica capillary (50 cm x 25 mum (ID) filled with acidic phosphate buffer (200 mmol/L phosphate, pH 2.0) - 1 mol/L phosphoric acid (9:1 v/v) and a separation voltage of 5 kV (25 muA), with end-column Ru(bpy)(3)(2+) ECL detection. A 5 mmol/L Ru(bpy)(3)(2+) solution plus 200 mmol/L phosphate buffer (pH 11.0) is added into the reagent reservoir. The calibration curve is linear over a concentration range of two or three orders of magnitude for the polyamines. The analysis time is less than 25 min. Detection limits for Put and Cad are 1.9 x 10(-7) mol/L and 7.6 x 10(-9) mol/L for Spd and Spm, respectively.

New technique for capillary electrophoresis directly coupled with end-column electrochemiluminescence detection

capillary electrophoresis (CE) is characterized. A 300 mum diameter Pt working electrode was used to directly couple with a 75 mum inner diameter separation capillary without an electric field decoupler. The hydrodynamic cyclic voltammogram (CV) of Ru(bpy)(3)(2+) showed that electrophoretic current did not affect the ECL reaction. The presence of high-voltage (HV) field only resulted in the shift of the ECL detection potential. The distance of capillary to electrode was an important parameter for optimizing detection performance as it determined the characteristics of mass transport toward the electrode and the actual concentration of Ru(bpy)(3)(2+) in the detection region. The optimum distance of capillary to electrode was decided by the inner diameter of the capillary, too. For a 75 mum capillary, the working electrode should be placed away from the capillary outlet at a distance within the range of 20-260 mum. The effects of pH value of ECL solution and molecular structure of analytes on peak height and theoretical plate numbers were discussed. Using the 75 mum capillary, under the optimum conditions, the method provided a linear range for tripropylamine (TPA) between 1 x 10(-10) and 1 X 10(-5) mol/L with correlation coefficient of 0.998. The detection limit (signal-to-noise ratio S/N = 3) was 5.0 x 10(-11) mol/L. The relative standard deviation in peak height for eight consecutive injections was 5.6%. By this new technique lidocaine spiked in a urine sample was determined. The method exhibited the linear range for lidocaine from 5.0 x 10(-8) to 1.0 X 10(-5) mol/L with correlation efficient of 0.998. The limit of detection (S/N = 3) was 2.0 x 10(-1) mol/L.

Electrochemiluminescence of tris(2,2 '-bipyridyl)ruthenium (II) ion-exchanged in polyelectrolyte-silica composite thin-films

The organic-inorganic hybrid, PSS-silica composite material was developed for the immobilization of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) on glassy carbon electrode via ion-exchange (PSS stands for poly(sodium 4-styrene-sulfonate)). The electrochemiluminescence (ECL) and electrochemistry of Ru(bpy)(3)(2-) immobilized in the composite thin films have been investigated with tripropylamine (TPA) as the coreactant. The immobilized Ru(bpy)(3)(2-) underwent a surface process. The modified electrode was used for the ECL detection of TPA and showed high sensitivity. Detection limit was 0,1 mumol L-1 for TPA (S/N = 3) with a linear range from 0.5 mumol L-1 to 5 mmol L-1 (R = 0.998), Moreover, the resulting modified electrode was stable over six months and the good stability may be due to the strong interaction between Ru(bpy)(3)(2-) and the high ion-exchange able PSS-silica composite films on GCE. Compared with other materials. the PSS-silica composite films containing incorporated Ru(bpy)(3)(2-) showed improved sensitivity and long-term stability, Thus, such composite thin film can be a promising material for the construction of ECL sensor.

Determination of sulpiride by capillary electrophoresis with end-column electrogenerated chemiluminescence detection

Background: Capillary electrophoresis (CE) with tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)(3)(2+)]-electro-generated chemiluminescence (ECL) detection is a promising method for clinical analysis. In this study, a method combining CE with Ru(bpy)(3)(2+) ECL (CE-ECL) detection that can be applied to amine-containing clinical species was developed, and the performance of CE-ECL as a quantitative method for determination of sulpiride in human plasma or urine was evaluated. Methods: Sulpiride was separated by capillary zone electrophoresis in uncoated fused-silica capillaries [510 cm x 25 mum (i.d.)] filled with phosphate buffer (pH 8.0 and a driving voltage of +15 kV, with end-column Ru(bpy)(3)(2+) ECL detection. A platinum disc electrode was used as working electrode. Sulpiride in human plasma or urine samples (100 muL) was extracted by a double-step liquid-liquid extraction procedure, dried under nitrogen at 35 degreesC in a water bath, and reconstituted with 100 muL of filtered water. The extraction solvent was ethyl acetate-dichloromethane (5:1 by volume). Results: Under optimum conditions (pH 8.0 phosphate buffer, injection for 6 s at 10 kV, and +1.2 V as detection potential), separation of sulpiride was accomplished within 4 min. The calibration curve was linear over a concentration range of 0.05-25.0 mumol/L, and the limit of detection was 2.9 x 10(-8) mol/L for sulpiride. Intra- and interday CVs for ECL intensities were <6%. Extraction recoveries of sulpiride were 95.6-101% with CVs of 2.9-6.0%. The method was,clinically validated for patient plasma and urine samples. Conclusions: CE combined with Ru(bpy)(3)(2+) ECL is reproducible, precise, selective, and enables the analysis of sulpiride in human plasma and urine. It thus is of value for rapid and efficient analysis of amine-containing analytes of clinical interest.

Synthesis and characterization of a novel hybrid single crystal [Ga-3(PO4)(3)F-2]H3O center dot (H3NCH2CH2)(2)NH2

A novel three-dimensional fluorinated gallium phosphate has been hydrothermally,synthesized by using diethylenetriamine as an organic structure-directing agent. X-ray single crystal structure analysis indicates this compound crystallizes in the orthorhombic space group P-bca, a = 1. 605 6 (7) nm, b = 1.011 4 (4) nm, c=1. 854 6(5) nm, V=3. 011 6(19) nm(3), Z=4. The three-dimensional framework based on linkage of corner-sharing polyhedron PO4, GaO4F and GaO4F2 delimit ten-ring channels along b axis in which the triply protonated amines are located serving as charge compensating guests and supporters.

Studies of the ortho effect in fragmentations of acetyl ion adducts of disubstituted benzenes

The ion-molecule reactions of disubstituted benzenes under chemical ionization conditions with acetyl chloride as reagent gas were examined, and the fragmentation reactions of the adduct ions (mostly proton and acetyl ion adducts) were studied by collision-induced dissociation. Electron-releasing substituents favored the adduct reactions, and electron-withdrawing groups did not. The position and properties of substituting groups had an effect on the relative abundances of the adduct ions. Several examples of the ortho effect were observed. The fragmentation reaction of the adduct ions formed by ortho-benzenediamine with the acetyl ion was similar to the reductive alkylation reaction of amines in the condensed phase. Copyright (C) 2001 John Wiley & Sons, Ltd.

Electrochemiluminescent determination of perchlorate by solvent extraction in the presence of Ru(bpy)(3)(2+)

A novel method for the highly sensitive determination of perchlorate was proposed. It was based on solvent extraction in the presence of Ru(bpy)(3)(2+) followed by Ru(bpy)(3)(2+) electrochemiluminescent determination. A linear calibration was obtained over the range of 0.1 to 10 mu mol l(-1) with a correlation coefficient of 0.998. The detection limit (S/N = 3) was 5.0 x 10(-8) mol l(-1). The relative standard deviation for 10 replicates of 1 mu mol l(-1) perchlorate was 1.6%. Interference studies suggest that this method is selective for the determination of perchlorate. Application of this method to the highly sensitive determination of other anions is suggested. (C) 1999 Elsevier Science S.A. All rights reserved.

Effects of heteropoly acids and surfactant on electrochemiluminescence of tris(2,2 '-bipyridine) ruthenium(II)

The effects of heteropoly acids and Triton X-100 on electrochemiluminescence (ECL) of Ru(bpy)(3)(2+) are investigated. Triton X-100 prevents the oxidation of oxalate and results in an increase of the ECL signal. H5SiW11VO40 prevents the direct oxidation of oxalate and makes the electrochemical behavior of Ru(bpy)(3)(2+) less reversible, which leads to a decrease of the ECL signal. In contrast, H3PMo12O40 has negligible effect on ECL intensity. Some possible reasons for the effects on the ECL of Ru(bpy)(3)(2+) are discussed based on the adsorption of SiW11VO405- on electrode surface and the ion association between SiW11VO405- and Ru(bpy)(3)(2+). The signal of ECL decreases linearly with the concentration of heteropoly acid in the range from 2x10-6 to 1x10(-4) mol l(-1). The results indicate that ECL of RU(bpy)(3)(2+) is a potential sensitive and selective detection method for heteropoly acids and hence for the elements comprised in them.

Effect of metal ions on Ru(bpy)(3)(2+) electrochemiluminescence

Ethylenediaminetetraacetate (EDTA) was chosen for the investigation of the effect of metal ions on Ru(bpy)(3)(2+) electrochemiluminescence (ECL). Metal ions that are preferentially bound to the oxygen atoms (MIO) have no effect on the intensity of ECL except for Al3+ and Y3+, whereas metal ions that are preferentially bound to the nitrogen atoms (MIN) preclude the oxidation of EDTA and decrease the ECL intensity.

Combination of amperometric detector & UV detector for capillary electrophoresis

A new electrochemical cell assembly with the combination of UV and amperometric detector (AD) based on their complementarity was described. A Nafion tubing junction was used to decouple the high voltage from the separation capillary in the rear of on-column UV detector. In this mode, the electroactive and inert compounds could be detected by UV and AD at the same time. Aromatic amines were determined with the UV and the end-column AD detection to evaluate the performances of the cell assembly. Such an improved electrochemical detector could match the capillary with different diameters. By simple adjustment of the screws, the positioning of the working electrode and the detection capillary was easily gained without microscope. It is also very easy to assemble and disassemble the working electrode when needed. (C) 1999 Elsevier Science B.V. All rights reserved.