Chemiluminescence from the reaction of tin(II) with tris(2,2'-bipyridyl)ruthenium(III)

Unlike many other metal and metalloid ions, tin(II) elicits intense, analytically useful chemiluminescence upon reaction with tris(2,2΄-bipyridyl)ruthenium(III) in acidic aqueous solution. This finding provides new insight into the nature of this widely used reagent and has enabled the first direct, selective determination of a metal ion with tris(2,2΄-bipyridyl)ruthenium(III).

A study of acid/base treatments of polypyrrole films using 13C n.m.r. spectroscopy

Electrodeposited polypyrrole films prepared with paratoluenesulfonate (pTS), dodecylsulfate (DDS) and perchlorate anions were treated with acidic and basic solutions, and their structure was investigated by 13C solid state n.m.r. spectroscopy. This technique has confirmed that pTS is completely removed from the film in both acidic and basic solutions whilst DDS is only partially removed and tends to decompose upon treatment with H2SO4. The appearance of shoulders at 143 ppm upon treatment with 0.5 M base indicates formation of a quinoid pyrrole structure. Substitution on the β-carbon by OH cannot be confirmed from the present spectra. Stronger base causes a more dramatic change in the polypyrrole backbone with an obvious increase in the electron density on the β-carbons, consistent with the reduction of the carbon backbone. There is no indication of quinoid units in this case. Acid treatments result in considerable broadening of the main 127 ppm polypyrrole peak.

Partial least squares and principal components analysis of wine vintage by high performance liquid chromatography with chemiluminescence detection

HPLC with acidic potassium permanganate chemiluminescence detection was employed to analyse 17 Cabernet Sauvignon wines across a range of vintages (1971–2003). Partial least squares regression analysis and principal components analysis was used in order to investigate the relationship between wine composition and vintage. Tartaric acid, vanillic acid, catechin, sinapic acid, ethyl gallate, myricetin, procyanadin B and resveratrol were found to be important components in terms of differences between the vintages.

High performance liquid chromatography with two simultaneous on-line antioxidant assays : evaluation and comparison of espresso coffees

The antioxidant profiles of various espresso coffees were established using HPLC with UV-absorbance detection and two rapid, simultaneous, on-line chemical assays that enabled the relative reactivity of sample components to be screened. The assays were based on (i) the colour change associated with reduction of the 2,2´-diphenyl-1-picrylhydrazyl radical (DPPH•); and (ii) the emission of light (chemiluminescence) upon reaction with acidic potassium permanganate. Results from the two approaches were similar and reflected the complex array of antioxidant species present in the samples. However, some differences in selectivity were observed. Chromatograms generated with the chemiluminescence assay contained more peaks, which was ascribed to the greater sensitivity of the reagent towards minor, readily oxidisable sample components. The three coffee samples produced closely related profiles, signifying their fundamentally similar chemical compositions and origin. Nevertheless, the overall intensity and complexity of the samples in both UV absorption and antioxidant assay chromatograms were aligned with the manufacturers description of flavour intensity and character.

Autocatalytic nature of permanganate oxidations exploited for highly sensitive chemiluminescence detection

Manganese(II) salts catalyze the chemiluminescent oxidation of organic compounds with acidic potassium permanganate. The formation of insoluble manganese(IV) species from the reaction between manganese(II) and permanganate can be prevented with sodium polyphosphate, and therefore, relatively high concentrations of the catalyst can be added to the reagent before the lightproducing reaction is initiated. The rapid and intense emissions from these manganese(II) catalyzed chemiluminescence reactions provide highly sensitive detection and greater compatibility with liquid chromatography.

Mechanism of permanganate chemiluminescence

Spectroscopic and synthetic methods have been exploited to deduce the mechanism for acidic potassium permanganate chemiluminescence. We have employed electron paramagnetic resonance (EPR) spectroscopy with a continuous flow assembly to monitor the formation of radical intermediates in real time generated from substrate oxidation by manganese(VII). These transient species react with manganese(III) in solution to produce the  previously characterized manganese(II)* emission source. Using UV-vis, EPR, attenuated total reflection (ATR)-FTIR, and chemiluminescence spectroscopies, we have established that there are two distinct enhancement mechanisms that in combination afford a 50-fold increase in emission intensity when the reaction is conducted in the presence of phosphate oligomers. In addition to preventing disproportionation of the manganese(III) precursor, the phosphate oligomers form protective "cagelike” structures around the manganese(II)* emitter, thus preventing nonradiative relaxation pathways.

An investigation of polypyrrole coated conductive textiles: this research aimed at clarifying some issues occurred in the research project on coloured conductive textiles

Coloured conducting textiles have shown a wide range of potential applications in heating fabrics, electromagnetic wave absorption, and wearable optoelectronic devices. This research aimed at clarifying some issues occurred in the research project on coloured conductive textiles. The investigation firstly clarified a possible chemical reaction that took place between a commercial dispersing dye (Terasil Red G) and the conducting polymer polypyrrole, through chemical separation, structural identification and spectrum characterisations. Then, a series of acidic dyes were introduced into polypyrrole matrix during the vapour coating of conducting polymer on the wool fabrics. Colour and thermal stability studies were conducted. Finally, the polypyrrole nanoparticles (particle size several~200nm) were prepared by a microemulsion polymerisation technique. An acid dye was used as the dopant to re-dope the nanoparticles. The effect of the acidic dye on the optical absorption of nanoparticles was studied. Applying the conducting nanoparticles on wool fabrics may open an alternative path to achieve the coloured conducting textiles.

Immobilized artificial membrane chromatography : quantitative structure-retention relationships of structurally diverse drugs

The chromatographic capacity factors (log k‘) for 32 structurally diverse drugs were determined by high performance liquid chromatography (HPLC) on a stationary phase composed of phospholipids, the so-called immobilized artificial membrane (IAM). In addition, quantitative structure-retention relationships (QSRR) were developed in order to explain the dependence of retention on the chemical structure of the neutral, acidic, and basic drugs considered in this study. The obtained retention data were modeled by means of multiple regression analysis (MLR) and partial least squares (PLS) techniques. The structures of the compounds under study were characterized by means of calculated physicochemical properties and several nonempirical descriptors. For the carboxylic compounds included in the analysis, the obtained results suggest that the IAM-retention is governed by hydrophobicity factors followed by electronic effects due to polarizability in second place. Further, from the analysis of the results obtained of two developed quantitative structure-permeability studies for 20 miscellaneous carboxylic compounds, it may be concluded that the balance between polarizability and hydrophobic effects is not the same toward IAM phases and biological membranes. These results suggest that the IAM phases could not be a suitable model in assessing the acid-membrane interactions. However, it is not possible to generalize this observation, and further work in this area needs to be done to obtain a full understanding of the partitioning of carboxylic compounds in biological membranes. For the non-carboxylic compounds included in the analysis, this work shows that the hydrophobic factors are of prime importance for the IAM-retention of these compounds, while the specific polar interactions, such as electron pair donor−acceptor interactions and electrostatic interactions, are also involved, but they are not dominant.

Evidence of changes in membrane pore characteristics due to filtration of dye bath liquors

This study was carried out to investigate the treatment of various salt solutions and synthetic dye bath liquors by nanofiltration using Nanomax-50 membrane in a stirred cell with 150 mL working volume. Donnan exclusion was compared by filtering salts with monovalent and divalent cations and anions. This was done by comparing three salts including sodium chloride (NaCl), calcium chloride (CaCl2) and sodium sulphate (Na2SO4). The rejection order determined was Na2SO4>NaCl>CaCl2 which is typical of a negatively charged membrane where Donnan and steric exclusion play an important role in separation. Studies on the flux and rejection characteristics of sodium sulphate were undertaken for concentrations ranging from 10 to 40 gl−1 thereby replicating actual dye bath salt concentrations. Synthetic dye bath liquors were prepared using acidic dye (Acid Green 25) at a fixed concentration of 100 mgl−1 with 10 and 15 gl−1 of sodium sulphate solutions. While, the results showed evidence of flux decline due to increased resistance and decreased transmembrane pressure, pore enlargement occurred after the filtration experiments with sodium sulphate solutions greater than 20 gl−1. Pore enlargement was even more prominent in the two synthetic dye bath liquors filtered. Pore enlargement was determined by observing the pure water flux before and after filtering sodium sulphate solutions or dye bath liquors. An increase in pore diameter of 58 and 94 %was estimated when dye bath liquors containing 10 and 15 gl−1 of sodium sulphate, respectively were filtered through the membrane. The following equation was derived in estimating the pore enlargement, where de1 and de2 are the apparent diameter of membrane pore sizes before and after filtration of salt solutions or dye bath liquors and Rm1 and Rm2 are the membrane resistance of pure water flux before and after filtration of salt solutions or dye bath liquors. These results have important implications for the application of nanofiltration technology to textile wastewater treatment and reuse.

Extraction of silver(i) from aqueous solutions in the absence and presence of copper(ii) with a methimazole-based ionic liquid

The ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf₂], facilitates the efficient extraction of silver(i) from aqueous media via interaction with both the cation and anion components of the IL. Studies with a conventional aqueous-IL two phase system as well as microextraction of silver(i) by a thick IL film adhered to an electrode monitored in situ by cyclic voltammetry, established that [mimSBu][NTf₂] can extract electroactive silver(i) ions from an aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu]⁺, which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of silver(i) further increase the acidity of the aqueous phase as a consequence of coordination with the IL cation component. Voltammetric and ¹H and ¹³C NMR techniques have been used to establish the nature of the silver(i) complexes extracted, and show that the form of interaction with the IL differs from that outlined previously for the extraction of copper(ii). Insights on the competition established when silver(i) is extracted in the presence of copper(ii) are provided. Finally, it is noted that metallic silver can be directly electrodeposited at the electrode surface after extraction of silver(i) into [mimSBu][NTf₂] and that back extraction of silver(i) into aqueous media is achieved by addition of an acidic aqueous solution.

Contact electrification induced by monolayer modification of a surface and relation to acid-base interactions

Electrical charge separation following contact between two materials (contact electrification or the triboelectric effect) is well known to occur between different materials as a consequence of their different electronic structures. Here we show that the phenomenon occurs between two surfaces of the same material if one is coated with a single chemisorbed monolayer. We use the surface force apparatus to study contact electrification and adhesion between two silica surfaces, one coated with an amino-silane. The presence of this monolayer results in significantly enhanced adhesion between the surfaces, owing to electrostatic attraction following contact electrification, in accord with Derjaguin's electrostatic theory of adhesion. At the same time, the observed increase in adhesion is consistent with Fowkes' acid-base model (in which acid-base interactions between surface groups are considered to be the predominant factor determining adhesion), as the monolayer converts the originally acidic silica surface to a basic (amine-terminated) one. These observations demonstrate a link between acid- base interactions and contact electrification.

Electrical charge separation following contact between two materials (contact electrification or the triboelectric effect) is well known to occur between different materials as a consequence of their different electronic structures. Here we show that the phenomenon occurs between two surfaces of the same material if one is coated with a single chemisorbed monolayer. We use the surface force apparatus to study contact electrification and adhesion between two silica surfaces, one coated with an amino-silane. The presence of this monolayer results in significantly enhanced adhesion between the surfaces, owing to electrostatic attraction following contact electrification, in accord with Derjaguin's electrostatic theory of adhesion. At the same time, the observed increase in adhesion is consistent with Fowkes' acid-base model (in which acid-base interactions between surface groups are considered to be the predominant factor determining adhesion), as the monolayer converts the originally acidic silica surface to a basic (amine-terminated) one. These observations demonstrate a link between acid-base interactions and contact electrification.

Effects of exercise on the isoelectric patterns of erythropoietin

Objectives: Recombinant erythropoietin has a strong impact on aerobic power and is therefore one of the most potent doping agents in endurance sports. The anti-doping control of this synthetic hormone relies on the detection, in the urine, of its isoelectric pattern, which differs from that of the corresponding natural hormone, the latter being typically more acidic than the former. However, a small number of natural urinary patterns, referred to as atypical patterns, are less acidic than the dominant form. Based on anecdotal evidence, the occurrence of such patterns seems to be related to particular strenuous exercises. This study aimed to demonstrate this relation using a strenuous exercise protocol.

Design: Seven athletes took part in a training protocol including a series of supramaximal short-duration exercises. Urine and blood samples were collected throughout the protocols.

Settings: World Cycling Center, Aigle, Switzerland, and research laboratories.

Participants: Seven top-level athletes (cyclists) were involved in this study.

Main Outcome Measures: Erythropoietin (EPO) isoelectric patterns were obtained by submitting blood and urine samples to isoelectric focusing. Additional protein dosages were performed.

Results: Supramaximal short-duration exercises induced the transformation of typical urinary natural EPO patterns into atypical ones. None of the obtained atypical patterns fulfilled the 3 criteria mandatory for reporting an adverse analytical finding. Serum EPO patterns were not affected by the exercises that caused the transformation of urinary patterns.

Conclusion: An exercise-induced transient renal dysfunction is proposed as a hypothetic explanation for these observations that rely on parallel investigations of proteinuria in the same samples.

Chemiluminescence detection flow cells for flow injection analysis and high-performance liquid chromatography

We have examined a range of new and previously described flow cells for chemiluminescence detection. The reactions of acidic potassium permanganate with morphine and amoxicillin were used as model systems representing the many fast chemiluminescence reactions between oxidising agents and organic analytes, and the preliminary partial reduction of the reagent was exploited to further increase the rates of reaction. The comparison was then extended to high-performance liquid chromatography separations of α- and β-adrenergic agonists, with permanganate chemiluminescence detection. Flow cells constructed by machining novel channel designs into white polymer materials (sealed with transparent films or plates) have enabled improvements in mixing efficiency and overall transmission of light to the photodetector.

Effect of vascular endothelial growth factor upregulation on retinal gene expression in the Kimba mouse

Background:  The Kimba mouse carries a human vascular endothelial growth factor transgene causing retinal neovascularisation similar to that seen in diabetic retinopathy. Here, we examine the relationship between differential gene expression induced by vascular endothelial growth factor overexpression and the architectural changes that occur in the retinae of these mice.

Methods:  Retinal gene expression changes in juvenile and adult Kimba mice were assayed by microarray and compared with age-matched wild-type littermates. Transcription of selected genes was validated by quantitative real-time polymerase chain reaction. Protein translation was determined using immunohistochemistry and enzyme-linked immunosorbent assay.

Results:  Semaphorin 3C was upregulated, and nuclear receptor subfamily 2, group 3, member 3 (Nr2e3) was downregulated in juvenile Kimba mice. Betacellulin and endothelin 2 were upregulated in adults. Semaphorin 3C colocalized with glial fibrillary acidic protein in Müller cells of Kimba retinae at greater signal intensities than in wild type. Endothelin 2 colocalised to Müller cell end feet and extended into the outer limiting membrane. Endothelin receptor type B staining was most pronounced in the inner nuclear layer, the region containing Müller cell somata.

Conclusions:  An early spike in vascular endothelial growth factor induced significant long-term retinal neovascularisation associated with changes to the retinal ganglion, photoreceptor and Müller cells. Overexpression of vascular endothelial growth factor led to dysregulation of photoreceptor metabolism through differential expression of Nr2e3, endothelin 2, betacellulin and semaphorin 3C. Alterations in the expression of these genes may therefore play key roles in the pathological mechanisms that result from retinal neovascularisation.

Comparative study on MoO3 and HxMoO3 nanobelts : structure and electric transport

In this study, the suspension of MoO3 nanobelts was first prepared in a hydrothermal way from Mo powders and H2O2 solution, which could be transformed into the suspension of HxMoO3 nanobelts under an acidic condition using N2H4 ·H2O as the reducing agent. Three paper-form samples made from MoO3 and HxMoO3 nanobelts (low or high hydrogen content) were then fabricated via a vacuum filtration method, followed by their structural comparative analysis such as FESEM, XRD, Raman spectra, and XPS, etc. The measurement of electric resistances at room temperature shows that the conductance of HxMoO3 nanobelts is greatly improved because of hydrogen doping. The temperature-dependent resistances of HxMoO3 nanobelts agree with the exponential correlation, supporting that the conducting carriers are the quasi-free electrons released from Mo5+. In addition, the formation process of HxMoO3 nanobelts from MoO3 nanobelts is also discussed.