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).

Chemiluminescence from reactions with bis-cyclometalated iridium complexes in acidic aqueous solution

Chemical reactions between certain bis-cyclometalated iridium complexes, cerium(IV) and organic reducing agents in aqueous solution produce an emission of light which in some cases is more intense than that from analogous reactions with conventional ruthenium-based reagents, thus providing a new avenue for chemically-initiated luminescence detection.

Emitting species in chemiluminescence reactions with acidic potassium permanganate : a re-evaluation based on new spectroscopic evidence

The reaction of acidic potassium permanganate with a wide range of compounds is known to produce a broad red emission, and there is strong evidence for an excited manganese(II) emitting species. Nevertheless, numerous researchers have proposed other emitters for reactions with acidic potassium permanganate, particularly for systems where fluorescent compounds were present, either as enhancers or reaction products. We have examined many reactions of this type and found that, in most cases, the same red emission was produced. There were, however, some exceptions, including the oxidation of dihydralazine, certain thiols and sulphite (each in the presence of an enhancer).

Precision milled flow-cells for chemiluminescence detection

Novel flow-cells with integrated confluence points and reaction channels designed for efficient mixing of fast chemiluminescence systems were constructed by machining opposing sides of a polymer chip and sealing the channels with transparent epoxy-acetate films. A hole drilled through the chip provided the conduit from the confluence point on one side to the centre of the reaction zone on the other side, allowing rapid presentation of the reacting mixture to the photodetector. The effectiveness of each flow-cell was evaluated by comparing the chemiluminescence intensity using flow injection analysis methodology, and examining the distribution of light emanating from the reaction zone (captured by photography in a dark room) when the reactants were continuously merged. Although previously reported chemiluminescence detectors constructed by machining channels into polymers have almost exclusively been prepared using transparent materials, we obtained far greater emission intensities using an opaque white chip with a thin transparent seal, which minimised the loss of light through surfaces not exposed to the photomultiplier tube. Furthermore, this approach enabled the exploration of reactor designs that could not be incorporated in traditional coiled-tubing flow-cells.

Corrosion of magnesium alloy ZE41 – The role of microstructural features

Magnesium alloy ZE41, used extensively in the aerospace industry, possesses excellent mechanical properties albeit poor corrosion resistance. This paper investigates the mechanism of corrosion and the interaction between the grain boundary intermetallic phases, the Zr-rich regions within the grains and the bulk Mg-rich matrix. The results of optical and scanning electron microscopy (SEM) together with energy-dispersive X-ray (EDX) and atomic force microscopy (AFM) potential map measurements have shown the importance of the microstructure in the initiation and propagation of corrosion in an aqueous environment, indicating that the Zr-rich regions play a distinct role in the early stages of corrosion in this alloy.

The assessment of тт-тт selective stationary phases for two-dimensional HPLC analysis of foods : application to the analysis of coffee

Differences between alkyl, dipole–dipole, hydrogen bonding, and π-π selective surfaces represented by non-resonance and resonance π-stationary phases have been assessed for the separation of ‘Ristretto’ café espresso by employing 2DHPLC techniques with C18 phase selectivity detection. Geometric approach to factor analysis (GAFA) was used to measure the detected peaks (N), spreading angle (β), correlation, practical peak capacity (n_p) and percentage usage of the separations space, as an assessment of selectivity differences between regional quadrants of the two-dimensional separation plane. Although all tested systems were correlated to some degree to the C18 dimension, regional measurement of separation divergence revealed that performance of specific systems was better for certain sample components. The results illustrate that because of the complexity of the ‘real’ sample obtaining a truly orthogonal two-dimensional system for complex samples of natural origin may be practically impossible.

The analysis of café espresso using two-dimensional reversed phase–reversed phase high performance liquid chromatography with UV-absorbance and chemiluminescence detection

In this study, an activity based screening technique combining two-dimensional liquid chromatography (2DHPLC) with UV-absorbance and chemiluminescence detection was applied to study “Ristretto”, "Decaffeinatto” and “Volluto” espresso coffees. This technique, which coupled the separation power of 2DHPLC with the sensitivity and selectivity of the chemiluminescence detection, offers great potential for screening complex samples for antioxidant compounds. Detailed information regarding the complexity of the sample, and the variation between these three coffees could be obtained using this multidimensional-hyphenated method of analysis.

High-performance liquid chromatography with post-column 2,2′-diphenyl-1-picrylhydrazyl radical scavenging assay : methodological considerations and application to complex samples

An improved post-column 2,2´-diphenyl-1-picrylhydrazyl (DPPH•) radical scavenging assay for the screening of antioxidants in complex matrices was developed. Experimental parameters believed to be influential to DPPH• response were studied in a univariate approach. Optimum conditions were found to be: 5×10⁻⁵M DPPH• reagent prepared in a 75% methanol: 25% 40mM citric acid–sodium citrate buffer (pH 6) solution, degassed with nitrogen; reaction coil of 2m×0.25mm i.d. PEEK tubing; detection at 521 nm; analysis at room temperature. The analytical utility of this protocol was evaluated by screening for antioxidants in thyme and green tea, in comparison with two commonly employed methodologies.

Correlation between acidic potassium permanganate chemiluminescence and in vitro cell culture assay : physiologically meaningful antioxidant activity

There is great interest in the activity of antioxidant molecules, including polyphenols, from food and plant sources. Acidic potassium permanganate chemiluminescence signal intensity was shown to predict the ability of polyphenols to positively act on cellular redox state and attenuate oxidative stress in cultured skeletal muscle cells.

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.