Ethanol as an alternative to formaldehyde for the enhancement of manganese(IV) chemiluminescence detection.

Previous applications of manganese(IV) as a chemiluminescence reagent have required the use of formaldehyde to enhance the emission intensity to analytically useful levels. However, this known human carcinogen (by inhalation) is not ideal for routine application. A wide range of alternative enhancers have been examined but to date none have been found to provide the dramatic increase in chemiluminescence intensities obtained using formaldehyde. Herein, we demonstrate that ethanol offers a simple, safe and inexpensive alternative to the use of formaldehyde for manganese(IV) chemiluminescence detection, without compromising signal intensity or sensitivity. For example, chemiluminescence signals for opiate alkaloids using 50-100% ethanol were 0.8-1.6-fold those using 2M formaldehyde. This innocuous alternative enhancer is shown to be a particularly effective for the direct detection of thiols and disulfides by manganese(IV) chemiluminescence, which we have applied to a simple HPLC procedure to determine a series of biomarkers of oxidative stress.

Acidic potassium permanganate as a chemiluminescence reagent – a review

A critical and comprehensive review of acidic potassium permanganate chemiluminescence is presented. This includes discussion on reaction conditions, the influence of enhancers such as polyphosphates, formaldehyde and sulfite, the relationship between analyte structure and chemiluminescence intensity, and the application of this chemistry to determine a wide variety of compounds, such as pharmaceuticals, biomolecules, antioxidants, illicit drugs, pesticides and pollutants. Previous proposals for the nature of the emitting species are re-evaluated in light of recent evidence.

Soluble manganese(IV) as a chemiluminescence reagent for the determination of opiate alkaloids, indoles and analytes of forensic Interest

We present the results of our investigations into the use of soluble manganese(IV) as a chemiluminescence reagent, which include a significantly faster method of preparation and a study on the effect of formaldehyde and orthophosphoric acid concentration on signal intensity. Chemiluminescence detection was applied to the determination of 16 analytes, including opiate alkaloids, indoles and analytes of forensic interest, using flow injection analysis methodology. The soluble manganese(IV) reagent was less selective than either acidic potassium permanganate or tris(2,2′-bipyridyl)ruthenium(III) and therefore provided a more universal chemiluminescence detection system for HPLC. A broad spectral distribution with a maximum at 730 ± 5 nm was observed for the reaction between the soluble manganese(IV) and a range of analytes, as well as the background emission from the reaction with the formaldehyde enhancer. This spectral distribution matches that reported for chemiluminescence reactions with acidic potassium permanganate, where a manganese(II) emitting species was elucidated. This provides further evidence that the emission evoked in reactions with soluble manganese(IV) also emanates from a manganese(II) species, and not bimolecular singlet oxygen as suggested by previous authors.

Determination of neurotransmitters and their metabolites using one- and two-dimensional liquid chromatography with acidic potassium permanganate chemiluminescence detection

High-performance liquid chromatography with chemiluminescence detection based on the reaction with acidic potassium permanganate and formaldehyde was explored for the determination of neurotransmitters and their metabolites. The neurotransmitters norepinephrine and dopamine were quantified in the left and right hemispheres of rat hippocampus, nucleus accumbens and prefrontal cortex, and the metabolites vanillylmandelic acid, 3,4-dihydrophenylacetic acid, 5-hydroxyindole-3-acetic acid and homovanillic acid were identified in human urine. Under optimised chemiluminescence reagent conditions, the limits of detection for these analytes ranged from 2.5 × 10−8 to 2.5 × 10−7 M. For the determination of neurotransmitter metabolites in urine, a two-dimensional high-performance liquid chromatography (2D-HPLC) separation operated in heart-cutting mode was developed to overcome the peak capacity limitations of the one-dimensional separation. This approach provided the greater separation power of 2D-HPLC with analysis times comparable to conventional one-dimensional separations.

Effects of different nutritional regimens on the productivity of Australian Cashmere goats and the partitioning of nutrients between cashmere and hair growth

The influence of energy or protein supplementation or energy restriction on cashmere growth was studied in 35 highly productive cashmere wether goats. The goats were shorn on 3 December and randomly allocated to 3 levels of energy intake: M, goats fed to maintain liveweight; 0.8M, goats fed to lose 5 kg liveweight from December to April and then fed ad libitum; and >M, goats fed to gain liveweight. Nested within >M were ADLIB (goats offered feed ad libitum), and 1.25M and l.5M (goats fed M plus 25 or 50% of the difference in mean intake between M and ADLIB). The metabolisable energy requirement to maintain liveweight was 250 kJ kg-0.75 day-1 but to maintain body condition (l.25M) it was 3 12 kJ kg-0.75 day-1. Goats fed 0.8M had a mean intake of 0.68M and lost 26 g day-1 liveweight until April, but when fed ad libitum consumed 2.15M in June and grew rapidly in late autumn and winter at 93 g day-1. Goats fed ADLIB consumed 2.30M in February and gained 87 g day-1 from December to February, but intake declined to 1.61 M in June and they gained 20 g day-1 from April to June. Cashmere growth and fibre diameters of fleeces shorn on 17 June of goats fed >M (221g, 17.69 pm) were significantly greater (P< 0.02) than those of goats fed 0.8M (146 g, 16.67 ¦m), with levels of M-fed goats being intermediate. Within >M, there were no significant differences in cashmere growth. Protein supplementation within M (27 or 54 g day -1 formaldehyde- treated casein) resulted in 40% more wool growth in sheep (P<0.001), but no increase in cashmere or hair growth in goats. Goats fed ADLIB had significantly reduced cashmere yields (P < 0.05) and grew more hair (P<0.05) than did goats in other treatments. About 4 weeks after energy supplementation, fibre diameter of previously energy-deprived goats increased (P< 0.01). Midside patches indicated that energy-deprived goats, which lost liveweight, diverted nutrients preferentially to cashmere growth, while goats fed ADLIB partitioned nutrients towards hair growth. To maximise cashmere growth, supplementary energy should be supplied to avoid liveweight loss from December to April. Goats that had small (1-2 kg) liveweight gains and maintained body condition achieved near maximal levels of cashmere growth.

A review of recent advances in chemiluminescence detection using nano-colloidal manganese(IV)

The application of 'soluble' (colloidal) manganese(IV) for chemiluminescence detection is reviewed, focussing on papers published since the last comprehensive review of the subject in 2008. Advances in this reagent system include: the on-line formation of manganese(IV); new insight into the light-producing pathway and selectivity of the reagent; its application to assess total antioxidants in plant derived samples and oxidative stress in biological fluids and tissues; and the replacement of the formaldehyde enhancer with ethanol.

Enhancing permanganate chemiluminescence detection for the determination of glutathione and glutathione disulfide in biological matrices

Acidic potassium permanganate chemiluminescence enables direct post-column detection of glutathione, but its application to assess the redox state of a wider range of biological fluids and tissues is limited by its sensitivity. Herein we show that the simple on-line addition of an aqueous formaldehyde solution not only enhances the sensitivity of the procedure by two orders of magnitude, but also provides a remarkable improvement in the selectivity of the reagent towards thiols such as glutathione (compared to phenols and amino acids that do not possess a thiol group). This enhanced mode of detection was applied to the determination of glutathione and its corresponding disulfide species in homogenised striatum samples taken from both wild type mice and the R6/1 transgenic mouse model of Huntington's disease, at both 8 and 12 weeks of age. No significant difference was observed between the GSH/GSSG ratios of wild type mice and R6/1 mice at either age group, suggesting that the early disease progression had not significantly altered the intracellular redox environment.

Oil-spill cleanup: the influence of acetylated curaua fibers on the oil-removal capability of magnetic composites

A magnetic resin based on cardanol, furfural, and curaua fibers was prepared and characterized. The material could be used in oil-spill cleanup processes, because of its aromatic/aliphatic balance. The resin was prepared through bulk polycondensation of cardanol and furfural in the presence of curaua fibers and maghemite nanoparticles. Hydrophobicity of the curaua fibers was improved by acetylation, increasing the oil-absorbing capability of the composites. The obtained magnetic composites were studied by Fourier-transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. Degree of cure, magnetic force, and oil-removal capability tests were also performed. The results show that the composites possess an elevated cure degree in addition to a considerable magnetic force. The materials exhibit a good oil removal capability in the presence of a magnetic field, which is improved by the use of acetylated curaua. In the best case, the composite filled with maghemite and curaua can remove 12 parts of oil from water.