Analytical applications of acidic potassium permanganate as a chemiluminescence reagent

A critical review presented is of the literature concerning the use of acidic solutions of potassium permanganate to generate chemiluminescence during the oxidation of both organic compounds and inorganic species. A brief overview of the reagent’s historical origin is followed by a chronological survey of its analytical applications, from what we believe to be the first report in 1975 through to those published up until mid-2001. This review does not include those papers where potassium permanganate has been used either in alkaline conditions or in conjunction with other chemiluminescence reagents.

Monitoring the total phenolic/antioxidant levels in wine using flow injection anaylsis with acidic potassium permanganate chemiluminescence detection

Flow injection methodology is described for the estimation of the total phenolic content of wine using acidic potassium permanganate chemiluminescence detection. Selected simple phenolic compounds including quercetin, rutin, catechin, epicatechin, ferulic acid, caffeic acid, gallic acid, 4-hydroxycinnamic acid and vanillin elicited analytically useful chemiluminescence with detection limits ranging between 4×10⁻¹⁰ and 7×10⁻⁷ M. A comparison between the chemiluminescence methodology and other total phenol/antioxidant assays, used by the food and beverage industry, resulted in a good correlation. The chemiluminescence detection was found to be selective with minimal interferences being observed from the non-phenolic components in wine. Analysis of 12 different wines showed that the chemiluminescence method was a rapid way to estimate their antioxidant or total phenolic content.

Decreasing dietary sodium while following a self-selected potassium-rich diet reduces blood pressure

Reducing dietary sodium reduces blood pressure (BP), a major risk factor for cardiovascular disease, but few studies have specifically examined the effect on BP of altering dietary sodium in the context of a high potassium diet. This randomized, crossover study compared BP values in volunteer subjects self-selecting food intake and consuming low levels of sodium (Na+; 50 mmol/d) with those consuming high levels of sodium (> or =20 mmol/d), in the context of a diet rich in potassium (K+). Sodium supplementation (NaSp) produced the difference in Na+ intake. Subjects (n = 108; 64 women, 44 men; 16 on antihypertensive therapy) had a mean age of 47.0 ± 10.1 y. Subjects were given dietary advice to achieve a low sodium (LS) diet with high potassium intake (50 mmol Na+/d, >80 mmol K+/d) and were allocated to NaSp (120 mmol Na+/d) or placebo treatment for 4 wk before crossover. The LS diet decreased urinary Na+ from baseline, 138.7 ± 5.3 mmol/d to 57.8 ± 3.8 mmol/d (P < 0.001). The NaSp treatment returned urinary Na+ to baseline levels 142.4 ± 3.7 mmol/d. Urinary K+ increased from baseline, 78.6 ± 2.3 to 86.6 ± 2.1 mmol/d with the LS diet and to 87.1 ± 2.1 mmol/d with NaSp treatment (P < 0.001). The LS diet reduced home systolic blood pressure (SBP) by 2.5 ± 0.8 mm Hg (P = 0.004), compared with the NaSp treatment. Hence, reducing Na+ intake from 140 to 60 mmol/d significantly decreased home SBP in subjects dwelling in a community setting who consumed a self-selected K+-rich diet, and this dietary modification could assist in lowering blood pressure in the general population.

Comparison of soluble manganese(IV) and acidic potassium permanganate chemiluminescence detection using flow injection and sequential injection analysis for the determination of ascorbic acid in vitamin C tablets

The limits of detection (3s) for ascorbic acid were 5×10⁻⁸ M with acidic potassium permanganate using both flow injection analysis (FIA) and sequential injection analysis (SIA) whereas the soluble manganese(IV) afforded 1×10⁻⁸ M and 5×10⁻⁹ M for FIA and SIA, respectively. Determinations of ascorbic acid in Vitamin C tablets were achieved with minimal sample pretreatment using a standard additions calibration and gave good agreement with those of iodimetric titration.

Preliminary evaluation of dual acidic potassium permanganate and tris(2,2`-bipyridyl)ruthenium(II) chemiluminescence detection for the HPLC determination of Papaver somniferum alkaloids

This paper describes a dual chemiluminescence reagent for the determination of the opiate alkaloids morphine, codeine, oripavine, and thebaine in Papaver somniferum extracts. Detection was achieved using a mixture of acidic potassium permanganate and tris(2,2′-bipyridyl)ruthenium(ii), where the former acted as both the oxidant for the latter and as a chemiluminescence reagent in its own right. The analytes were separated on a C₈ column using ion-pairing HPLC. The application of the mixed reagent detection compared favourably with results obtained using standard HPLC methodology. Detection limits for the alkaloids were 10^-6, 5 × 10^-7, 3 × 10^-6, and 2 × 10^-6 mol L^-1 for morphine, codeine, oripavine, and thebaine, respectively.

Detection of pyrrolizidine alkaloids using flow analysis with both acidic potassium permanganate and tris(2,2’-bipyridyl)ruthenium(II) chemiluminescence

For the first time, analytically useful chemiluminescence was elicited from the reactions of the pyrrolizidine alkaloids. Heliotrine, retronecine, supinine, monocrotaline and echinatine N-oxide yielded chemiluminescence upon reaction with tris(2,2′-bipyridyl)ruthenium(II) whilst lasiocarpine, its N-oxide and supinine elicited light upon reaction with acidic potassium permanganate. Detection limits for heliotrine were 1.25 × 10⁻⁷ M and 9 × 10⁻⁹ M for tris(2,2′-bipyridyl)ruthenium(III) perchlorate with flow injection analysis (FIA) and the silica-immobilised reagent (4-[4-(dichloromethylsilanyl)-butyl]-4′-methyl-2,2′-bipyridine)bis(2,2′-bipyridyl)ruthenium(II) with sequential injection analysis (SIA), respectively. Lasiocarpine was detectable at 1.4 × 10⁻⁷ M using acidic potassium permanganate with FIA. Additionally, the silica-immobilised reagent was optimised with respect to the oxidant (ammonium ceric nitrate) concentration and the aspiration times which afforded a detection limit for codeine of 5 × 10⁻¹⁰ M using SIA.

Determination of psilocin and psilocybin using flow injection analysis with acidic potassium permanganate and tris(2,2’-bipyridyl) ruthenium(II) chemiluminescence detection respectively

A simple, rapid and sensitive method for the determination of psilocin and psilocybin is described. This is the first report on the determination of psilocin and psilocybin using flow injection analysis with acidic potassium permanganate and tris(2,2′-bipyridyl)ruthenium(II) chemiluminescence. The limits of detection (signal-to-noise ratio = 3) are 9 × 10⁻¹⁰ M and 3 × 10⁻¹⁰ M for psilocin and psilocybin, respectively.A concise synthetic route for psilocin in three steps from readily available starting materials is also described. The structures were elucidated on the basis of spectroscopic data.

New light from an old reagent: chemiluminescence from the reaction of potassium permanganate with sodium borohydride

When aqueous sodium borohydride (50 mM) is added to a solution of potassium permanganate (1mM, in sodium hexametaphosphate) at acidic pH, bright red-orange emission is easily visible in a darkened room. This chemiluminescence emission is due to an excited state of manganese (II) that undergoes solution phase phosphorescence and provides an excellent opportunity for students to explore the relationship between the initial oxidation state of the manganese and the likelihood of luminescence. Not surprisingly Mn(VII), Mn(IV) and Mn(III) all give rise to chemiluminescence where as Mn(II) fails to react.

The determination of psilocin and psilocybin in hallucinogenic mushrooms by HPLC utilizing a dual reagent acidic potassium permanganate and tris(2,2´-bipyridyl)ruthenium(II) chemiluminescence detection system

This paper describes a procedure for the determination of psilocin and psilocybin in mushroom extracts using high-performance liquid chromatography with postcolumn chemiluminescence detection. A number of extraction methods for psilocin and psilocybin in hallucinogenic mushrooms were investigated, with a simple methanolic extraction being found to be most effective. Psilocin and psilocybin were extracted from a variety of hallucinogenic mushrooms using methanol. The analytes were separated on a C₁₂ column using a (95:5% v/v) methanol:10 mM ammonium formate, pH 3.5 mobile phase with a run time of 5 min. Detection was realized through a dual reagent chemiluminescence detection system of acidic potassium permanganate and tris(2,2'-bipyridyl)ruthenium(II). The chemiluminescence detection system gave improved detectability when compared with UV absorption at 269 nm, with detection limits of 1.2 × 10⁻⁸ and 3.5 × 10⁻⁹ mol/L being obtained for psilocin and psilocybin, respectively. The procedure was applied to the determination of psilocin and psilocybin in three Australian species of hallucinogenic mushroom.

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.

Determination of synephrine in weight-loss products using high performance liquid chromatography with acidic potassium permanganate chemiluminescence detection

Adrenergic amines found in extracts of Citrus aurantium (bitter orange) evoke analytically useful chemiluminescence with acidic potassium permanganate in the presence of polyphosphates. From corrected chemiluminescence spectra, the wavelength of maximum intensity for these reactions was 680 ± 5 nm and, using flow injection analysis methodology, limits of detection for synephrine, octopamine, tyramine and hordenine were found to be between 1 × 10⁻⁹ and 1 × 10⁻⁸ M. We have applied this method of detection to the rapid determination of synephrine in dietary supplements using monolithic column chromatography.

Potassium phosphonate alters the defence response of Xanthorrhoea australis following infection by Phytophthora cinnamomi

Potassium phosphonate (phosphite) is widely used in the management of Phytophthora diseases in agriculture, horticulture and natural environments. The Austral grass tree, Xanthorrhoea australis, a keystone species in the dry sclerophyll forests of southern Australia, is susceptible to Phytophthora cinnamomi, but is protected by applications of phosphite. We examined the effect of phosphite application on the infection of X. australis seedlings and cell suspension cultures by zoospores of P. cinnamomi. Phosphite induced more intense cellular responses to pathogen challenge and suppressed pathogen ingress in both seedlings and cell cultures. In untreated X. australis seedlings, hyphal growth was initially intercellular, became intracellular 24 h after inoculation, and by 48 h had progressed into the vascular tissue. In phosphite-treated seedlings, growth of P. cinnamomi remained intercellular and was limited to the cortex, even at 72 h after inoculation. The cell membrane retracted from the cell wall and phenolic compounds and electron dense substances were deposited around the wall of infected and neighbouring cells. Suspension cells were infected within 6 h of inoculation. Within 24 h of inoculation, untreated cells were fully colonised, had collapsed cytoplasm and died. The protoplast of phosphite-treated suspension cells collapsed within 12 h of inoculation, and phenolic material accumulated in adjacent, uninfected cells. No anatomical response to phosphite treatment was observed before infection of plant tissues, suggesting that the phosphite-associated host defence response is induced following pathogen challenge. Anatomical changes provide evidence that phosphite stimulates the host defence system to respond more effectively to pathogen invasion.

The characteristic red chemiluminescence from reactions with acidic potassium permanganate : further spectroscopic evidence for a manganese(II) emitter

A direct comparison of the laser-induced photoluminescence of manganese(II) with the chemiluminescence from the reaction between acidic potassium permanganate and sodium borohydride was used to confirm that the characteristic red emission from this widely used chemiluminescence reagent emanates from an electronically excited manganese(II) species.

Dietary fiber, potassium, magnesium and calcium in relation to the risk of preeclampsia

To explore the relation between preeclampsia risk and maternal intake of dietary fiber, potassium, magnesium and calcium. STUDY DESIGN: We conducted a case-control study of 172 preeclamptics and 339 normotensive controls. Maternal dietary intake was assessed using a food frequency questionnaire. Logistic regression procedures were used to estimate the association between each dietary factor and preeclampsia risk. RESULTS: Fiber intake was inversely associated with the risk of preeclampsia. When extreme quartiles of total fiber intake were compared, the odds ratio (OR) for preeclampsia was 0.46 (95% confidence interval [CI] 0.23-0.92). The multivariate OR for preeclampsia for women in the top quartile of potassium intake (>4.1 g/d) versus the lowest quartile (<2.4 g/d) was 0.49 (95% CI 0.24-0.99). There was some evidence of a reduced risk of preeclampsia with a high intake of magnesium and calcium, though these results were not statistically significant. Intake of fruits and vegetables, low-fat dairy products, total cereal and dark bread were each associated with a reduced risk of preeclampsia. CONCLUSION: Our results support previous reports that suggest that diets high in fiber and potassium are associated with a reduced risk of hypertension. Maternal intake of recommended amounts of foods rich in fiber, potassium and other nutrients may reduce the risk of preeclampsia.