Aqueous Permanganate Research Articles

Corrosion inhibition of magnesium alloy AZ31 in chloride-containing solutions by aqueous permanganate

In this work, corrosion of the AZ31 magnesium alloy was examined in 0.05 M NaCl solutions containing 0.01–0.150 mol/dm3 of potassium permanganate as a corrosion inhibitor. A set of electrochemical impedance spectroscopy, linear sweep voltammetry, and hydrogen evolution measurements revealed high inhibitor effectiveness at relatively high (0.150 mol/dm3) KMnO4 concentrations. Based on data of energy-dispersive X-ray analysis, scanning electron microscopy, and Raman spectroscopy, a mechanism of the corrosion inhibition of AZ31 alloy by potassium permanganate in chloride-containing media was proposed.

Unrecognized role of humic acid as a reductant in accelerating fluoroquinolones oxidation by aqueous permanganate

A great concern has been raised regarding the issue of fluoroquinolones (FQs) in the environment. In this work, the transformation of FQs by commonly used oxidant permanganate (Mn(VII)) in the absence and presence of humic acid (HA), ubiquitously existing in aquatic environments, was systematically investigated. Here, the catalytic role of in-situ formed MnO2 on Mn(VII) oxidation of FQs depending on solution pH and co-existing substrates was firstly reported. It was interestingly found that HA could appreciably accelerate FQs degradation by Mn(VII) at environmentally relevant pH. HA as a reductant in accelerating FQs by Mn(VII) oxidation was distinctly elucidated for the first time, where MnO2in situ formed from the reduction of Mn(VII) by HA served as a catalyst. Similar products were observed in the presence versus absence of HA. Considering that the accelerating role of HA was related to its reducing ability, an activation method based on Mn(VII) and reductant (i.e., Fe(II), Mn(II) and (bi)sulfite) was proposed, which exhibited considerable potential for application in the treatment of FQs contaminated water.

Simultaneous photometric determination of oxidation kinetics and average manganese valence in manganese products in situ formed in the reactions of aqueous permanganate with model organic compounds and natural organic matters

In this study, a colorimetric method using 2,2′-azino-bis(3-ethylbenzothiazoline)-6-sulfonate (ABTS) was adopted to investigate oxidation kinetics by permanganate (Mn(VII)) in trace levels (lower than 1 mg/L or 6 µM) and measure average manganese valence in manganese product bulks in (i) synthetic waters containing selected model compounds with electron-rich moieties, (ii) natural organic matters (NOM) isolate solution, and (iii) real water samples including river water, reservoir water and secondary wastewater effluent. The second-order rate constant for Mn(VII) oxidation of phenol determined using ABTS method was demonstrated to be comparable to that measured by traditional high-performance liquid chromatography (HPLC) method at pH 5–9. This method was applied to measure the rate constants of the reactions between Mn(VII) and model compounds with electron-rich moieties. Average manganese valence in manganese product bulks from Mn(VII) oxidation of selected model compounds was lower than 4 at acidic pH, suggesting that Mn(III) was likely to be generated during Mn(VII) oxidation. Possible mechanisms for Mn(III) formation via one/two-electron process were also proposed. Mn(VII) reaction with NOM isolate sample followed two-phase kinetics with rate constants of 3.47 × 10-5 s−1 (mg C/L)-1 and 6.94 × 10-6 s−1 (mg C/L)-1 in the initial and secondary phases at pH 8. Similarly, two-phase kinetics were also found in the consumption of Mn(VII) in real waters. Mn(VII) consumption rates in different real waters followed the order of their dissolved organic carbon levels. In contrast, chlorine decay rates were mainly based on the order of their dissolved organic nitrogen levels. Moreover, average valence in manganese products in real water samples was determined as around 4, which was mainly ascribed to the one-electron-transfer processes of Mn(VII) with NOM constituents in real water samples such as phenols and amines at ambient weak alkaline pH.

Analytical quantification of aqueous permanganate: Direct and indirect spectrophotometric determination for water treatment processes

Three spectrophotometric methods have been developed and compared for the quantification of low concentrations (0.03–63 μM) of aqueous permanganate in neutral pH conditions. Although permanganate is a widely used oxidant in drinking water and wastewater treatment, no widely accepted method of quantification has been reported to date. While one method presented does not require the need for any reagent chemicals (direct spectrophotometric analysis), it yielded a relatively low molar absorption coefficient of 3340 M−1 cm−1 at 525 nm and a level of detection (LOD) and quantification (LOQ) of 0.45 and 1.51 μM, respectively. Some instability of permanganate species during direct quantification was found to occur over 60 min, with a total decrease of 0.002 (arbitrary units) of absorbance, equivalent to a decrease in concentration of 0.6 μM. Beyond 60 min, no further degradation was observed. Indirect spectrophotometric analyses using 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and sodium iodide (NaI) provided a significantly more sensitive method for permanganate quantification, yielding molar absorption coefficients of 140,030 and 61,130 M−1 cm−1, respectively. The LOD and LOQ were determined to be 0.01 and 0.03 μM for the ABTS method and 0.02 and 0.08 μM for the NaI method, respectively. Although conservative and accurate limits of quantification for both the ABTS and NaI methods are presented, which should be sufficient of most practical applications, lower limits may be possible with further refinement of the methods.

The elusive dynamics of aqueous permanganate photochemistry.

Despite decades of investigation, mechanistic details of aqueous permanganate photo-decomposition remain unclear. Here we follow photoinduced dynamics of aqueous permanganate with femtosecond spectroscopy. Photoexcitation of KMnO4(aq) in the visible unleashes a sub-picosecond cascade of non-radiative transitions, leading to a distinct species which relaxes to S0 with a lifetime of 16 ps. Tuning excitation to the UV shows increasing formation of a metastable intermediate, which outlives our ∼1 ns window of detection. Guided by electronic structure calculations and observations from three pulse excitation experiments, we assign the 16 ps species as the lowest Jahn-Teller component of the 3T1 triplet state and suggest a plausible sequence of radiationless transitions, which rapidly populate it. In conjunction with photodecomposition quantum yields obtained from the literature, these results demonstrate that aqueous permanganate photo-decomposition proceeds through a long-lived intermediate which is formed in parallel to the triplet in less than one ps upon UV absorption. The possibility that this is the postulated highly oxidative peroxo species, a fraction of which leads to the stable (MnO2- + O2) fragments, is discussed. Finally, periodic modulations detected in the pump-probe signal are assigned to ground-state vibrational coherences excited by impulsive Raman. Their wavelength-dependent absolute phases outline the borders between adjacent electronic transitions in the linear spectrum of permanganate.

The electronic structure of the aqueous permanganate ion: aqueous-phase energetics and molecular bonding studied using liquid jet photoelectron spectroscopy

Permanganate aqueous solutions, MnO4-(aq.), were studied using liquid-micro-jet-based soft X-ray non-resonant and resonant photoelectron spectroscopy to determine valence and core-level binding energies. To identify possible differences in the energetics between the aqueous bulk and the solution-gas interface, non-resonant spectra were recorded at two different probing depths. Similar experiments were performed with different counter ions, Na+ and K+, with the two solutions yielding indistinguishable anion electron binding energies. Our resonant photoelectron spectroscopy measurements, performed near the Mn LII,III- and O K-edges, selectively probed valence charge distributions between the Mn metal center, O ligands, and first solvation shell in the aqueous bulk. Associated resonantly-enhanced solute ionisation signals revealed hybridisation of the solute constituents' atomic orbitals, including the inner valence Mn 3p and O 2s. We identified intermolecular coulombic decay relaxation processes following resonant X-ray excitation of the solute that highlight valence MnO4-(aq.)-H2O(l) electronic couplings. Furthermore, our results allowed us to infer oxidative reorganisation energies of MnO4˙(aq.) and adiabatic valence ionisation energies of MnO4-(aq.), revealing the Gibbs free energy of oxidation and permitting estimation of the vertical electron affinity of MnO4˙(aq.). Finally, the Gibbs free energy of hydration of isolated MnO4- was determined. Our results and analysis allowed a near-complete binding-energy-scaled MnO4-(aq.) molecular orbital and a valence energy level diagram to be produced for the MnO4-(aq.)/MnO4˙(aq.) system. Cumulatively, our mapping of the aqueous-phase electronic structure of MnO4- is expected to contribute to a deeper understanding of the exceptional redox properties of this widely applied aqueous transition-metal complex ion.

Oxidation kinetics of anilines by aqueous permanganate and effects of manganese products: Comparison to phenols

In this study, the potential applicability of potassium permanganate (Mn(VII)) for anilines elimination was systematically investigated firstly, with a focus on the effect of manganese intermediates on the kinetics of anilines versus phenols. It was found that Mn(VII) could fairly oxidize anilines, where the second-order rate constants (kMn(VII)) values for anilines always decreased as pH increased from 5 to 9. This interesting pH-dependency was successfully described by the kinetic models proposed in literature to account for the unusual pH-rate profiles for phenols, where the formation of intermediates between Mn(VII) and phenols or anilines was likely involved. The effect of manganese products such as MnO2 and Mn(III) on the oxidation of anilines by Mn(VII) was demonstrated. Under slightly acidic conditions, the reactions of Mn(VII) with anilines displayed autocatalysis, suggesting a similar catalytic role of MnO2 formed in situ as compared to phenols. Several ligands (e.g., pyrophosphate) inhibited the formation of MnO2 colloids and lowered the oxidation rates of anilines by Mn(VII) at acidic pH, while these ligands greatly accelerated the kinetics of phenols under similar conditions. The contrasting effects of ligands might be mainly attributed to the different reactivity of ligand-stabilized Mn(III) formed in situ toward anilines vs phenols. The complex effect of humic acid was highly dependent on solution pH, possible due to the dual role of humic acid that it could act as a reductant (competitively consuming Mn(VII) and phenoxy or aniline radical) as well as a ligand (stabilizing manganese intermediates such as Mn(III) species) to affect Mn(VII) reactions.

The Mechanism of C-H Bond Oxidation by Aqueous Permanganate.

The permanganate ion (MnO4-) has been widely used as a reagent for water treatment for over a century. It is a strong enough oxidant to activate carbon-hydrogen bonds, one of the most important reactions in biological and chemical systems. Our current textbook understanding of the oxidation mechanism in aqueous solution involves an initial, rate-limiting hydride abstraction by permanganate followed by reaction of the carbocation with bulk water to form an alcohol. This mechanism fits well into the classic oxidation sequence of alkane → alcohol → aldehyde → carboxylate, the central paradigm for both abiotic and biotic alkane oxidation in aqueous environments. In this study, we provide three lines of evidence through (1) a broken-symmetry density functional theory approach, (2) isotope labeling experiments, and (3) kinetic network modeling to demonstrate that aqueous permanganate can circumvent prior alcohol formation and produce aldehydes directly via a reaction path that bifurcates after the initial transition state. In contrast to classic transition state theory, the rate-limiting step is found to not determine product distribution, bearing critical implications for pathway and rate predictions. This complex reaction network provides new insights into the oxidation mechanisms of organic compounds involving transition metal complexes as well as enzyme or metal oxide surface active sites.

Quinone group enhances the degradation of levofloxacin by aqueous permanganate: Kinetics and mechanism

Quinone group is an important fraction of humic acid. The pseudo-first-order rate constant (kobs) of levofloxacin (LF) degradation by permanganate (MnO4−) significantly increased from 0.010 (without benzoquinone, BQ) to 0.042–0.443 min−1 at [BQ]o:[MnO4−]o (molar ratio) = 0.03–0.25 at pH 7.5, and an acidic pH facilitated LF degradation. In the presence of BQ, MnO4− was first reduced to Mn(II). Then, Mn(II) reacted with BQ to produce Mn(III) and semiquinone radical, which was promoted under acidic conditions. With dissolved oxygen available, Mn(III) further oxidized semiquinone radical to produce singlet oxygen (1O2) and superoxide radical (O2−) as well as regenerate BQ. In addition, MnO4− could also react with Mn(II) to produce Mn(III), whose complexation with semiquinone radical in turn promoted this reaction. Due to the predominant scavenging of O2− by BQ, 1O2 and Mn(III) mainly contributed to the accelerated LF degradation, with a notable formation of hydroxyl, ketone and endoperoxide groups in the degradation byproducts. This study helps better understand the role of natural organic matter in the degradation of organic micropollutants by MnO4− in water treatment.

Does Soluble Mn(III) Oxidant Formed in Situ Account for Enhanced Transformation of Triclosan by Mn(VII) in the Presence of Ligands?

In previous studies, we interestingly found that several ligands (e.g., pyrophosphate, nitrilotriacetate, and humic acid) could significantly accelerate the oxidation rates of triclosan (TCS; the most widely used antimicrobial) by aqueous permanganate (Mn(VII)) especially at acid pH, which was ascribed to the contribution of ligand-stabilized Mn(III) (defined Mn(III)L) formed in situ as a potent oxidant. In this work, it was found that the oxidation of TCS by Mn(III)L resulted in the formation of dimers, as well as hydroxylated and quinone-like products, where TCS phenoxy radical was likely involved. This transformation pathway distinctly differed from that involved in Mn(VII) oxidation of TCS, where 2,4-dichlorophenol (DCP) was the major product with a high yield of ∼80%. Surprisingly, we found that the presence of various complexing ligands including pyrophosphate, nitrilotriacetate, and humic acid, as well as bisulfite slightly affected the yields of DCP, although they greatly enhanced the oxidation kinetics of TCS by Mn(VII). This result could not be reasonably explained by taking the contribution of Mn(III)L into account. Comparatively, the degradation of TCS by manganese dioxide (MnO2) was also greatly enhanced in the presence of these ligands with negligible formation of DCP, which could be rationalized by the contribution of Mn(III)L. In addition, it was demonstrated that DCP could not be generated from Mn(VII) oxidation of unstable phenoxy radical intermediates and stable oxidation products formed from TCS by Mn(III)L. These findings indicate that manganese intermediates other than Mn(III) are likely involved in the Mn(VII)/TCS/ligand systems responsible for the high yields of DCP product.

Degradation kinetics and transformation products of chlorophene by aqueous permanganate

This paper evaluates the oxidation of an antibacterial agent, chlorophene (4-chloro-2-(phenylmethyl)phenol, CP), by permanganate (Mn(VII)) in water. Second-order rate constant (k) for the reaction between Mn(VII) and CP was measured as (2.05 ± 0.05) × 101 M−1 s−1 at pH 7.0 for an initial CP concentration of 20.0 μM and Mn(VII) concentration of 60.0 μM. The value of k decreased with increasing pH in the pH range of 5.0–7.0, and then increased with an increase in solution pH from 7.0 to 10.0. The presence of MnO2 and Fe3+ in water generally enhanced the removal of CP, while the effect of humic acid was not obvious. Fourteen oxidation products of CP were identified by an electrospray time-of-flight mass spectrometer, and direct oxidation, ring-opening, and decarboxylation were mainly observed in the reaction process. The initial reaction sites of CP by Mn(VII) oxidation were rationalized by density functional theory calculations. Toxicity changes of the reaction solutions were assessed by the luminescent bacteria P. phosphoreum, and the intermediate products posed a relatively low ecological risk during the degradation process. The efficient removal of CP in secondary clarifier effluent and river water demonstrated the potential application of this Mn(VII) oxidation method in water treatment.

Transformation of Methylparaben by aqueous permanganate in the presence of iodide: Kinetics, modeling, and formation of iodinated aromatic products

This work investigated impacts of iodide (I−) on the transformation of the widely used phenolic preservative methylparaben (MeP) as well as 11 other phenolic compounds by potassium permanganate (KMnO4). It was found that KMnO4 showed a low reactivity towards MeP in the absence of I− with apparent second-order rate constants (kapp) ranging from 0.065 ± 0.0071 to 1.0 ± 0.1 M−1s−1 over the pH range of 5–9. The presence of I− remarkably enhanced the transformation rates of MeP by KMnO4 via the contribution of hypoiodous acid (HOI) in situ formed, which displayed several orders of magnitude higher reactivity towards MeP than KMnO4. This enhancing effect of I− was greatly influenced by solution conditions (e.g., I− or KMnO4 concentration or pH), which could be well simulated by a kinetic model involving competition reactions (i.e., KMnO4 with I−, KMnO4 with MeP, HOI with KMnO4, and HOI with MeP). Similar enhancing effect of I− on the transformation kinetics of 5 other selected phenols (i.e., p-hydroxybenzoic acid, phenol, and bromophenols) at pH 7 was also observed, but not in the cases of bisphenol A, triclosan, 4-n-nonylphenol, and cresols. This discrepancy could be well explained by the relative reactivity of KMnO4 towards phenols vs I−. Liquid chromatography-tandem mass spectrometry analysis showed that iodinated aromatic products and/or iodinated quinone-like product were generated in the cases where I− enhancing effect was observed. Evolution of iodinated aromatic products generated from MeP (10 μM) treated by KMnO4 (50-150 μM) in the presence of I− (5-15 μM) suggested that higher I− or moderate KMnO4 concentration or neutral pH promoted their formation. A similar enhancing effect of I− (1 μM) on the transformation of MeP (1 μM) by KMnO4 (12.6 μM) and formation of iodinated aromatic products were also observed in natural water. This work demonstrates an important role of I− in the transformation kinetics and product formation of phenolic compounds by KMnO4, which has great implications for future applications of KMnO4 in treatment of I−-containing water.

Impact of humic acid on the degradation of levofloxacin by aqueous permanganate: Kinetics and mechanism

Levofloxacin (LF) is a frequently detected fluoroquinolone in surface water, and permanganate (MnO4−) is a commonly used oxidant in drinking water treatment. This study investigated the impact of humic acid (HA) on LF degradation by aqueous MnO4− from both kinetic and mechanistic aspects. In the absence of HA, the second-order rate constant (k) of LF degradation by MnO4− was determined to be 3.9 M−1 s−1 at pH 7.5, which increased with decreasing pH. In the presence of HA, the pseudo-first-order rate constant (kobs) of LF degradation at pH 7.5 was significantly increased by 3.8- and 2.8-fold at [HA]o:[KMnO4]o (mass ratio) = 0.5 and 1, respectively. Secondary oxidant scavenging and electron paramagnetic resonance tests indicated that HA could form a complex with Mn(III), a strongly oxidative intermediate produced in the reaction of MnO4− with HA, to induce the successive formation of superoxide radicals (O2−) and hydroxyl radicals (OH). The resulting OH primarily contributed to the accelerated LF degradation, and the complex [HA-Mn(III)] could account for the rest of acceleration. The degradation of LF and its byproducts during MnO4− oxidation was mainly through hydroxylation, dehydrogenation and carboxylation, and the presence of HA led to a stronger destruction of LF. This study helps better understand the degradation of organic micropollutants by MnO4− in drinking water treatment.

Oxidation of inorganic compounds by aqueous permanganate: Kinetics and initial electron transfer steps

Abstract In this study, the kinetics of the reactions between aqueous permanganate (Mn(VII)) and selected inorganic compounds (e.g. KSCN, NaNO2, Na2SO3, Na2S2O3, KI, N2H4, H2O2, and NH2OH) were investigated in aqueous solutions at pH 5–9 with excess pyrophosphate (L) by detecting the decay of Mn(VII) using a stopped-flow technique. With excess L, soluble Mn(III)L rather than MnO2 was generated, which had negligible interference on examining the change of the absorbance of Mn(VII) at 525 nm (∼45 M−1 cm−1 for Mn(III)L vs 2500 M−1 cm−1 for Mn(VII)). The reactions of Mn(VII) with Na2SO3, Na2S2O3, KSCN, NaNO2, and KI (referred to as SA) exhibited second-order kinetics. Comparatively, the reactions of Mn(VII) with N2H4, H2O2, and NH2OH (referred to as SB) showed two-phase kinetics (i.e., an initial lag phase and a secondary fast phase), and the second-order rate constants (k1, M−1 s−1) were calculated in the initial phase. In the second phase, Mn(III)L reacted with SB producing Mn(II), and then Mn(II) reacted fast with Mn(VII) producing Mn(III)L. The kinetics of the reaction between Mn(II) and Mn(VII) with excess L at pH 4–9 were examined and the loss rate of Mn(VII) increased with increasing pH value. The species-specific second-order rate constants (k1i, M−1 s−1) for the reactions of Mn(VII) with inorganic compounds were determined by the experimental k1 values. Furthermore, a linear free energy relationship (LFER) was found (log(k1i) = 2.86 − 1.90E(2)0) between log k1i and 2−e− reduction potentials for inorganic species (i.e., SO32−, S2O32−, SCN−, H2O2, NH2OH, I−, and N2H4) while only NO2− showed 1−e− transfer process, indicating highly active aqueous manganese intermediates (Mn(V) and Mn(VI)) formed in situ upon Mn(VII) reduction.

ABTS as an Electron Shuttle to Enhance the Oxidation Kinetics of Substituted Phenols by Aqueous Permanganate.

In this study, it was, interestingly, found that 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulfonate (ABTS), a widely used electron shuttle, could greatly accelerate the oxidation of substituted phenols by potassium permanganate (Mn(VII)) in aqueous solutions at pH 5-9. This was attributed to the fact that these substituted phenols could be readily oxidized by the stable radical cation (ABTS(•+)), which was quickly produced from the oxidation of ABTS by Mn(VII). The reaction of Mn(VII) with ABTS exhibited second-order kinetics, with stoichiometries of ∼5:1 at pH 5-6 and ∼3:1 at pH 7-9, and the rate constants varied negligibly from pH 5 to 9 (k = (9.44 ± 0.21) × 10(4) M(-1) s(-1)). Comparatively, the reaction of ABTS(•+) with phenol showed biphasic kinetics. The second-order rate constants for the reactions of ABTS(•+) with substituted phenols obtained in the initial phase were strongly affected by pH, and they were several orders of magnitude higher than those for the reactions of Mn(VII) with substituted phenols at each pH. Good Hammett-type correlations were found for the reactions of ABTS(•+) with undissociated (log(k) = 2.82-4.31σ) and dissociated phenols (log(k) = 7.29-5.90σ). The stoichiometries of (2.2 ± 0.06):1 (ABTS(•+) in excess) and (1.38 ± 0.18):1 (phenol in excess) were achieved in the reaction of ABTS(•+) with phenol, but they exhibited no pH dependency.

Synthesis and Electrochemical Characterization of a Sodium Manganese Oxide By Facile Reduction Reaction for Sodium Ion Batteries

A non-stoichiometric composition of sodium manganese oxide (NaxMnO2+δ) cathode useful for sodium batteries was synthesized by an ambient temperature strategy that involves the facile reduction of aqueous sodium permanganate in sodium iodide and subsequent heat treatment at 600 °C. A combined powder X-ray diffraction (PXRD) and synchrotron X-ray diffraction (SXRD) analyses confirmed the annealed sample to belong to a NaxMnO2 phase with a P2-hexagonal structure. The ICP results confirmed the stoichiometry of the sample to be Na0.53MnO2+δ. Electron microscopy studies revealed the particle size of the electrode to be in the range of a few hundred nanometers. The Na0.53MnO2+δ cathode delivered average discharge capacities of 170 mAhg-1 with a stable plateau at 2.1 V for the initial 25 cycles versus sodium. Ex-situ XANES studies confirmed the reversible intercalation of sodium into Na0.53MnO2+δ and suggested the accommodation of over-stoichiometric Mn4+ ions to contribute towards electrode performance. Figure 1

Reactivity of β-blockers/agonists with aqueous permanganate. Kinetics and transformation products of salbutamol

The possible oxidation of two β-blockers, atenolol and propranolol, and one β-agonist, salbutamol, with aqueous potassium permanganate (KMnO4) was investigated by liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-QTOF-MS). Under strong oxidation conditions (2 mg L−1 KMnO4, 24 h), only salbutamol did significantly react. In this way, the oxidation kinetics of salbutamol was further investigated at different concentrations of KMnO4, chloride, phosphate and sample pH by means of a full factorial experimental design. Depending on these factors, half-lives were in the range 1–144 min for drug and it was observed that KMnO4 concentration was the most significant factor, resulting in increased reaction rate as it is increased. Moreover, the reaction of salbutamol is also enhanced at basic pH and to a minor extent by the presence of phosphates, being both factors more relevant at low KMnO4 concentrations. The use of an accurate-mass LC-QTOF-MS system permitted the identification of a total of seven transformation products (TPs). The transformation path of the drug begins by the attack of KMnO4 on two double bonds of the aromatic ring of salbutamol via 3 + 2 and 2 + 2 addition reactions, which resulted in the ring opening and that continues with oxidative reactions to finally produce smaller size TPs, ending with tert-butyl-formamide, as the smallest TP identified. Reaction in real samples showed a slower and partial oxidation of the pharmaceutical, due to other competing water organic constituents, but still exceeding 60%. Moreover, the software predicted toxicity of TPs indicates that they are expected not to be more toxic than salbutamol, in contrast to the results obtained for the predicted toxicity of chlorination TPs, excepting predicted developmental toxicity.

Understanding the role of manganese dioxide in the oxidation of phenolic compounds by aqueous permanganate.

Recent studies have shown that manganese dioxide (MnO2) can significantly accelerate the oxidation kinetics of phenolic compounds such as triclosan and chlorophenols by potassium permanganate (Mn(VII)) in slightly acidic solutions. However, the role of MnO2 (i.e., as an oxidant vs catalyst) is still unclear. In this work, it was demonstrated that Mn(VII) oxidized triclosan (i.e., trichloro-2-phenoxyphenol) and its analogue 2-phenoxyphenol, mainly generating ether bond cleavage products (i.e., 2,4-dichlorophenol and phenol, respectively), while MnO2 reacted with them producing appreciable dimers as well as hydroxylated and quinone-like products. Using these two phenoxyphenols as mechanistic probes, it was interestingly found that MnO2 formed in situ or prepared ex situ greatly accelerated the kinetics but negligibly affected the pathways of their oxidation by Mn(VII) at acidic pH 5. The yields (R) of indicative products 2,4-dichlorophenol and phenol from their respective probes (i.e., molar ratios of product formed to probe lost) under various experimental conditions were quantified. Comparable R values were obtained during the treatment by Mn(VII) in the absence vs presence of MnO2. Meanwhile, it was confirmed that MnO2 could accelerate the kinetics of Mn(VII) oxidation of refractory nitrophenols (i.e., 2-nitrophenol and 4-nitrophenol), which otherwise showed negligible reactivity toward Mn(VII) and MnO2 individually, and the effect of MnO2 was strongly dependent upon its concentration as well as solution pH. These results clearly rule out the role of MnO2 as a mild co-oxidant and suggest a potential catalytic effect on Mn(VII) oxidation of phenolic compounds regardless of their susceptibility to oxidation by MnO2.

Directly detected 55Mn MRI: Application to phantoms for human hyperpolarized 13C MRI development

In this work we demonstrate for the first time directly detected manganese-55 (55Mn) magnetic resonance imaging (MRI) using a clinical 3T MRI scanner designed for human hyperpolarized 13C clinical studies with no additional hardware modifications. Due to the similar frequency of the 55Mn and 13C resonances, the use of aqueous permanganate for large, signal-dense, and cost-effective “13C” MRI phantoms was investigated, addressing the clear need for new phantoms for these studies. Due to 100% natural abundance, higher intrinsic sensitivity, and favorable relaxation properties, 55Mn MRI of aqueous permanganate demonstrates dramatically increased sensitivity over typical 13C phantom MRI, at greatly reduced cost as compared with large 13C-enriched phantoms. A large sensitivity advantage (22-fold) was demonstrated. A cylindrical phantom (d=8cm) containing concentrated aqueous sodium permanganate (2.7 M) was scanned rapidly by 55Mn MRI in a human head coil tuned for 13C, using a balanced steady state free precession acquisition. The requisite penetration of radiofrequency magnetic fields into concentrated permanganate was investigated by experiments and high frequency electromagnetic simulations, and found to be sufficient for 55Mn MRI with reasonably sized phantoms. A sub-second slice-selective acquisition yielded mean image signal-to-noise ratio of ~60 at 0.5cm3 spatial resolution, distributed with minimum central signal ~40% of the maximum edge signal. We anticipate that permanganate phantoms will be very useful for testing HP 13C coils and methods designed for human studies.

Activated carbon/manganese dioxide hybrid electrodes for high performance thin film supercapacitors

We combine the activated carbon (AC) and the manganese dioxide (MnO2) in a AC/MnO2 hybrid electrode to overcome the low capacitance of activated carbon and MnO2 by exploiting the large surface area of AC and the fast reversible redox reaction of MnO2. An aqueous permanganate (MnO4−) is converted to MnO2 on the surface of the AC electrode by dipping the AC electrode into an aqueous permanganate solution. The AC/MnO2 hybrid electrode is found to display superior specific capacitance of 290 F/g. This shows that supercapacitors classified as electric double layer capacitors and pseudocapacitors can be combined together.