Regioselective oxidation of tetracycline by permanganate through alternating susceptible moiety and increasing electron donating ability.

Permanganate has attracted much attention in wide range of chemistry and particularly in degradation of environmental pollutants. However, few studies have discussed the feature of regioselective reactivity of permanganate with specific moiety of the target compound. Herein, we studied the reaction between permanganate and tetracycline that is an emerging micropollutant with different species containing several electron-rich groups. The second-order rate constants increased from 6.0 to 9.0 and could be quantitatively modeled by considering the speciation of both reactants, yielding kTC0 = 11.7 (mol/L)-1 sec-1, kTC- = 35.7 (mol/L)-1 sec-1, kTC2- = 43.1 (mol/L)-1 sec-1 for individual reaction channels. Degradation products were then identified as the hydroxylated and demethylated compounds. The result suggested a rate-limiting step of simple hydroxylation at the phenolic and/or alkene moieties, while the demethylation should be caused by the unavoidably formed manganese oxide via single electron oxidation. This is supported by the DFT calculation, indicating the primary oxidation of phenolic group of TC0 with activation barrier of 44.5 kcal/mol and of alkene group of TC- and TC2- with activation barriers of 44.0 and 43.4 kcal/mol, respectively. This is in agreement with the experimental results, implying the alternation of regioselectivity associated with the deprotonation process. The result was further supported by performing the Fukui function and electrostatic potential analysis, reflecting the more probable site and better electron donating tendency beneficial to the permanganate oxidation.

High efficient removal of 4-aminophenylarsonic acid from aqueous solution via enhanced FeOOH using Mn(VII).

Efficient removal of 4-aminophenylarsonic acid from contaminated water sources is essential to mitigate arsenic pollution. We proposed a competent technique to achieve 4-aminophenylarsonic acid removal via adsorption on enhanced α-FeOOH using various concentrations of Mn(VII). The elimination rate of 4-aminophenylarsonic acid applying FeOOH with Mn(VII) was dependent on acidic conditions. More than 99.9% of 4-aminophenylarsonic acid was eliminated in a 6-min reaction time under acidic conditions. The reaction of 4-aminophenylarsonic acid was fast at 4.0 and 5.0 pH, with its complete oxidation into arsenate and the liberation of manganese Mn(II) in the initial stage of the reaction. Similarly, the reaction rate constant (kobs) decreased from 0.7048 ± 0.02 to 0.00155 ± 0.00007 as the pH increased from 4.0 to 9.0. Oxidation capacity was considerably enhanced via the removal of electrons from 4-aminophenylarsonic acid to Mn(VII) after the creation of its radical intermediate and further change in Mn(III) to Mn(II) in the solution. The results showed that Mn(VII) played a crucial role in 4-aminophenylarsonic acid degradation at a low pH (e.g., 4.0), and the oxidation process proceeded in different manners, namely, electron transfer, hydroxylation, and ring-opening. These results illustrated that Mn(VII) is an effective, economic purification process to mitigate 4-aminophenylarsonic acid generated from poultry waste.

Acidic permanganate oxidation of sulfamethoxazole by stepwise electron-proton transfer.

Permanganate is a versatile chemical oxidant, and has undergone a dramatic evolution toward deep insight into its reaction mechanism. However, the hydrogen abstraction of the NH bond by permanganate remains unclear. We studied the permanganate oxidation of the emerging micropollutant sulfamethoxazole in acidic aqueous solution. The reaction followed autocatalytic kinetics and demonstrated first-order with respect to each reactant. The presence of HMnO4 accelerated the reaction rate, which was four orders of magnitude higher than that of MnO4-. Based on the identified products, the rate-limiting step was determined to be simple NH bond oxidation by metal-oxo species permanganate. The mechanism was then studied computationally by density functional theory (DFT) using ammonia as the simplest model. Results showed that the NH bond oxidation by MnO4- (32.86 kcal/mol) was a concerted mechanism similar to that of CH bond oxidation, whereas HMnO4 oxidation of the NH bond (10.44 kcal/mol) was a stepwise electron-proton transfer. This reminds us that coordination of Brønsted acid could not only produce the stronger electrophile but also change the reaction mode by avoiding the bond cleavage in electron transfer process.

Oxidative removal of quinclorac by permanganate through a rate-limiting [3 + 2] cycloaddition reaction.

Quinclorac, a widely used herbicide in agriculture, has been recognized as an emerging environmental pollutant owing to its long persistence and potential risk to humans. However, no related information is available on the degradation of quinclorac by employing oxidants. Herein, the reactivity of quinclorac with permanganate was systematically investigated in water by combining experimental and computational approaches. The reaction followed overall second-order kinetics pointing to a bimolecular rate-limiting step. The second-order rate constant was found to be 3.47 × 10-3 M-1 s-1 at 25 °C, which was independent of pH over the range from 5 to 9 and was dependent on temperature over the range from 19 to 35 °C. The initial product was identified by UPLC-Q-TOF-MS to be mono-hydroxylated quinclorac, which was more susceptible to further oxidation. The result could be supported by the complete simulation of the reaction process in DFT calculations, indicating the [3 + 2] cycloaddition oxidation of the benzene ring in the rate-limiting step. The plausible mechanism was then proposed, accompanied by the analysis of the HOMO indicating the hydroxylation position and of the ESP suggesting a more electron-rich moiety. Considering the high effectiveness and low toxicity, permanganate oxidation was considered to be a very promising technique for removing quinclorac from aquatic environments.

Transformation of para arsanilic acid by manganese oxide: Adsorption, oxidation, and influencing factors.

Aromatic organoarsenic compounds tend to transform into more mobile toxic inorganic arsenic via several processes, and can inadvertently spread toxic inorganic arsenic through the environment to water sources. To gain insight into the transformation mechanisms, we herein investigated how the process of para arsanilic acid (p-ASA) transformation works in detail on the surface of adsorbents by comparing it with phenylarsonic acid (PA) and aniline, which have similar chemical structures. In contrast to the values of 0.23 mmol g-1 and 0.68 mmol g-1 for PA and aniline, the maximum adsorption capacity was determined to be 0.40 mmol g-1 for p-ASA at pH 4.0. The results of FTIR and XPS spectra supported the presence of a protonated amine, resulting in a suitable condition for the oxidation of p-ASA. Based on the combined results of UV-spectra and UPLC-Q-TOF-MS, we confirmed that the adsorbed p-ASA was first oxidized through the transfer of one electron from p-ASA on MnO2 surface to form a radical intermediate, which through further hydrolysis and coupling led to formation of benzoquinone and azophenylarsonic acid, which was identified as a major intermediate. After that, p-ASA radical intermediate was cleaved to form arsenite (III), and then further oxidized into arsenate (V) with the release of manganese (Mn) into solution, indicating a heterogeneous oxidation process.

Permanganate oxidation of diclofenac: The pH-dependent reaction kinetics and a ring-opening mechanism.

In this work, the fate of diclofenac (DCF) during permanganate (Mn(VII)) oxidation was investigated at environmentally relevant pH conditions (from 5 to 9). The batch experiments showed that the kinetics of the Mn(VII)/DCF reaction follows a second-order rate law with an apparent rate constant of 1.57±0.02 M(-1) s(-1) at pH 7 and 20 °C. The half-value of DCF was calculated to be 37.5 min, when the concentration of Mn(VII) (0.4 mM) was 20-fold excess of DCF. The pH-dependence of the reaction kinetics was investigated, and the DCF reactivity with Mn(VII) was found to decrease with increasing pH. The second-order rate constants were then quantitatively described by incorporating the species distribution of DCF. A lower reactivity of the anionic DCF (DCF(-)) in comparison with its neutral counterpart (DCF(0)) was most likely attributable to the interaction between the ionized carboxylate group and amine nitrogen position, which can reduce the nucleophilicity of amine nitrogen by inductive and resonance effects. Moreover, a range of degradation products and the corresponding structures were proposed on the basis of the LC-Q-TOF-MS analysis. A detailed ring-opening reaction mechanism was proposed as follows: Mn(VII) acts as an electrophile to attack the amine moiety, leading to the formation of the primary intermediate products 2,6-dichloroaniline and 5-hydroxy-diclofenac, which can be further transformed. The further degradation proceeded through a multistep process including ring-opening, decarboxylation, hydroxylation, and cyclation reactions.

Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products.