Oxidation of cefazolin by potassium permanganate: Transformation products and plausible pathways

Li, Liping; Wei, Dongbin; Wei, Guohua; Du, Yuguo

doi:10.1016/j.chemosphere.2016.01.117

Cited by 24 publications

(13 citation statements)

References 46 publications

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“…As an oxidant, PMS is expected to attack the atoms/moiety with available electrons. The thioether sulfur in the six- or five-membered ring, and the double bond in the six-membered dihydrothiazine ring are electron-rich and thus are regarded as potential reactive sites for various oxidants such as SO 4 •– , O 3 , and MnO 4 – . If present, the phenylglycine primary amine on the side chain is also electron-rich, reactive toward oxidants such as Cu(II) and ferrate(VI) .…”

Section: Resultsmentioning

confidence: 99%

“…29,30 The β-lactam antibiotics are expected to be susceptible to oxidative degradation owing to the presence of some electron-rich moieties, for example, primary amine and thioether sulfur. 31 Indeed, certain β-lactam antibiotics showed considerable reactivity with various oxidants, such as KMnO 4 , 32 ClO 2 , 33 ferrate (VI), 34 ozone, 35 and peracetic acid. 36…”

Section: Somentioning

confidence: 99%

“…Various techniques have been explored to eliminate β-lactam antibiotics, including membrane separation, activated carbon adsorption, photodegradation, and biological degradation. , The β-lactam antibiotics are expected to be susceptible to oxidative degradation owing to the presence of some electron-rich moieties, for example, primary amine and thioether sulfur . Indeed, certain β-lactam antibiotics showed considerable reactivity with various oxidants, such as KMnO 4 , ClO 2 , ferrate (VI), ozone, and peracetic acid . SO 4 •– generated from UV/PDS was very reactive toward β-lactam antibiotics .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Selective Transformation of β-Lactam Antibiotics by Peroxymonosulfate: Reaction Kinetics and Nonradical Mechanism

Chen

Fang

Xia

et al. 2018

Environ. Sci. Technol.

164

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While the β-lactam antibiotics are known to be susceptible to oxidative degradation by sulfate radical (SO), here we report that peroxymonosulfate (PMS) exhibits specific high reactivity toward β-lactam antibiotics without SO generation for the first time. Apparent second-order reaction constants (k) were determined for the reaction of PMS with three penicillins, five cephalosporins, two carbapenems, and several structurally related chemicals. The pH-dependency of k could be well modeled based on species-specific reactions. On the basis of reaction kinetics, stoichiometry, and structure-activity assessment, the thioether sulfur, on the six- or five-membered rings (penicillins and cephalosporins) and the side chain (carbapenems), was the main reaction site for PMS oxidation. Cephalosporins were more reactive toward PMS than penicillins and carbapenems, and the presence of a phenylglycine side chain significantly enhanced cephalosporins' reactivity toward PMS. Product analysis indicated oxidation of β-lactam antibiotics to two stereoisomeric sulfoxides. A radical scavenging study and electron paramagnetic resonance (EPR) technique confirmed lack of involvement of radical species (e.g., SO). Thus, the PMS-induced oxidation of β-lactam antibiotics was proposed to proceed through a nonradical mechanism involving direct two-electron transfer along with the heterolytic cleavage of the PMS peroxide bond. The new findings of this study are important for elimination of β-lactam antibiotic contamination, because PMS exhibits specific high reactivity and suffers less interference from the water matrix than the radical process.

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Section: Resultsmentioning

confidence: 99%

Section: Somentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Selective Transformation of β-Lactam Antibiotics by Peroxymonosulfate: Reaction Kinetics and Nonradical Mechanism

Chen

Fang

Xia

et al. 2018

Environ. Sci. Technol.

164

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“…The CFX-sulfoxide products were generated by the electrophilic attack of the positively charged Mn atom in PM on the thioether sulfur to form Mn-sulfur intermediate 1. Subsequently, a pair of electrons of sulfur were donated to a d-orbital of Mn, inducing the formation of a coordinate covalent intermediate 2, which were further decomposed to sulfoxide products by rearrangement [ 33 ] ( Figure 5 , scheme 1). For the 379 product, the double bond on the six-membered ring was the reaction site for PM oxidation.…”

Section: Resultsmentioning

confidence: 99%

“…The positively charged Mn electrophile attacked the unsaturated C=C bond on the ring, and then forming cyclic hypomanganate(V) ester (intermediate 3) via an activated organometallic complex. Afterwards, the cyclic manganite(VI) ester (intermediate 4) was generated from the cyclic hypomanganate(V) ester by the oxidation of PM, and subsequently hydrolyzed to generate di-ketone-containing product [ 33 ] ( Figure 5 , scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Oxidation of Cefalexin by Permanganate: Reaction Kinetics, Mechanism, and Residual Antibacterial Activity

et al. 2018

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The oxidation of cefalexin (CFX), a commonly used cephalosporin antibiotic, was investigated by permanganate (PM) in water. Apparent second-order rate constant of the reaction between CFX and PM was determined to be 12.71 ± (1.62) M−1·s−1 at neutral pH. Lower pH was favorable for the oxidation of CFX by PM. The presence of Cl− and HCO3− could enhance PM-induced oxidation of CFX, whereas HA had negligible effect on CFX oxidation by PM. PM-induced oxidation of CFX was also significant in the real wastewater matrix. After addition of bisulfite (BS), PM-induced oxidation was significantly accelerated owing to the generation of Mn(III) reactive species. Product analysis indicated oxidation of CFX to three products, with two stereoisomeric sulfoxide products and one di-ketone product. The thioether sulfur and double bond on the six-membered ring were the reactive sites towards PM oxidation. Antibacterial activity assessment indicated that the activity of CFX solution was significantly reduced after PM oxidation.

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Remediation of TCE-contaminated groundwater using KMnO4 oxidation: laboratory and field-scale studies

Yang¹,

Dong

et al. 2018

Environ Sci Pollut Res

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The objectives of this study were to (1) conduct laboratory bench and column experiments to determine the oxidation kinetics and optimal operational parameters for trichloroethene (TCE)-contaminated groundwater remediation using potassium permanganate (KMnO) as oxidant and (2) to conduct a pilot-scale study to assess the efficiency of TCE remediation by KMnO oxidation. The controlling factors in laboratory studies included soil oxidant demand (SOD), molar ratios of KMnO to TCE, KMnO decay rate, and molar ratios of NaHPO to KMnO for manganese dioxide (MnO) production control. Results show that a significant amount of KMnO was depleted when it was added in a soil/water system due to the existence of natural soil organic matters. The presence of natural organic material in soils can exert a significant oxidant demand thereby reducing the amount of KMnO available for the destruction of TCE as well as the overall oxidation rate of TCE. Supplement of higher concentrations of KMnO is required in the soil systems with high SOD values. Higher KMnO application resulted in more significant H and subsequent pH drop. The addition of NaHPO could minimize the amount of produced MnO particles and prevent the clogging of soil pores, and TCE oxidation efficiency would not be affected by NaHPO. To obtain a complete TCE removal, the amount of KMnO used to oxidize TCE needs to be higher than the theoretical molar ratio of KMnO to TCE based on the stoichiometry equation. Relatively lower oxidation rates are obtained with lower initial TCE concentrations. The half-life of TCE decreased with increased KMnO concentrations. Results from the pilot-scale study indicate that a significant KMnO decay occurs after the injection due to the reaction of KMnO with soil organic matters, and thus, the amount of KMnO, which could be transported from the injection point to the downgradient area, would be low. The effective influence zone of the KMnO oxidation was limited to the KMnO injection area (within a 3-m radius zone). Migration of KMnO to farther downgradient area was limited due to the reaction of KMnO to natural organic matters. To retain a higher TCE removal efficiency, continuous supplement of high concentrations of KMnO is required. The findings would be useful in designing an in situ field-scale ISCO system for TCE-contaminated groundwater remediation using KMnO as the oxidant.

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Oxidation of cefazolin by potassium permanganate: Transformation products and plausible pathways

Cited by 24 publications

References 46 publications

Selective Transformation of β-Lactam Antibiotics by Peroxymonosulfate: Reaction Kinetics and Nonradical Mechanism

Selective Transformation of β-Lactam Antibiotics by Peroxymonosulfate: Reaction Kinetics and Nonradical Mechanism

Oxidation of Cefalexin by Permanganate: Reaction Kinetics, Mechanism, and Residual Antibacterial Activity

Remediation of TCE-contaminated groundwater using KMnO4 oxidation: laboratory and field-scale studies

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