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1. Oxidation of Amino Acids by Peracetic Acid: Reaction Kinetics, Pathways and Theoretical Calculations

   https://doi.org/https://doi.org/10.1016/j.wroa.2018.09.002  

   Du, P.; Liu, W.; Cao, H.; Zhao, H.; Huang, C.-H. (January 2018, Water research. X)

   Peracetic acid (PAA) is a sanitizer with increasing use in food, medical and water treatment industries. Amino acids are important components in targeted foods for PAA treatment and ubiquitous in natural waterbodies and wastewater effluents as the primary form of dissolved organic nitrogen. To better understand the possible reactions, this work investigated the reaction kinetics and transformation pathways of selected amino acids towards PAA. Experimental results demonstrated that most amino acids showed sluggish reactivity to PAA except cysteine (CYS), methionine (MET), and histidine (HIS). CYS showed the highest reactivity with a very rapid reaction rate. Reactions of MET and HIS with PAA followed second-order kinetics with rate constants of 4.6 ± 0.2, and 1.8 ± 0.1 M−1s−1 at pH 7, respectively. The reactions were faster at pH 5 and 7 than at pH 9 due to PAA speciation. Low concentrations of H2O2 coexistent with PAA contributed little to the oxidation of amino acids. The primary oxidation products of amino acids with PAA were [O] addition compounds on the reactive sites at thiol, thioether and imidazole groups. Theoretical calculations were applied to predict the reactivity and regioselectivity of PAA electrophilic attacks on amino acids and improved mechanistic understanding. As an oxidative disinfectant, the reaction of PAA with organics to form byproducts is inevitable; however, this study shows that PAA exhibits lower and more selective reactivity towards biomolecules such as amino acids than other common disinfectants, causing less concern of toxic disinfection byproducts. This attribute may allow greater stability and more targeted actions of PAA in various applications. 

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2. Lewis-Base-Catalyzed Reductive Aldol Reaction To Access Quaternary Carbons

   https://doi.org/doi.org/10.1021/acs.orglett.8b00507  

   DePorre, Y.C.; Annand, J.R.; Bar, S.; Schindler, C.S. (April 2018, Organic letters)

   A synthetic method for the efficient construction of β-hydroxylactones and lactams bearing α-quaternary carbon centers is described. This transformation relies on an electronically differentiated Lewis base catalyst, which is uniquely capable of promoting a reductive aldol reaction of α,α-disubstituted and α,α,β-trisubstituted enones. This approach provides a valuable synthetic alternative for carbon–carbon bond formation in complex molecular settings due to its orthogonal reactivity compared to that of traditional aldol reactions. Based on this method described herein, lactones, lactams, and morpholine amides bearing α-quaternary carbon centers are accessible in yields up to 85% and 50:1 dr. 

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3. Chloramination of Nitromethane: Incomplete Chlorination and Unexpected Substitution Reaction

   https://doi.org/10.1021/acs.est.2c09821  

   Shi, Jiaming Lily; Kim, Euna; Cardosa, Georgia B.; McCurry, Daniel L. (May 2023, Environmental Science & Technology)

   Ozone is commonly used as a pre-disinfectant in potable water reuse treatment trains. Nitromethane was recently found as a ubiquitous ozone byproduct in wastewater, and the key intermediate toward chloropicrin during subsequent secondary disinfection of ozonated wastewater effluent with chlorine. However many utilities have switched from free chlorine to chloramines as a secondary disinfectant. The reaction mechanism and kinetics of nitromethane transformation by chloramines, unlike free chlorine, are unknown. In this work, the kinetics, mechanism, and products of nitromethane chloramination were studied. The expected principal product was chloropicrin, because chloramines are commonly assumed to react similarly, although more slowly, compared to free chlorine. Different molar yields of chloropicrin were observed at acidic, neutral, and basic conditions, and surprisingly, transformation products other than chloropicrin were found. Monochloronitromethane and dichloronitromethane were detected at basic pH, and the mass balance was initially poor at neutral pH. Much of the missing mass was later attributed to nitrate formation, from a newly-identified pathway involving monochloramine reacting as a nucleophile rather than halogenating agent, through a presumed SN2 mechanism. The study indicates that nitromethane chloramination, unlike chlorination, is likely to produce a range of products, whose speciation is a function of pH and reaction time. 

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4. Sunlight photolysis of SARS-CoV-2 N1 gene target in the water environment: considerations for the environmental surveillance of wastewater-impacted surface waters

   https://doi.org/10.2166/wh.2023.091  

   Dunn, Fiona B.; Silverman, Andrea I. (August 2023, Journal of Water and Health)

   Abstract Wastewater surveillance of SARS-CoV-2 has been used around the world to supplement clinical testing data for situational awareness of COVID-19 disease trends. Many regions of the world lack centralized wastewater collection and treatment infrastructure, which presents additional considerations for wastewater surveillance of SARS-CoV-2, including environmental decay of the RT-qPCR gene targets used for quantification of SARS-CoV-2 virions. Given the role of sunlight in the environmental decay of RNA, we evaluated sunlight photolysis kinetics of the N1 gene target in heat-inactivated SARS-CoV-2 with a solar simulator under laboratory conditions. Insignificant photolysis of the N1 target was observed in a photosensitizer-free matrix. Conversely, significant decay of the N1 target was observed in wastewater at a shallow depth (<1 cm). Given that sunlight irradiance is affected by several environmental factors, first-order decay rate models were used to evaluate the effect of water column depth, time of the year, and latitude on decay kinetics. Decay rate constants were found to decrease significantly with greater depth of the well-mixed water column, at high latitudes, and in the winter. Therefore, sunlight-mediated decay of the N1 gene target is likely to be minimal, and is unlikely to confound results from wastewater-based epidemiology programs utilizing wastewater-impacted surface waters. 

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5. Unveiling the environmental significance of acetylperoxyl radical: Reactivity quantification and kinetic modeling

   https://doi.org/10.1093/pnasnexus/pgae330  

   Wang, Junyue; Schaefer, Thomas; Lisouskaya, Aliaksandra; Firak, Daniele_S; Xin, Xiaoyue; Meng, Lingjun; Herrmann, Hartmut; Sharma, Virender_K; Huang, Ching-Hua; Xu, ed., Yi-Jun (August 2024, PNAS Nexus)

   Abstract Acetylperoxyl radical (CH3C(O)OO•) is among highly reactive organic radicals which are known to play crucial roles in atmospheric chemistry, aqueous chemistry and, most recently, peracetic acid (PAA)-based advanced oxidation processes. However, fundamental knowledge for its reactivity is scarce and severely hampers the understanding of relevant environmental processes. Herein, three independent experimental approaches were exploited for revelation and quantification of the reaction rates of acetylperoxyl radical. First, we developed and verified laser flash photolysis of biacetyl, ultraviolet (UV) photolysis of biacetyl, and pulse radiolysis of acetaldehyde, each as a clean source of CH3C(O)OO•. Then, using competition kinetics and selection of suitable probe and competitor compounds, the rate constants between CH3C(O)OO• and compounds of diverse structures were determined. The three experimental approaches complemented in reaction time scale and ease of operation, and provided cross-validation of the rate constants. Moreover, the formation of CH3C(O)OO• was verified by spin-trapped electron paramagnetic resonance, and potential influence of other reactive species in the systems was assessed. Overall, CH3C(O)OO• displays distinctively high reactivity and selectivity, reacting especially favorably with naphthyl and diene compounds (k ∼ 107–108 M−1 s−1) but sluggishly with N- and S-containing groups. Significantly, we demonstrated that incorporating acetylperoxyl radical-oxidation reactions significantly improved the accuracy in modeling the degradation of environmental micropollutants by UV/PAA treatment. This study is among the most comprehensive investigation for peroxyl radical reactivity to date, and establishes a robust methodology for investigating organic radical chemistry. The determined rate constants strengthen kinetic databases and improve modeling accuracy for natural and engineered systems. 

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