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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 HISmore »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.« less
2. Mechanism of proton transfer in class A β-lactamase catalysis and inhibition by avibactam

   https://doi.org/10.1073/pnas.1922203117  

   Pemberton, Orville A. ; Noor, Radwan E. ; Kumar M. V., Vasantha ; Sanishvili, Ruslan ; Kemp, M. Trent ; Kearns, Fiona L. ; Woodcock, H. Lee ; Gelis, Ioannis ; Chen, Yu ( March 2020 , Proceedings of the National Academy of Sciences)

   Gram-negative bacteria expressing class A β-lactamases pose a serious health threat due to their ability to inactivate all β-lactam antibiotics. The acyl–enzyme intermediate is a central milestone in the hydrolysis reaction catalyzed by these enzymes. However, the protonation states of the catalytic residues in this complex have never been fully analyzed experimentally due to inherent difficulties. To help unravel the ambiguity surrounding class A β-lactamase catalysis, we have used ultrahigh-resolution X-ray crystallography and the recently approved β-lactamase inhibitor avibactam to trap the acyl–enzyme complex of class A β-lactamase CTX-M-14 at varying pHs. A 0.83-Å-resolution CTX-M-14 complex structure at pH 7.9more »revealed a neutral state for both Lys73 and Glu166. Furthermore, the avibactam hydroxylamine-O-sulfonate group conformation varied according to pH, and this conformational switch appeared to correspond to a change in the Lys73 protonation state at low pH. In conjunction with computational analyses, our structures suggest that Lys73 has a perturbed acid dissociation constant (pK_a) compared with acyl–enzyme complexes with β-lactams, hindering its function to deprotonate Glu166 and the initiation of the deacylation reaction. Further NMR analysis demonstrated Lys73 pK_ato be ∼5.2 to 5.6. Together with previous ultrahigh-resolution crystal structures, these findings enable us to follow the proton transfer process of the entire acylation reaction and reveal the critical role of Lys73. They also shed light on the stability and reversibility of the avibactam carbamoyl acyl–enzyme complex, highlighting the effect of substrate functional groups in influencing the protonation states of catalytic residues and subsequently the progression of the reaction.

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3. Rapid Formation of Sulfate Aerosols through Aqueous Aerosol Oxidation by Isoprene Hydroxy Hydroperoxides (ISOPOOH)

   YUE ZHANG, Jin Yan ( January 2020 , 38th Annual Meeting American Association for Aerosol Research)

   Abstract Number: 530 Working Group: Aerosol Chemistry Abstract Isoprene is the most abundant non-methane volatile organic compound (VOC) emitted globally. Isomeric isoprene hydroxy hydroperoxides (ISOPOOH), key photooxidation products of isoprene, likely comprise the second most abundant class of peroxides in the atmosphere, following hydrogen peroxide. Studies have shown that hydrogen peroxide plays important roles in the formation of inorganic sulfates in cloud water mimics. However, the potential for ISOPOOH to play a role in sulfate formation in wet aerosol oxidation from reduced sulfur species (such as inorganic sulfite) is not well understood. This study systematically investigates the reaction kinetics andmore »products of ISOPOOH reacting with particle phase inorganic sulfite and discusses implications to the sulfate aerosol budget. In order to examine the reaction kinetics of ISOPOOH with aqueous sulfite, ammonium bisulfite particles were injected into the UNC indoor environmental chamber under dark conditions with 70% RH. After the inorganic sulfite concentrations stabilized, selected concentrations of gas-phase 1,2-ISOPOOH was injected into the chamber to initiate the multiphase reaction. The gas-phase ISOPOOH and particle-phase species were sampled with online instruments, including a chemical ionization mass spectrometer (CIMS), an aerosol chemical speciation monitor (ACSM), and a particle-into-liquid sampler (PILS), and also collected by Teflon filters for offline molecular-level analyses by an ultra-performance liquid chromatography coupled to an electrospray ionization high resolution quadrupole time-of-flight mass spectrometry (UPLC-ESI-HR-QTOFMS). Results show that a significant amount of inorganic sulfite was converted to inorganic sulfate and organosulfates in the particle phase at relatively fast reaction rates, altering the chemical and physical properties of the particles including phase state, pH, reactivity, and composition. Given the high abundance and water solubility of ISOPOOH in the ambient environment, the multiphase reactions examined in our study indicate significant impacts of ISOPOOH on the atmospheric lifecycle of sulfur and the physicochemical properties of ambient particles. Access: https://aaarabstracts.com/2020/viewabstract.php?pid=530« less
4. 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.
5. Effects of residual disinfectants on the redox speciation of lead( ii )/( iv ) minerals in drinking water distribution systems

   https://doi.org/10.1039/d0ew00706d  

   Avasarala, Sumant ; Orta, John ; Schaefer, Michael ; Abernathy, Macon ; Ying, Samantha ; Liu, Haizhou ( February 2021 , Environmental Science: Water Research & Technology)

   This study investigated the reaction kinetics on the oxidative transformation of lead( ii ) minerals by free chlorine (HOCl) and free bromine (HOBr) in drinking water distribution systems. According to chemical equilibrium predictions, lead( ii ) carbonate minerals, cerussite PbCO 3(s) and hydrocerussite Pb 3 (CO 3 ) 2 (OH) 2(s) , and lead( ii ) phosphate mineral, chloropyromorphite Pb 5 (PO 4 ) 3 Cl (s) are formed in drinking water distribution systems in the absence and presence of phosphate, respectively. X-ray absorption near edge spectroscopy (XANES) data showed that at pH 7 and a 10 mM alkalinity, themore »majority of cerussite and hydrocerussite was oxidized to lead( iv ) mineral PbO 2(s) within 120 minutes of reaction with chlorine (3 : 1 Cl 2  : Pb( ii ) molar ratio). In contrast, very little oxidation of chloropyromorphite occurred. Under similar conditions, oxidation of lead( ii ) carbonate and phosphate minerals by HOBr exhibited a reaction kinetics that was orders of magnitude faster than by HOCl. Their end oxidation products were identified as mainly plattnerite β-PbO 2(s) and trace amounts of scrutinyite α-PbO 2(s) based on X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. A kinetic model was established based on the solid-phase experimental data. The model predicted that in real drinking water distribution systems, it takes 0.6–1.2 years to completely oxidize Pb( ii ) minerals in the surface layer of corrosion scales to PbO 2(s) by HOCl without phosphate, but only 0.1–0.2 years in the presence of bromide (Br − ) due the catalytic effects of HOBr generation. The model also predicts that the addition of phosphate will significantly inhibit Pb( ii ) mineral oxidation by HOCl, but only be modestly effective in the presence of Br − . This study provides insightful understanding on the effect of residual disinfectant on the oxidation of lead corrosion scales and strategies to prevent lead release from drinking water distribution systems.« less