This study investigated the expediated transformation of halophenols in the presence of nitrite (NO) under slightly acidic conditions in ice, whereas such transformation was negligible in liquid water at 4 °C. We proposed that this phenomenon was attributed to the freeze-concentration effect, incurring a pH drop and the aggregation of NO and halophenols within the liquid-like grain boundary layer amid ice crystals. Within this micro-environment, NO underwent protonation to generate reactive nitrous acid (HNO) and nitrosonium ions (NO) that facilitate the nitration and oxidation of halophenols. When 10 μМ halophenol was treated by freezing in the presence of 5 μМ NO, the total yields of nitrated products reached 2.4 μМ and 1.4 μМ within 12 h for 2-chlorophenol (2CP) and 2-bromophenol (2BP), respectively. NO drove oxidative coupling reactions, generating hydroxyl polyhalogenated diphenyl ethers (OH-PBDEs) and hydroxyl polyhalogenated diphenyls via C-O or C-C coupling. These two pathways were intricately intertwined. The presence of natural organic matter (NOM) mitigated the formation of nitrated products and completely suppressed the coupling products. This study offers valuable insights into the fate of halophenols in ice and suggests potential pathways for the formation of nitrophenolic compounds and OH-PBDEs in natural cold environments. These findings also open up a new avenue in environmental chemistry research.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1016/j.watres.2024.122158 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Nitrite facilitated transformation of halophenols in ice.
Water Res
October 2024
Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing, 210095, China. Electronic address:
This study investigated the expediated transformation of halophenols in the presence of nitrite (NO) under slightly acidic conditions in ice, whereas such transformation was negligible in liquid water at 4 °C. We proposed that this phenomenon was attributed to the freeze-concentration effect, incurring a pH drop and the aggregation of NO and halophenols within the liquid-like grain boundary layer amid ice crystals. Within this micro-environment, NO underwent protonation to generate reactive nitrous acid (HNO) and nitrosonium ions (NO) that facilitate the nitration and oxidation of halophenols.
View Article and Find Full Text PDFDearomative [2 + 1] Spiroannulation of Bromophenols with Electron-Deficient Alkenes.
J Org Chem
June 2024
State Key Laboratory of Antiviral Drugs, Pingyuan Laboratory, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, Henan, China.
A base-assisted dearomative [2 + 1] spiroannulation of /-bromophenols with activated olefins (methylenemalonates) to construct various cyclopropyl spirocyclohexadienone skeletons is reported. Furthermore, several other halophenols (X = Cl, I) were also tolerated in this process. Control experiments reveal a dearomative Michael addition of phenols at their halogenated positions to methylenemalonates, followed by intramolecular radical-based S1 dehalogenative cyclopropanation.
View Article and Find Full Text PDFDisinfection byproducts and their cytotoxicity contribution from dissolved black carbon in source water during chlor(am)ination.
Sci Total Environ
June 2024
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China. Electronic address:
Dissolved black carbon (DBC), the soluble component of black carbon, which mainly comes from the incomplete combustion of fossil fuels or biomass, is widely spread in source water and significantly contributes to the formation of dissolved organic matter (DOM). However, the origin of DBC in different types of source water in China has not been well studied, as well as its subsequent transformation and toxicity contribution during disinfection of source water DOM by chlor(am)ine. In this study, DBC from 17 different source water in East China at different seasons was collected.
View Article and Find Full Text PDFUnprecedented 100% conversion from pyridinic to pyrrolic nitrogen configuration for electrochemically active nitrogen-doped carbon materials.
J Colloid Interface Sci
May 2024
State Key Laboratory of Metastable Materials Science and Technology, Hebei Key Laboratory of Heavy Metal Deep-Remediation in Water and Resource Reuse, School of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao, Hebei 066004, China. Electronic address:
Nitrogen-doped carbons with promising electrochemical performance exhibit a strong dependence on nitrogen configuration. Therefore, accurate control of nitrogen configurations is crucial to clarify their influence. Unfortunately, there is still no well-defined conversion route to finely control nitrogen configuration.
View Article and Find Full Text PDFDearomatization/Spiroannulation of Halophenols Enables the Forging of Contiguous Quaternary Carbon Cyclohexadienones.
Org Lett
November 2023
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710127, China.
A dearomatization/spiroannulation process has been successfully achieved between simple halophenols and α,β-unsaturated olefins under mild reaction conditions. This transformation addresses the chemoselectivity issue in the dearomatizative transformation of phenol scaffolds (6π-electron) caused by the SE process, enabling the construction of versatile cyclohexadienone frameworks containing contiguous quaternary all-carbon centers in high yields. Further studies have provided valuable insights into the process, revealing that debromination/spiroannulation occurs through the S1 pathway.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!