scholarly journals Selective Generation of Singlet Oxygen in Chloride Accelerated Copper Fenton Chemistry

Author(s):  
Andrew Carrier ◽  
Collins Nganou ◽  
David Oakley ◽  
Yongli Chen ◽  
Ken Oakes ◽  
...  

<p>Singlet oxygen (<sup>1</sup>O<sub>2</sub>), a widely used reactive oxygen species (ROS) in industry and biomedical applications, plays a fundamental role throughout nature. We report a novel method to generate <sup>1</sup>O<sub>2</sub>selectively and efficiently through copper-based Fenton chemistry under circumneutral conditions enhanced by chloride as co-catalyst, with reactivity completely different than that observed in classical iron-based Fenton chemistry. The mechanism of its formation was elucidated through the kinetic studies of orthogonally reactive reporter molecules, i.e., singlet oxygen sensor green, 4-hydroxy-2,2,6,6-tetramethylpiperidine, and phenol, and selective ROS quenchers. This method selectively generates <sup>1</sup>O<sub>2</sub><i>in situ</i>neither relying on photosensitization nor resulting in side reactions, and together with the mechanistic understanding of the Cu-Fenton reaction, not only opens new possibilities in many industries, such as organic synthesis and antimicrobial treatments, but also provides insight into Cu and H<sub>2</sub>O<sub>2</sub>containing chemical, environmental, and biological systems.</p>

2018 ◽  
Author(s):  
Andrew Carrier ◽  
Collins Nganou ◽  
David Oakley ◽  
Yongli Chen ◽  
Ken Oakes ◽  
...  

<p>Singlet oxygen (<sup>1</sup>O<sub>2</sub>), a widely used reactive oxygen species (ROS) in industry and biomedical applications, plays a fundamental role throughout nature. We report a novel method to generate <sup>1</sup>O<sub>2</sub>selectively and efficiently through copper-based Fenton chemistry under circumneutral conditions enhanced by chloride as co-catalyst, with reactivity completely different than that observed in classical iron-based Fenton chemistry. The mechanism of its formation was elucidated through the kinetic studies of orthogonally reactive reporter molecules, i.e., singlet oxygen sensor green, 4-hydroxy-2,2,6,6-tetramethylpiperidine, and phenol, and selective ROS quenchers. This method selectively generates <sup>1</sup>O<sub>2</sub><i>in situ</i>neither relying on photosensitization nor resulting in side reactions, and together with the mechanistic understanding of the Cu-Fenton reaction, not only opens new possibilities in many industries, such as organic synthesis and antimicrobial treatments, but also provides insight into Cu and H<sub>2</sub>O<sub>2</sub>containing chemical, environmental, and biological systems.</p>


2014 ◽  
Vol 86 (6) ◽  
pp. 945-952 ◽  
Author(s):  
Erbay Kalay ◽  
Hamdullah Kılıç ◽  
Mustafa Catir ◽  
Murat Cakici ◽  
Cavit Kazaz

AbstractA novel method for the production of singlet oxygen from H2O2 was developed. A combination of iodoarene (ArI), methyltrioxorhenium (MTO), and H2O2 in the presence of pyridine as the co-catalyst efficiently produced singlet molecular oxygen (1O2) under biphasic conditions. The existence of 1O2 was demonstrated by trapping experiments with aromatic dienes, 1,3-cyclodienes, and alkenes. The mechanism of 1O2 production from the iodoarene/MTO/35 % H2O2 system and the reaction scope was also discussed.


2016 ◽  
Vol 7 (3) ◽  
pp. 1862-1866 ◽  
Author(s):  
Youyong Yuan ◽  
Chong-Jing Zhang ◽  
Shidang Xu ◽  
Bin Liu

A probe for the in situ monitoring of singlet oxygen generation during targeted theranostic photodynamic therapy is developed based on a photosensitizer with aggregation-induced emission (AIE) characteristics and conjugated to a fluorogenic rhodol dye via a singlet oxygen cleavable linker.


1999 ◽  
Author(s):  
Philip B. Keating ◽  
Michael F. Hinds ◽  
Steven J. Davis

2020 ◽  
Vol 74 (11) ◽  
pp. 866-870
Author(s):  
Lewis C. H. Maddock ◽  
Alan Kennedy ◽  
Eva Hevia

While fluoroaryl fragments are ubiquitous in many pharmaceuticals, the deprotonation of fluoroarenes using organolithium bases constitutes an important challenge in polar organometallic chemistry. This has been widely attributed to the low stability of the in situ generated aryl lithium intermediates that even at –78 °C can undergo unwanted side reactions. Herein, pairing lithium amide LiHMDS (HMDS = N{SiMe3}2) with FeII(HMDS)2 enables the selective deprotonation at room temperature of pentafluorobenzene and 1,3,5-trifluorobenzene via the mixed-metal base [(dioxane)LiFe(HMDS)3] (1) (dioxane = 1,4-dioxane). Structural elucidation of the organometallic intermediates [(dioxane)Li(HMDS)2Fe(ArF)] (ArF = C6F5, 2; 1,3,5-F3-C6H2, 3) prior electrophilic interception demonstrates that these deprotonations are actually ferrations, with Fe occupying the position previously filled by a hydrogen atom. Notwithstanding, the presence of lithium is essential for the reactions to take place as Fe II (HMDS)2 on its own is completely inert towards the metallation of these substrates. Interestingly 2 and 3 are thermally stable and they do not undergo benzyne formation via LiF elimination.


Author(s):  
Hongtao Zhong ◽  
Chao Yan ◽  
Chu C. Teng ◽  
Timothy Y. Chen ◽  
Gerard Wysocki ◽  
...  

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Marco Veneranda ◽  
Nagore Prieto-Taboada ◽  
Jose Antonio Carrero ◽  
Ilaria Costantini ◽  
Aitor Larrañaga ◽  
...  

AbstractThe conservation of iron objects exposed to marine aerosol is threatened by the formation of akaganeite, a highly unstable Cl-bearing corrosion phase. As akaganeite formation is responsible of the exfoliation of the rust layer, chlorides trigger a cyclic alteration phenomenon that often ends with the total consumption of the iron core. To prevent this degradation process, movable iron elements (e.g. archaeometallurgical artefacts) are generally immersed in alkaline dechlorination baths. Aiming to transfer this successful method to the treatment of immovable iron objects, we propose the in-situ application of alkaline solutions through the use of highly absorbent wraps. As first step of this novel research line, the present work defines the best desalination solution to be used and optimizes its extraction yield. After literature review, a screening experimental design was performed to understand the single and synergic effects of common additives used for NaOH baths. Once the most effective variables were selected, an optimization design was carried out to determine the optimal conditions to be set during treatment. According to the experimental work here presented, the use of 0.7 M NaOH solutions applied at high temperatures (above 50 °C) is recommended. Indeed, these conditions enhance chloride extraction and iron leaching inhibition, while promoting corrosion stabilization.


2021 ◽  
Vol 13 (2) ◽  
pp. 320
Author(s):  
José P. Granadeiro ◽  
João Belo ◽  
Mohamed Henriques ◽  
João Catalão ◽  
Teresa Catry

Intertidal areas provide key ecosystem services but are declining worldwide. Digital elevation models (DEMs) are important tools to monitor the evolution of such areas. In this study, we aim at (i) estimating the intertidal topography based on an established pixel-wise algorithm, from Sentinel-2 MultiSpectral Instrument scenes, (ii) implementing a set of procedures to improve the quality of such estimation, and (iii) estimating the exposure period of the intertidal area of the Bijagós Archipelago, Guinea-Bissau. We first propose a four-parameter logistic regression to estimate intertidal topography. Afterwards, we develop a novel method to estimate tide-stage lags in the area covered by a Sentinel-2 scene to correct for geographical bias in topographic estimation resulting from differences in water height within each image. Our method searches for the minimum differences in height estimates obtained from rising and ebbing tides separately, enabling the estimation of cotidal lines. Tidal-stage differences estimated closely matched those published by official authorities. We re-estimated pixel heights from which we produced a model of intertidal exposure period. We obtained a high correlation between predicted and in-situ measurements of exposure period. We highlight the importance of remote sensing to deliver large-scale intertidal DEM and tide-stage data, with relevance for coastal safety, ecology and biodiversity conservation.


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