On‐surface Fenton and Fenton‐like reactions appraised by paper spray ionization mass spectrometry

Resende, S.F.; Oliveira, B.S.; Augusti, Rodinei

doi:10.1002/jms.4252

Cited by 4 publications

(3 citation statements)

References 33 publications

(34 reference statements)

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“…In addition to iron and copper ions, other metal ions with H 2 O 2 can also form Fenton-like reactions. Augusti et al compared the efficiency of different metal ions in generating ·OH on a paper surface and found that the activity of metal ions obeyed the following order: Fe 2+ ≫ Cu 2+ > Fe 3+ , Co 2+ , Mn 2+ . Although some methods have been adopted to slow down the corrosion of transition metal species on paper by using a metal-paper isolating agent, metal complexing agent, and antioxidant, such as recombinant protein, magnesium phytate, , and 1-ethyl-3-methylimidazolium bromide (EMIMBr), , the detailed mechanism on Fenton oxidative degradation of paper is still ambiguous.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Degradation Mechanism and Antidegradation Strategy of Paper-Based Relics with Transition Metal Pigments: From the Cellobiose Model to Cellulose Paper

Yan

Yao

et al. 2023

ACS Sustainable Chem. Eng.

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Paper-based cultural relics often experience various deterioration by acid hydrolysis, alkaline degradation, and oxidative degradation during their long-term preservation. Some pigments containing transition metal species would damage the paper substrates seriously due to their possible catalytic effects on the in situ formation of hydroxyl radical (•OH) and the simultaneous occurrence of Fenton-like oxidation. By using cellobiose (the smallest unit of cellulose macromolecule) as the model, the oxidative degradation mechanism of cellulose paper is explored in the Cu 2+ -H 2 O 2 system. The •OH radical that originated from H 2 O 2 will attack the α-H atom dominantly at the C 1 position in the glucopyranose ring and promote the cleavage of the adjacent β-1,4-glycosidic bond, thus leading to the cracking of cellobiose. In addition to Cu species, the transition metal pigments containing Fe, Cr, and Hg species also exhibit relatively high catalytic activity for the degradation of cellobiose or cellulose paper via the Fenton-like oxidation. To protect paper from being oxidatively deteriorated, a series of scavengers for •OH radicals are investigated since they will not react with cellulose paper directly and have no specificity to metal ions or pigments. Remarkably, 2,5-hexanediol (2,5-HDO) not only retards the cleavage of cellulose chains but also inhibits the generation of reducible carbonyl and carboxyl groups by effectively capturing • OH generated in the Fenton-like system. Such a good performance combining its low volatility, high water solubility, and quite low impact on the paper substrates makes 2,5-HDO a novel, safe, and sustainable antidegradation agent for the conservation of pigmentcontaining paper relics.

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Section: Introductionmentioning

confidence: 99%

Oxidative Degradation Mechanism and Antidegradation Strategy of Paper-Based Relics with Transition Metal Pigments: From the Cellobiose Model to Cellulose Paper

Yan

Yao

et al. 2023

ACS Sustainable Chem. Eng.

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“…Owing to the lack of easily ionized chemical groups, general brominated organic compounds are difficult to ionize by matrix-assisted laser desorption ionization (MALDI), electrospray ionization (ESI), paper spray ionization, and other ambient ionization sources, leading to low-sensitivity in MS analysis. With the benefits of low cost, no sample pretreatment, minimal matrix effect, and high analytical efficiency, PSI-MS has been commonly used in clinical diagnosis, − environmental analysis, and reaction monitoring. ,,− To improve the sensitivity of weakly polar and nonpolar substances by MS detection, online derivatization of the target analytes has been integrated into PSI (termed as reactive PSI). Huang’s group quantitatively determined quinones in complex samples by reactive PSI-MS, where quinones were in situ derivatized with cysteamine to significantly improve the ionization efficiency of quinones.…”

Section: Introductionmentioning

confidence: 99%

Suzuki C–C Coupling in Paper Spray Ionization: Microsynthesis of Biaryls and High-Sensitivity MS Detection of Aryl Bromides

Lin

Xue

Sun

et al. 2022

J. Am. Soc. Mass Spectrom.

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Suzuki–Miyaura cross-coupling is one of the most powerful strategies for constructing biaryl compounds. However, classic Suzuki–Miyaura coupling suffers from hour-scale reaction time and competitive protodeboronation. To address these problems, a mild nonaqueous potassium trimethylsilanolate (TMSOK)-assisted Suzuki–Miyaura coupling strategy was designed for the microsynthesis of biaryls in paper spray ionization (PSI). Due to the acceleration power facilitated by microdroplet chemistry in reactive PSI, the microsynthesis of biaryls by reactive PSI was accomplished within minutes with comparable yields to the bulk, showing good substrate applicability from 32 Suzuki–Miyaura reactions of aryl bromides and aryl boronic acid/borates bearing different substituents. Based on the above TMSOK-assisted Suzuki–Miyaura coupling strategy, we further developed a high-sensitivity and selective PSI mass spectrometry (MS) method for quantitative analysis of aryl bromides, a class of environmentally persistent organic pollutants that cannot be directly detected by ambient mass spectrometry due to their low ionization efficiency. In situ derivatization of aryl bromides was achieved with aryl borates bearing quaternary ammonium groups in PSI. The proposed PSI-MS method shows good linearity over the 0.01–10 μmol L–1 range with low detection limits of 1.8–4.8 nmol L–1 as well as good applicability to the rapid determination of six aryl bromides in three environmental water samples. The proposed PSI-MS method also shows good applicability to brominated flame retardants (polybrominated diphenyls/diphenyl esters). Overall, this study provides a simple, rapid, low-cost, high-sensitivity, and high-selectivity strategy for trace aryl bromides and other brominated pollutants in real samples with minimal/no sample pretreatment.

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“…Herein, we use paper spray mass spectrometry (PS-MS), because of its unique features (e.g., simplicity, low cost, and without sample pretreatment) and success in chemical reactivity assessment, − to characterize the reaction mechanisms between triazine and H 2 S, as a function of the pH of the reaction solution. Evidences from experimental observations using high-resolution and tandem mass spectrometry identify the ionic species involved in the reaction procedures, and plausible mechanisms are proposed to elucidate the complex reaction inside the process.…”

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confidence: 99%

Elucidating the Reaction Mechanisms between Triazine and Hydrogen Sulfide with pH Variation Using Mass Spectrometry

et al. 2018

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Triazine is one of the most economical and effective scavengers for hydrogen sulfide (HS) removal, but the reaction mechanisms between triazine and HS with pH variation in solution are still poorly understood. Herein, we show that the reaction process can be directly probed by means of paper spray mass spectrometry, in which an aprotic solvent (e.g., acetonitrile) is more favorable to the observation of reaction intermediates than a protic solvent (e.g., methanol), because of hydrogen bond interaction. Varying the pH of the reaction leads to completely different reaction pathways. With the pH in the range of 5.58 to 7.73, the major product was thiadiazine. With a pH of 3.02-3.69, thiadiazine is converted to 2-(5-(2-hydroxyethyl)-1,3,5-thiadiazinan-3-yl)acetaldehyde, which differs from the traditional pathway of analogous reactions. However, as ammonia was added into the reaction and the pH was adjusted to the range 8.45-9.43, triazine readily undergoes hydrolysis, and the formed intermediate reacts with ammonia and formaldehyde generated in situ from triazine to produce 1-(2-hydroxyethyl)-3,5,7-triaza-1-azoniatricyclo [3.3.1.1]decane (HTAD). Further increasing the pH up to 10.27-11.21 leads to the decomposition of HTAD. Based on the experimental observation and evidence from high-resolution and tandem mass spectrometry, we propose the plausible reaction mechanisms between triazine and HS, as well as the derived reaction from triazine under different pH conditions.

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On‐surface Fenton and Fenton‐like reactions appraised by paper spray ionization mass spectrometry

Cited by 4 publications

References 33 publications

Oxidative Degradation Mechanism and Antidegradation Strategy of Paper-Based Relics with Transition Metal Pigments: From the Cellobiose Model to Cellulose Paper

Oxidative Degradation Mechanism and Antidegradation Strategy of Paper-Based Relics with Transition Metal Pigments: From the Cellobiose Model to Cellulose Paper

Suzuki C–C Coupling in Paper Spray Ionization: Microsynthesis of Biaryls and High-Sensitivity MS Detection of Aryl Bromides

Elucidating the Reaction Mechanisms between Triazine and Hydrogen Sulfide with pH Variation Using Mass Spectrometry

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