Deciphering the incognito role of water in a light driven proton coupled electron transfer process

Thiyagarajan, S.; Suresh, R.; Ramanan, Vadivel; Ramamurthy, P.

doi:10.1039/c7sc03161k

Cited by 8 publications

(5 citation statements)

References 72 publications

(75 reference statements)

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“…The UV–vis absorption spectra of AP-DEA, AP-ML, and AP-PZ in tetrahydrofuran (THF) at a concentration of 10 μM were shown in Figure A and the relevant data are listed in Table . They had similar absorption spectra of π–π and charge transfer (CT) band for enol-form, which was corresponding with the trend of theoretical calculation data (Table S1). AP-DEA showed high proportion of keto-form emission as opposed to enol-form in comparison with AP-ML and AP-PZ, implying that close-heterocyclic alkyl-ring (morpholine and methyl-piperazine) limits the ESIPT effect of molecules maybe.…”

Section: Resultssupporting

confidence: 80%

SwissKnife-Inspired Multifunctional Fluorescence Probes for Cellular Organelle Targeting Based on Simple AIEgens

Lee

Zhang

et al. 2018

Anal. Chem.

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Facile, efficient, and mass production of aggregation-induced emission (AIE) luminogens (AIEgens) with excited-state intramolecular proton transfer (ESIPT) characteristics was achieved by a one-step condensation reaction of 2-(hydrazonomethyl)phenol with benzaldehydes. The function of as-prepared AIEgens could be tuned easily by varying the functional group being carried on the phenyl ring of benzaldehyde just like a Swiss knife handle. The suitable distance and angle of the intramolecular hydrogen bond in these AIEgens endowed them with ESIPT properties, intense solid-state luminescence, and large Stokes shifts (155−169 nm). These AIEgens could not only serve as biological probes showing specific targeting to lipid droplets, endoplasmic reticulum, and lysosomes, respectively, but also generate reactive oxygen species upon visible light irradiation to make them promise for photodynamic therapy.

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Section: Resultssupporting

confidence: 80%

SwissKnife-Inspired Multifunctional Fluorescence Probes for Cellular Organelle Targeting Based on Simple AIEgens

Lee

Zhang

et al. 2018

Anal. Chem.

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“…Unlike the SO 4 2− generated in PMS-based oxidation, the residual CH 3 COO − could accept H + to form a weak acid (CH 3 COOH, p Ka = 4.8). These reactions might be assisted by the intramolecular hydrogen bond in the PAA molecule, which has been reported to enhance proton transfer efficiency ( 41 ). In addition, a high pH value would promote the ionization of PAA (CH 3 COOOH, p Ka = 8.2), leading to increased spontaneous decomposition of PAA ( 42 ).…”

Section: Resultsmentioning

confidence: 99%

Unveiling singlet oxygen spin trapping in catalytic oxidation processes using in situ kinetic EPR analysis

Chen

Yang

et al. 2023

Proc. Natl. Acad. Sci. U.S.A.

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Singlet oxygen ( 1 O 2 ) plays a pivotal role in numerous catalytic oxidation processes utilized in water purification and chemical synthesis. The spin-trapping method based on electron paramagnetic resonance (EPR) analysis is commonly employed for 1 O 2 detection. However, it is often limited to time-independent acquisition. Recent studies have raised questions about the reliability of the 1 O 2 trapper, 2,2,6,6-tetramethylpiperidine (TEMP), in various systems. In this study, we introduce a comprehensive, kinetic examination to monitor the spin-trapping process in EPR analysis. The EPR intensity of the trapping product was used as a quantitative measurement to evaluate the concentration of 1 O 2 in aqueous systems. This in situ kinetic study was successfully applied to a classical photocatalytic system with exceptional accuracy. Furthermore, we demonstrated the feasibility of our approach in more intricate 1 O 2 -driven catalytic oxidation processes for water decontamination and elucidated the molecular mechanism of direct TEMP oxidation. This method can avoid the false-positive results associated with the conventional 2D 1 O 2 detection techniques, and provide insights into the reaction mechanisms in 1 O 2 -dominated catalytic oxidation processes. This work underscores the necessity of kinetic studies for spin-trapping EPR analysis, presenting an avenue for a comprehensive exploration of the mechanisms governing catalytic oxidation processes.

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“…[1][2][3][4][5][6][7][8][9][10][11] Naturally, researchers have long endeavored to understand the mechanism of PCET and harness it in molecular systems synthesized to achieve higher energy conversion efficiencies by mimicking natural biological systems. [12][13][14][15][16][17][18][19] Previous studies on PCET discovered that PCET occurs through three representative mechanisms; (i) stepwise ET-PT, (ii) stepwise PT-ET, and (iii) concerted PCET. 5,7,11,20,21 Moreover, to gain further insight into strategies for designing articial photosynthetic devices, the photoinduced PCET has been intensively studied.…”

Section: Introductionmentioning

confidence: 99%

Solvent-modulated proton-coupled electron transfer in an iridium complex with an ESIPT ligand

et al. 2022

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Deciphering the incognito role of water in a light driven proton coupled electron transfer process

Abstract: The incognito role of solvent water as a proton transfer bridge in a multi-site electron proton transfer process was depicted.

Cited by 8 publications

References 72 publications

SwissKnife-Inspired Multifunctional Fluorescence Probes for Cellular Organelle Targeting Based on Simple AIEgens

SwissKnife-Inspired Multifunctional Fluorescence Probes for Cellular Organelle Targeting Based on Simple AIEgens

Unveiling singlet oxygen spin trapping in catalytic oxidation processes using in situ kinetic EPR analysis

Solvent-modulated proton-coupled electron transfer in an iridium complex with an ESIPT ligand

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