Transient Chemiluminescence Assay for Real-Time Monitoring of the Processes of SO₃^2–-Based Advanced Oxidation Reactions

Abstract

The hydroxyl radical (·OH) is a strong oxidizing agent in situ generated in advanced oxidation processes (AOPs) and crucial for assessing the performances of AOPs toward organic contaminants’ degradation. Herein, we developed a specific luminescent probe, APDI (N′ N′-di­(propylethylenediamine)-perylene-3,4,9,10-tetracarboxylic diimide), to selectively detect ·OH among diverse reactive oxygen species and other radicals. Based on the transient chemiluminescence (TCL) spectra, the in situ concentration profile of ·OH within 0.01 s interval time in classical Fenton reactions and four kinds of SO3 2–-based AOPs was obtained, which provides insights into the high dynamic processes of the whole ·OH generation and consumption processes. Besides, compared with acidic conditions, reduced degradation efficiencies in Fe2+–SO3 2– and Fe2+–SO3 2––H2O2 systems were found under neutral conditions. The complete depletion of active free radicals due to SO2 –̇ radicals generated from Fe2+ and SO3 2– should account most for decreased degradation efficiencies evidenced by a new SO2* TCL signal discovered in the TCL spectra. In addition, similar phenomena have also been found in other M(n–1)+–SO3 2–-related AOPs. As SO3 2– and HSO3 – often exist naturally in wastewater, more efforts are needed to improve the performance of Fe2+–H2O2 systems. This discovery has important significance for organic contaminant degradation in a natural environment.

Organic Semiconductor Nanosheets for Sulfite Detecting Based on Activation of Sulfite and a Synergetic Chemiluminescence Resonance Energy Transfer Process in a Mild System of Fe2+-SO32–

“…APDI was synthesized according to our previous work . In brief, 1-propylethylenediamine (50 μL, 0.4 mmol) and 1,6,7,12-tetrachloroperylene tetracarboxylic acid dianhydride (PDI, 106.0 mg, 0.2 mmol) were both added in a round-bottomed flask with 40 mL of DMSO.…”

“…APDI was synthesized according to our previous work. 12 In brief, 1-propylethylenediamine (50 μL, 0.4 mmol) and 1,6,7,12-tetrachloroperylene tetracarboxylic acid dianhydride (PDI, 106.0 mg, 0.2 mmol) were both added in a round-bottomed flask with 40 mL of DMSO. The reactions were brought to reflux at 110 °C for 12 h. After cooling, solid APDI was obtained through vacuum distillation and then drying it overnight in a vacuum drying chamber.…”

“…Sulfur dioxide (SO 2 ) as one kind of air pollution exists in the form of two derivatives of sulfite (SO 3 2– ) and bisulfite (HSO 3 – ) in an aqueous solution. , Excess sulfite not only causes extreme environmental pollution like acid rain but also negatively affects human health, particularly for those who suffer from asthma. − Therefore, the direct and accurate detection of sulfite is of great significance for environmental monitoring and disease diagnosis. Activation of sulfite (SO 3 2– ) to produce more active free radicals plays an important role in sulfite detection and wastewater treatment. − Chemiluminescence (CL) is a spectral analysis method based on the light radiation phenomenon in the absence of an external light source. − Specifically, as in situ spectral analysis method, a CL signal is used to monitor intermediate substances by capturing the light signal emitted during the reaction with short detecting time resolution (from μs to ms). , It is well known that CL emissions can be generated by chemical activation of sulfite with oxidants like MnO 4 – , Ce 4+ , I 2 , Mn 3+ , et al The CL reaction mechanism of sulfite oxidation occurs from autodecomposition of S 2 O 6 2– generated by SO 3 ̇ – as follows: , M n + + S O 3 2 − → H S O 3 • + M ( n − 1 )+ 2 S O 3 •− → S 2 O 6 2 …”

“…Perylene-3,4,9,10-tetracarboxylic diimide (PDI) and its derivatives as one of the best n -type organic semiconductors behave with unique optical and electronic properties like high electron affinity and charge carrier mobilities. , Recently, the supramolecular architectures of chemically modified PDI such as aminopropanoic acid-modified PDI, alanine-modified PDI, and NHPDI, as photocatalysts with wide visible-light responses, have shown excellent performances in degradation of organic contaminants and splitting water for O 2 evolution and as catalysts in CO sensing . In our previous work, we had provided a water-soluble PDI molecular probe toward the hydroxyl radical (•OH) and applied it to study the •OH generation process in a SO 3 2– -based Fenton system . But due to the weak resistance to matrix interference and inhibited by the CL effect of a high concentration of sulfite, this system could not be used for sulfite sensing.…”

Time-Resolved Persistent Luminescence Encoding for Multiplexed Severe Acute Respiratory Syndrome Coronavirus 2 Detection

“…Notably, persistent luminescence (PersL)-based nanoplatforms (NPs) can emit afterglow for seconds to minutes or even days after ceasing the excitation. − The ultralong luminescence lifetime of PersL NPs not only offered an elegant strategy to thoroughly eliminate background autofluorescence but also expanded the wide lifetime tunable range. In addition, PersL-NPs featured with a narrow emission band and high chemical stability have evoked considerable interests in multiplexed nucleic acid analysis and protein profiles. − Similar to manipulating emission colors, the PersL lifetime of PersL-NPs can be effectively regulated by engineering surface functionalization, adjusting luminescence resonance energy transfer (LRET) processes, as well as designing dopant concentration. , However, limited by the precise PersL lifetime tunability of nanotechnology and associated PersL decoding methodology, developing PersL barcodes for high-throughput multiplexing remains a huge challenge.…”