Electron Paramagnetic Resonance Spin Trapping Research Articles

Eosin Y derivatives for visible light-mediated free-radical polymerization: Applications in 3D-photoprinting and bacterial photodynamic inactivation

This study reports the design and the subsequent use of mono-allylated (EY-MA) and di-allylated (EY-DA) derivatives of eosin Y (EY) as highly efficient visible light-sensitive photosensitizers (PS) of bio-based H-donor molecules (cysteamine (Cys) or N-acetyl-L-cysteine (NAC)) and an electron donor (N-methyldiethanolamine, MDEA) for free-radical and thiol-acrylate polymerizations of a biobased monomer derived from soybean oil (SOA) upon exposure to visible light. High final acrylate conversions for SOA polymerization (up to 80 %) evidence the efficient photoinitiating properties of the eosin derivatives systems under irradiation with light emitting diodes (LEDs) centred at 405, 455 and 505 nm, and outperform those obtained with EY and other common photosensitizers such as camphorquinone or benzophenone. As described by fluorescence and phosphorescence analyses, laser flash photolysis (LFP) and electron paramagnetic resonance spin-trapping (EPR-ST) experiments, EY-MA and EY-DA can react via a proton/proton-coupled electron transfer reaction with Cys (or NAC) and MDEA respectively. The efficient singlet oxygen generation of the EY-MA-based materials upon exposure to visible light leads to excellent antibacterial properties, against both Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli). A 3-log decrease of E. coli adhesion on the surface of the materials is observed and 100 % adhesion inhibition of S. aureus is also demonstrated. The co-polymerization of the eosin-derived PS with the polymer matrix ensures sustainable antibacterial properties against both bacteria strains upon visible light exposure as it prevents their leakage out of the polymer network. Finally, finely complex 3D structures are successfully obtained by a 3D-photoprinting technology with the investigated EY-MA-based formulation using LED@405 nm.

EPR Spin-Trapping for Monitoring Temporal Dynamics of Singlet Oxygen during Photoprotection in Photosynthesis.

A central goal of photoprotective energy dissipation processes is the regulation of singlet oxygen (1O2*) and reactive oxygen species in the photosynthetic apparatus. Despite the involvement of 1O2* in photodamage and cell signaling, few studies directly correlate 1O2* formation to nonphotochemical quenching (NPQ) or lack thereof. Here, we combine spin-trapping electron paramagnetic resonance (EPR) and time-resolved fluorescence spectroscopies to track in real time the involvement of 1O2* during photoprotection in plant thylakoid membranes. The EPR spin-trapping method for detection of 1O2* was first optimized for photosensitization in dye-based chemical systems and then used to establish methods for monitoring the temporal dynamics of 1O2* in chlorophyll-containing photosynthetic membranes. We find that the apparent 1O2* concentration in membranes changes throughout a 1 h period of continuous illumination. During an initial response to high light intensity, the concentration of 1O2* decreased in parallel with a decrease in the chlorophyll fluorescence lifetime via NPQ. Treatment of membranes with nigericin, an uncoupler of the transmembrane proton gradient, delayed the activation of NPQ and the associated quenching of 1O2* during high light. Upon saturation of NPQ, the concentration of 1O2* increased in both untreated and nigericin-treated membranes, reflecting the utility of excess energy dissipation in mitigating photooxidative stress in the short term (i.e., the initial ∼10 min of high light).

Photocatalytic Degradation of Tetracycline Hydrochloride Based on the Structure-Property Exploration of BiOCl.

The correlation between structure and properties in the photodegradation reaction of bismuth oxychloride (BiOCl) was explored in this work. Three BiOCl samples with different sizes, morphological structures, and defects were prepared through a hydrothermal method with experimental manipulation. Their structural properties were comprehensively characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, electron spin resonance, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, and photoluminescence. Taking the photodegradation of tetracycline hydrochloride (TC-HCl) as the probe reaction, we found that high activity could be achieved by decreasing their crystal size and thickness, introducing proper defects in the structure, and assembling the nanosheets to get microball structure. Combined with radical-scavenge experiments and electron spin resonance (ESR) spin-trap spectra, we conclude that ̇O2- was the dominant reactive oxygen species for the degradation reaction. The degradation detailed pathway of TC-HCl was further analyzed using liquid chromatography-mass spectrometry. This work explores the structure-property correlation of BiOCl and provides strategies for the rational design of active photocatalysts for water remediation.

Ultrafast Sunlight-Induced Polymerization: Unveiling 2-Phenylnaphtho[2,3-d]Thiazole-4,9-dione as a Unique Scaffold for High-Speed and Precision 3D Printing.

A series of 15 dyes based on the 2-phenylnaphtho[2,3-d]thiazole-4,9-dione scaffold and 1 compound based on the 2,3-diphenyl-1,2,3,4-tetrahydrobenzo[g]quinoxaline-5,10-dione scaffold are studied as photoinitiators. These compounds are used in two- and three-component high-performance photoinitiating systems for the free radical polymerization of trimethylolpropane triacrylate (TMPTA) and polyethylene glycol diacrylate (PEGDA) under sunlight. Remarkably, the conversion of TMPTA can reach ≈60% within 20s, while PEGDA attains a 96% conversion within 90s. To delve into the intricate chemical mechanisms governing the polymerization, an array of analytical techniques is employed. Specifically, UV-vis absorption and fluorescence spectroscopy, steady-state photolysis, stability experiments, fluorescence quenching experiments, cyclic voltammetry, and electron spin resonance spin trapping (ESR-ST) experiments, collectively contribute to a comprehensive understanding of the photochemical mechanisms. Photoinitiation capacities of these systems are determined using real-time Fourier transformed infrared spectroscopy (RT-FTIR). Of particular interest is the revelation that, owing to the superior initiation ability of these dyes, high-resolution 3D patterns can be manufactured by direct laser write (DLW) technology and 3D printing. This underscores the efficient initiation of free radical polymerization processes by the newly developed dyes under both artificial and natural light sources, presenting an avenue for energy-saving, and environmentally friendly polymerization conditions.

Nickel-doped microtubular CeVO4 inspired by wood powder structure for visible light photocatalytic degradation of methylene blue and bacterial inactivation

In this study, inspired by natural wood powder structure, nickel-doped microtubular cerium vanadate (Ni/T-CeVO4) was obtained using wood powder as a biological template. Photocatalytic experiments under visible light revealed that Ni/T-CeVO4-3wt possessed the highest photocatalytic activity, with a degradation efficiency of up to 99 % for methylene blue. The enhanced photocatalytic performance was not only attributed to the microtubule wood powder structure assigned the composite a larger specific surface area but also the nickel doping narrowed the band gap of the composites while introducing more oxygen vacancies. The rapidly generated current in transient photocurrent responses and small arc radius in electrochemical impedance spectra further indicated the higher photogenerated carrier separation and smaller photogenerated electron transfer resistance within the composite. ESR spin-trapping tests proved that O2− and OH dominated the photocatalytic process. Furthermore, owing to its unique structural characteristics, the composite showed excellent photocatalytic antibacterial activity against Staphylococcus aureus and Escherichia coli. The present study provides a theoretical basis for developing efficient dual-effect photocatalysts using visible light to remove organic dyes and pathogenic bacteria from the water environment.

Vascular protein disulfide isomerase A1 mediates endothelial dysfunction induced by angiotensin II in mice.

Protein disulfide isomerases (PDIs) are involved in platelet aggregation and intravascular thrombosis, but their role in regulating endothelial function is unclear. Here, we characterized the involvement of vascular PDIA1 in angiotensin II (Ang II)-induced endothelial dysfunction in mice. Endothelial dysfunction was induced in C57BL/6JCmd male mice via Ang II subcutaneous infusion, and PDIA1 was inhibited with bepristat. Endothelial function was assessed invivo with magnetic resonance imaging and exvivo with a myography, while arterial stiffness was measured as pulse wave velocity. Nitric oxide (NO) bioavailability was measured in the aorta (spin-trapping electron paramagnetic resonance) and plasma (NO2 - and NO3 - levels). Oxidative stress, eNOS uncoupling (DHE-based aorta staining), and thrombin activity (thrombin-antithrombin complex; calibrated automated thrombography) were evaluated. The inhibition of PDIA1 by bepristat in Ang II-treated mice prevented the impairment of NO-dependent vasodilation in the aorta as evidenced by the response to acetylcholine invivo, increased systemic NO bioavailability and the aortic NO production, and decreased vascular stiffness. Bepristat's effect on NO-dependent function was recapitulated exvivo in Ang II-induced endothelial dysfunction in isolated aorta. Furthermore, bepristat diminished the Ang II-induced eNOS uncoupling and overproduction of ROS without affecting thrombin activity. In Ang II-treated mice, the inhibition of PDIA1 normalized the NO-ROS balance, prevented endothelial eNOS uncoupling, and, thereby, improved vascular function. These results indicate the importance of vascular PDIA1 in regulating endothelial function, but further studies are needed to elucidate the details of the mechanisms involved.

Preparation of core-shell structure Ag@TiO2 plasma photocatalysts and reduction of Cr(VI): Size dependent and LSPR effect

The poor light absorption and low carrier separation efficiency of Titanium dioxide (TiO2) limit its further application. The introduction of plasma metal Ag have the potential to solve these drawbacks owing to its plasma resonance effect. Thus core-shell structure Ag@TiO2 plasma photocatalysts was prepared by using facile reduction method in this work. More specifically, Ag@TiO2 composite catalysts with different Ag loading amounts were prepared in the presence of surfactant PVP. Ag@TiO2 demonstrates excellent light absorption performance and photoelectric separation efficiency compared with pure TiO2. As a result, it displays excellent performance of Cr(VI) reduction under visible light. The optimal composite catalysts Ag@TiO2–5P achieves exceptional visible-light-driven photocatalytic Cr(VI) reduction efficiency of 0.01416 min−1 that is 2.29 times greater than pure TiO2. To investigate the role of PVP, we also synthesized Ag@TiO2-5 without PVP. The experimental results show that although Ag@TiO2-5 Cr(VI) reduction performance is superior to pure TiO2, it significantly decreases compared with Ag@TiO2–5P. The results of TEM and optoelectronic testing show that agglomeration of Ag particles leads to a decrease in the photoelectric separation efficiency of Ag@TiO2-5. The smaller Ag particles provide more active sites and demonstrating a stronger overall local surface plasmon resonance (LSPR) effect. DMPO spin-trapping ESR spectra testing indicates that ∙O2− and ∙OH are the main reactive species. This research provides a potential strategy to prepare Ag-based plasma photocatalysts for environment protection.

Designing step-scheme AgI decorated Ta2O5-x heterojunctions for boosted photodegradation of organic pollutants

Step-scheme (S-scheme) AgI decorated Ta2O5-x heterojunctions have been designed and synthesized via a combination of solvothermal and chemical deposition methods for enhanced visible-light harvesting and high-performance photocatalysis. The AgI nanoparticles showed great influences on the visible-light absorption and charge separation between AgI and Ta2O5-x microspheres. The experimental results indicated that the as-prepare AgI/Ta2O5-x composites achieved enhanced photocatalytic performance towards tetracycline degradation under visible light, and the AgI/Ta2O5-x-11 sample displayed the highest photocatalytic performance and the maximum rate constant of approximately 0.09483 min−1, which was 7.22 times that of Ta2O5-x microspheres and 2.56 times that of AgI, respectively. The highly enhanced photocatalytic performance was mainly attributed to the construction of S-scheme heterostructure and formation of oxygen vacancies in Ta2O5-x microspheres. In addition, the trapping experimental and DMPO spin-trapping ESR spectra confirmed the ⸱O2− and ⸱OH species as the main radicals during tetracycline degradation. Current work indicates an S-scheme tantalum-based composites for high-performance environmental photocatalysis.

Fine-tuning metal nodes accessibility of metal-organic frameworks for boosting net photocatalytic H2O2 production

Coordination unsaturated metal nodes in metal-organic frameworks (MOFs) work as photocatalytic active sites in H2O2 production, but over-exposed metal nodes also act as decomposing sites towards the photogenerated H2O2, resulting in low net yield. Herein, fine-tuning of metal nodes accessibility in MOFs was applied for boosting net photocatalytic H2O2 production. The accessibility of the nodes was fine-tuning through varying the feeding amount of benzoic acid (BA) during synthesis, treated MOFs with HCl, re-installed with variable BA, etc. The correlation between nodes accessibility and H2O2 production was systematically investigated, which demonstrates that the NH2-UiO-66-XBA with higher compensated BA possessing large steric effect at nodes would hinder the decomposition of photogenerated H2O2, thus promoting the net H2O2 yield. As a contrary, NH2-UiO-66-HCl without BA showed a distinctive decomposition rate of H2O2, resulting in a low net H2O2 production yield. The re-installed NH2-UiO-66-ReBA10 with compensated BA showed a recovered H2O2 production yield. A combination of O2 sorption isothermals, PL spectra, ESR spin-trap plots, and Koutecky-Levich plots disclosed that O2 was enriched by the framework and then reduced at the metal nodes mainly through two-electron pathway, especially for highly compensated MOFs. This strategy had been applied to other MOFs for boosting the H2O2 production like NU-1401 and PCN-222. This work reveals the fine-tuning of metal nodes accessibility in MOFs is an effective way for boosting H2O2 production.

Study on the photoinitiation mechanism of carbazole-based oxime esters (OXEs) as novel photoinitiators for free radical photopolymerization under near UV/visible-light irradiation exposure and the application of 3D printing

In this work, twenty-two oxime esters bearing different functional groups and based on carbazole as the chromophore were designed and synthesized as Type I photoinitiators. Interestingly, all structures mentioned in this work have never been reported before (even for their synthesis). These oxime esters were found to have good light absorption properties in the UV–visible range, and especially at 405 nm which is a reference wavelength in photopolymerization. Noticeably, several structures showed better photoinitiation abilities than the benchmark photoinitiator i.e. diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), evidencing the interest of these structures. In order to investigate the photoinitiation mechanism of the two series of oxime esters differing by the position of the photocleavable groups, electronic absorption spectra were determined by molecular modeling and density functional theory calculations. Photopolymerization abilities of the different oxime esters and release of CO2 during the polymerization experiments were determined by Real-Time Fourier Transformed Infrared (RT-FTIR). Active free radicals were characterized by mean of Electron Spin Resonance Spin Trapping (ESR-ST) experiments. On the basis of these different complementary experiments, chemical mechanisms occurring during photopolymerization could be proposed. Experimental results showed that the decarboxylation reaction occurring subsequent to the photocleavage of oxime esters had a beneficial effect on the photoinitiation ability. Finally, 3D printed objects were successfully obtained by using oxime esters exhibiting the best photoinitiating abilities.

Visible-light-driven quantitative photooxidation of anthracene to anthraquinone under mild conditions

This paper discloses a mild and atom-economic photo-oxidation protocol for visible-light-driven quantitative oxidation of anthracene (AN) to anthraquinone (AQ), which can obtain excellent AN conversion (∼100%) and AQ yield (99.2%) without any catalysts and additives under 10 h of visible light illumination. In addition, the protocol also works well with other chemical molecules that have a similar structure. In this protocol, AN is directly oxidized from AN to AQ without the observation of the intermediate anthrone (AO). Based on a series of control tests, as well as free radical quenching and electron paramagnetic resonance (EPR) spin trapping studies, it can be inferred that the process of photo-oxygenation in AN is most likely initiated by its photo-excited state, denoted as AN*. This photo-excited state has the ability to activate molecular oxygen (O2) by an electron transfer mechanism, resulting in the formation of a superoxide free radical (O2•-). Following this, the process of photo-oxidation is progressively controlled by the oxygenated product AQ, which acts as an active photo-catalyst. AQ is derived from the oxidation of AN by O2•- and its presence accelerates the process of photo-oxidation due to its rapid accumulation. Furthermore, the yield of AQ can be improved by enhancing the light intensity of the light source, timely separating the yellow solid oxidation product AQ formed during the reaction, and pre-adding the oxidation product AQ to the protocol as an active photocatalyst.

New visible-light-driven Bi2MoO6/Cs3Sb2Br9 heterostructure for selective photocatalytic oxidation of toluene to benzaldehyde

Herein, new Bi2MoO6/Cs3Sb2Br9 heterostructure (BiMo/CSB) was investigated for the first time as a visible-light-driven photocatalyst for C(sp3)–H bond activation using molecular oxygen as a green oxidant and toluene as a model substrate. The optimized BiMo/CSB photocatalyst exhibited enhanced toluene oxidation activity (2,346 μmol g-1h−1), which was almost two- and five-fold that of pristine CSB (1,165 μmol g-1h−1) and BiMo (482 μmol g-1h−1), respectively. The improved photocatalytic performance was essentially attributed to the formation of staggered band energy lineup in the BiMo/CSB hybrid, which promoted S-scheme charge transfer across the BiMo/CSB heterointerface as supported by ultraviolet photoelectron spectroscopy (UPS), density functional theoretical (DFT), time-resolve photoluminescence (TRPL), and photoelectrochemical studies. Spin–trapping electron paramagnetic resonance (EPR) and radical scavenging studies revealed that photoinduced hole, molecular oxygen, and superoxide radical are key active species in this photocatalytic system. The developed BiMo/CSB catalyst provided good selectivity toward benzaldehyde product (94–98 %), presumably due to the inhibiting effect of benzyl alcohol on benzaldehyde oxidation. No significant change in structure and morphology was observed for the spent catalyst, however small negative shift of Sb 3d and Bi 4f binding energy was found suggesting partial reduction of Sb3+ and Bi3+. This work not only provides a new visible-light-driven photocatalyst for C(sp3)–H bond activation but also opens the doors for exploitation of the conversion and functionalization of this inert bond toward the production of high value-added organic chemicals.

Triggering “signal-on” photoelectrochemical responses by heterojunction transition for selective detection of copper(II) based on Pd/MoS2@g-C3N4 nanocomposites

Controlling the concentration of copper(II) in aquatic systems is of importance for human health. Numerous traditional technologies to detect Cu2+ may encounter with limitations, such as high signal background and complicated operation. Herein, a highly selective photoelectrochemical (PEC) sensor is proposed for the “signal-on” detection of Cu2+ employing g-C3N4 nanosheets with MoS2 and Pd quantum dots deposited (Pd/MoS2@g-C3N4). Pd/MoS2@g-C3N4 could present the enhanced photocurrents of specific responses to Cu2+ under light irradiation. MoS2 quantum dots on the sensor are agglomerated into MoS2 bulk during sensing Cu2+, forming an efficient Z-scheme heterojunction. The heterojunction transition induced photoelectrons transferring from the bulk MoS2 to g-C3N4, resulting in “signal-on” PEC responses. Such Z-scheme heterojunction has conquered the traditional heterojunction towards “signal-on” mechanism, that was further verified by band structure measurements and DMPO spin trapping ESR analysis. Photocurrent intensities increased gradually with the addition of incremental Cu2+ concentrations, achieving a detection limit of 0.21 μM and a broad linear interval range from 1 μM to 1 mM with high selectivity and stability. This work may open a new door towards the in situ construction of g–C3N4–based Z-scheme heterojunctions for the signal-on PEC sensing platform, providing wide applications in environmental monitoring and food safety.

The photoinitiator of bifunctional α-hydroxy ketone with long-wavelength in photopolymerization under UV-LEDs

α-hydroxy ketone photoinitiators have been widely used in the photopolymerization industry, such as coating, ink and adhesive, for they have high initiating activity, good thermal stability, and yellowing resistance. However, few works have been reported in developing α-hydroxy ketone photoinitiators that match the absorption of long wavelength LEDs. In this work, a new bifunctional α-hydroxy ketone photoinitiator, (1,4-phenylene) bis (4-hydroxy-4-methylpent-1-en-3-one) (B-HMP), was synthesized and characterized. B-HMP exhibited excellent absorption among the wavelength of 300– 400 nm due to the introduction of unsaturated double bonds which could be employed to match 365/405 nm LEDs. From the results of electron spin resonance spin-trapping (EPR-ST) and steady-state photolysis investigations, the mechanism of the generation of radicals of B-HMP may be via not only the cleavage of CC bonds, but also intermolecular hydrogen abstraction. The efficiency of photopolymerization of B-HMP and triethanolamine (TEOA) was better than those of B-HMP alone because of the synergistic effect. Furthermore, the B-HMP/TEOA had a significantly yellowing resistance property.

Peroxymonocarbonate activation via Co nanoparticles confined in metal-organic frameworks for efficient antibiotic degradation in different actual water matrices.

Traditional advanced oxidation processes suffer from low availability of ultrashort lifetime radicals and declining stability of catalysts. Co nanoparticles in hollow bimetallic metal-organic frameworks (Co@MOFs) were synthesized via a solvothermal method. Nanoconfinement and peroxymonocarbonate (PMC) degradation system endows Co@MOFs with high catalytic activity and stability even in the actual water matrices. The nanocomposites exhibited 100-200nm polyhedron structure with irregular nanocavity between the 20nm shell and multicores. Co nanoparticles were completely encapsulated by the FeIII-MOF-5 shell according to the X-ray diffraction and photoelectron spectra. Both 0.8nm micropores and 3.6nm mesopores were proven to be present. The yolk-shell Co@MOFs exhibited higher catalytic performance than that of Co nanoparticles, hollow FeIII-MOF-5 and its core-shell counterpart toward PMC activation during sulfamethoxazole degradation. The catalytic activities of Co@MOFs for the activation of unsymmetrical peroxides (PMC and peroxymonosulfate) were much higher than those for the symmetrical peroxides (H2O2 and persulfate) and the heterogeneous catalysis was dominant in the Co@MOFs activated H2O2 and PMC systems. The MOF stability was the highest and metal leakages were the least in the activated PMC system among the four peroxides because of mild reaction conditions and the alkalescent solution (pH=8.3-8.4). Furthermore, the high removal efficiencies (>94%) and degradation rates could be maintained in the different actual water matrices due to the confinement effects. The contributions of carbonate and hydroxyl radicals were primary for sulfamethoxazole degradation, and superoxide anion and singlet oxygen also played essential roles according to scavenging experiments and time-series spin-trapping electron spin resonance spectra. Six degradation pathways were proposed according to 26 intermediate identification and the pharmacophores of more than 80% intermediates were destroyed, which would benefit subsequent biological treatment. Successful combination of nanoconfinement and PMC might provide a new effective solution for pollution remediation.

Complexation of AAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride) with cucurbit[7]uril enhances the yield of AAPH-derived radicals

AAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride), a water-soluble azo compound is widely employed to produce peroxyl radicals for chemical and biological studies. This compound is shown herein to form a stable inclusion complex with cucurbit[7]uril (CB7), a well-established supramolecular host. Competitive binding assays using berberine dye, isothermal titration calorimetry (ITC), and nuclear magnetic resonance (1H NMR) experiments, provided evidence for the inclusion of AAPH inside the CB7 cavity with a binding constant of 2.51 ± 0.76 × 105 M−1 (determined by ITC). Computational analysis at B3LYP-D3BJ/6-311G(d,p) of the complex (AAPH@CB7) showed interactions of the positively-charged amino groups of AAPH with carbonyl functions at the CB7 entrances. Photolysis of AAPH@CB7 by illumination at 365 nm, gave a higher yield of carbon-centered radicals when compared to the absence of CB7, as evidenced by electron paramagnetic resonance spin trapping using α-phenyl-N-t-butylnitrone. Enhanced radical formation was corroborated by increased consumption of pyrogallol red, free Trp and Trp-containing peptides when these were exposed to AAPH@CB7 in the presence of light. The increased yield of radicals generated by AAPH@CB7 is believed to arise from a pull effect of CB7 portals on initial AAPH-derived carbon-centered radicals generated by photolysis. It is proposed that these radicals are exposed and released to the bulk solution and react with O2 to give peroxyl radicals. These results suggest that the AAPH@CB7 complex can be used to generate high yields of peroxyl radicals for their use in studying these species in material, environmental and biomedical sciences amongst others.

Systematical comparison of antibiotic degradation in the activated peroxymonocarbonate and Fenton systems: Kinetics, matrix influence, mechanisms and intermediate toxicities

The degradation of representative antibiotics and their mechanisms in the activated peroxymonocarbonate (PMC) and Fenton systems were systematically investigated and compared in this work. The PMC can exist and be reliable at high ratios for 1 h according to the 13C nuclear magnetic resonance spectra. The activated PMC system was proven to be more efficient than the Fenton system for the degradation of sulfamethoxazole, ciprofloxacin and ceftriaxone under same experiment conditions. The activated PMC system exhibited higher sulfamethoxazole removal performance in different actual water matrices due to the insignificant effect of coexisting substances, while the impurities had an adverse impact on the Fenton system. The pH of the activated PMC system was relatively stable and ranged from 7.8 to 8.2, while the pH of the Fenton system dropped from 5.2 to 4.1. The slight decreases of sulfamethoxazole removal efficiencies were observed after bubbling O2, N2 and CO2 in the Fenton system, while removal rates in the activated PMC system were greatly prohibited and the inhibition ratios increased with gas solubility. The selective 1O2 and CO3− played primary roles in the activated PMC system according to scavenging experiments and time-series spin-trapping electron spin resonance spectra, which resulted in higher removal efficiencies and lower oxidation degree. The non-selective OH contribution was dominant in the Fenton system. The activated PMC system was more suitable for subsequent biological treatment and friendlier to the ecosystem than the Fenton system according to intermediate pharmacophore removal and toxicity comparisons. The activated PMC system showed apparent advantages over the Fenton system in most cases, which might encourage more researchers to devote their interest and time on this promising degradation system.

Molecular mechanism for the activation of the potent hepatotoxin acetylhydrazine: Identification of the initial N-centered radical and the secondary C-centered radical intermediates.

Acetylhydrazine (AcHZ), a major human metabolite of the widely-used anti-tuberculosis drug isoniazid (INH), was considered to be responsible for its serious hepatotoxicity and potentially fatal liver injury. It has been proposed that reactive radical species produced from further metabolic activation of AcHZ might be responsible for its hepatotoxicity. However, the exact nature of such radical species remains not clear. Through complementary applications of ESR spin-trapping and HPLC/MS methods, here we show that the initial N-centered radical intermediate can be detected and identified from AcHZ activated by transition metal ions (Mn(III)Acetate and Mn(III) pyrophosphate) and myeloperoxidase. The exact location of the radical was found to be at the distal-nitrogen of the hydrazine group by 15N-isotope-labeling techniques via using 15N-labeled AcHZ we synthesized. Additionally, the secondary C-centered radical was identified unequivocally as the reactive acetyl radical by complementary applications of ESR spin-trapping and persistent radical TEMPO trapping coupled with HPLC/MS analysis. This study represents the first detection and unequivocal identification of the initial N-centered radical and its exact location, as well as the reactive secondary acetyl radical. These findings should provide new perspectives on the molecular mechanism of AcHZ activation, which may have potential biomedical and toxicological significance for future research on the mechanism of INH-induced hepatotoxicity.

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

Singlet oxygen (1O2) 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 1O2 detection. However, it is often limited to time-independent acquisition. Recent studies have raised questions about the reliability of the 1O2 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 1O2 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 1O2-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 1O2 detection techniques, and provide insights into the reaction mechanisms in 1O2-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.

Oxidative stability and oxygen permeability of oil-loaded capsules produced by spray-drying or electrospraying measured by electron spin resonance

The oxidative stability and the oxygen permeability of oil-loaded capsules were investigated by Electron Spin Resonance (ESR). The capsules were produced by spray-drying or electrospraying in the monoaxial or coaxial configuration using glucose syrup as the encapsulating agent. ESR-spin trapping results showed that electrosprayed capsules oxidized faster and during the early stages of incubation, irrespective of the emitter configuration (monoaxial or coaxial), when compared to those produced by spray-drying. Furthermore, ESR oximetry showed that oxygen inside the spray-dried capsules reached equilibrium with the surrounding atmosphere significantly slower than the monoaxially electrosprayed capsules (i.e., ∼2h and ∼10 min, respectively). These findings have been attributed to the larger particle size of the spray-dried capsules influencing the oxygen diffusion area (i.e., lower surface-to-volume ratio) and diffusion path (i.e., thicker encapsulating wall for a fixed oil load). Together, the lower oxygen uptake reported for the spray-dried capsules correlated well with their higher oxidative stability.