Search Results (30)

This study explored the influence of high silver (Ag) loading (5–10 mol%) on the photocatalytic performance of zirconium (Zr) co-doped TiO₂ (AZT) with a low Zr content. Although various Ag/Zr ratios have been reported, the effect of high Ag loading combined with low Zr content remains largely unrevealed, particularly in low-temperature synthesis where the role of Zr as a phase inhibitor is less critical. To address this gap, the AZT photocatalyst was fabricated via a solvothermal method combined with organic-free peroxy route. Characterization indicated Zr⁴⁺ incorporated into the TiO₂ lattice, inducing structural distortions and promoting Ti³⁺ defect states. Simultaneously, silver existed as ternary Ag species, which functioned as visible light responsive co-catalysts that enhanced light absorption via Surface Plasmon Resonance (SPR) and facilitated efficient charge separation. Photocatalytic performance was evaluated through Methylene Blue (MB) decolorization under household LED lamp. The optimized 7% Ag loaded catalyst achieved 99.4% removal efficiency within 6 h, with a reaction rate ten times higher than the Zr-doped sample. This superior activity was attributed to a p-n heterojunction and the SPR effect, narrowing the optical band gap to 2.60 eV. Radical scavenger experiments confirmed that the process was primarily driven by photogenerated holes. Full article

Cross-reactions between peroxy radicals (RO₂) derived from different volatile organic compound (VOC) precursors have been proposed as an important pathway during atmospheric oxidation. However, direct molecular evidence has been limited. In this study, α-pinene and fully deuterated toluene (d8-toluene) were oxidized separately and as a mixture in a potential aerosol mass (PAM) flow reactor, and the resulting secondary organic aerosol (SOA) was characterized by a high-resolution mass spectrometer (ESI FT-ICR-MS). A constrained chemical mass balance (CMB) model attributed 82.9% of the mixed-SOA signal to single-precursor sources (66.5% α-pinene, 16.4% d8-toluene), leaving a 17.1% signal-based residual fraction unexplained by linear mixing. Among 2450 residual molecular formulas exclusive to the mixed-SOA, 1858 were identified as cross-reaction candidates, with carbon, oxygen, and double bond equivalents (DBE) distributions consistent with RO₂-RO₂ cross-reactions between toluene- and α-pinene-derived fragments. We also identified representative monomer-dimer pairs, where one monomer corresponded to a known α-pinene oxidation product, while the other matched a primary oxidation product of d8-toluene oxidation based on the Master Chemical Mechanism (MCM), providing strong molecular-level evidence for RO₂-RO₂ cross-reactions. Our findings demonstrate that the mixed VOCs generate unique SOA products that extend beyond simple additive chemistry, with implications for SOA yield parameterizations and chemical transport models. Full article

Organic peroxy (ROO•) and hydroperoxy (•QOOH) radicals are key reactive intermediates that are formed via the oxidation of volatile organic compounds during combustion or in the Earth’s atmosphere. Their primary fate is continued unimolecular decay or bimolecular chemistry, the relative branching for which is heavily structure- and temperature-dependent. This article outlines a combined single- and multi-reference quantum chemical study to characterize the near-UV accessible electronically excited states of the prototypical ROO• and •QOOH intermediates, tert-butyl peroxy and hydroperoxy-tert-butyl radicals—the ground-state chemistries of which have been well studied both experimentally and computationally. Additionally, we simulate the electronic absorption profiles of these ROO• and •QOOH intermediates with a variety of multi- and single-reference methods. The results show an interesting conformer dependence on the electronically excited-state character and electronic absorption maxima of •QOOH. The results show promise for electronic absorption spectroscopy to be used as a selected probe for determining •QOOH conformers. Additionally, electronic absorption may contribute to the daytime removal of long-lived •QOOH intermediates formed in the troposphere. We expect that our studies will motivate experiments on the electronic absorption spectra of experimentally achievable ROO• and •QOOH. Full article

Hydroperoxyalkylperoxy radicals (•OOQOOH) are important intermediates in the low-temperature oxidation chemistry of conventional fuels. In these species, a hydrogen atom may migrate from a non-adjacent carbon to the peroxy group, forming a dihydroperoxyalkyl radical (•P(OOH)₂). This research delves into the theoretical kinetics of a set of 110 H-migration reactions in normal-alkyl cyclohexanes, calculating high-pressure limit rate constants for these reactions. The reactions are further classified into 15 subclasses based on distinctions in the reaction center and its environment, with rate rules derived by averaging the rate constants within each subclass. A comparison of our calculated rate constants for specific H-migration reactions of •OOQOOH with existing mechanisms and similar reactions in non-cyclic alkanes reveals significant disparities, emphasizing the necessity for precise rate constants tailored to normal-alkyl cyclohexanes. Ethyl cyclohexane mechanisms and n-propyl cyclohexane mechanisms sourced from studies have been improved with high-pressure limit rate constants from this study. Simulations of the low-temperature combustion of ethyl cyclohexane and n-propyl cyclohexane show that the predictions from the updated mechanisms align more closely with the experimental data under specific conditions compared to the original mechanism. Full article

Epoxidation of long-chain α-olefins (LAOs) is a process of paramount importance, particularly in the preparation of epoxides. Traditional epoxidation methods, such as the chlorohydrin method and peracid method, suffer from issues such as poor selectivity, by-product formation, and environmental pollution. Mukaiyama epoxidation, with its mild reaction conditions and exceptional selectivity, has attracted widespread attention and considerable research. Transition metal oxide catalysts show potential in the reaction; however, the catalytic efficiency still require substantial improvement due to dilemma of substance activation. In this study, a synergistic enhancement method was employed, achieved through the creation of oxygen vacancies and the electron-rich nature of Cu. The substitution of Cu with Sn in CuO facilitates the creation of oxygen vacancy (Vo), thereby enhancing absorption and activation of O₂. The conversion for O₂ activation paves the way for the formation of benzoyl peroxy radicals. Moreover, the interaction between Sn and Cu promotes charge transfer from Sn to Cu, resulting in an electron-rich Cu surface that significantly accelerates the dehydrogenation of benzaldehyde. The synergistic enhancement protocol exhibits near-quantitative performance, delivering an oxide yield of 92.9%. This study introduces an innovative dual-promotion catalytic strategy for Mukaiyama epoxidation utilizing readily available O₂, providing profound insights into the optimization design of transition metal oxide catalysts and beyond. Full article

Automotive formulated lubricants are high value products composed of 80% base oil and 20% various additives. During their life service, lubricants are exposed to several factors that will cause degradation over time, such as high temperature, shear, and oxidation. Base oil is a complex combination of hydrocarbons that are relatively sensitive to oxidation. During the initiation phase of oxidation, free radicals are formed, leading to the production of hydroperoxide ROOH and an alkyl radical R^•. These compounds will react with the base oil molecules to form aldehydes, ketones, and carboxylic acids in the termination phase. Owing to the molecular complexity of these mixtures, Fourier transform mass spectrometry seems to be the most appropriate tool to cover their wide range of compounds due to its ultra-high resolving power and mass accuracy. In this study, a native formulated lubricant and its different oxidized states at 140 °C under air flow (3, 5, 7, 8, and 9 days of oxidation) were analyzed by FTICR MS. The combination of atmospheric pressure chemical ionization (APCI) was used to achieve a non-selective ionization of molecules, including base oils, while Electrospray ionization (ESI) was used to selectively ionize acidic molecules. Apparent Kendrick mass defect (aKMD) plots were used to separate homologous series of molecules on different horizontal lines on the basis of the CH₂ repetition unit. Aging of lubricants was mainly characterized by a rapid consumption of certain additive families, such as molybdenum dithiocarbamates (MoDTCs) and zinc dithiophosphate (ZnDTPs), but also by the emergence of many oxidation products. Thus, the presence of aldehydes, ketones, and acids was characterized in the early stage of aging while larger products from polymerization were observed in a more advanced stage of aging. Interaction products between peroxy radicals and hindered phenols/alkyl diphenylamines (ADPAs) antioxidations were elucidated toward the high m/z. The formation of such products can be explained by trapping mechanisms of these additives at high temperature (>120 °C). Other types of interaction products were observed with the formation of antioxidant complexes. Additive degradation products were also characterized. For instance, polyisobutenyl succinimide dispersant oxidation products were clearly evidenced on the aKMD plots due to the gaps of 56 Da between each point. Overall, this study demonstrated the efficiency of the aKMD approach, and the use of ESI/APCI to characterize base oil and additive oxidation products. Full article

The well-known small-molecule biothiols have been used to maintain the normal metabolism of peroxy radicals, forming protein structures, resisting cell apoptosis, regulating metabolism, and protecting the homeostasis of cells in the organism. A large amount of research has found that abnormal levels of the above biothiols can cause some adverse diseases, such as changes in hair pigmentation, a slower growth rate, delayed response, excessive sleep and skin diseases. In order to further investigate the exact intracellular molecular mechanism of biothiols, it is imperative to explore effective strategies for real-time biothiol detection in living systems. In this work, a new near-infrared (NIR) emission fluorescence probe (probe 1) for sensitive and selective detection of biothiols was devised by combining dicyanoisophorone derivatives with the dinitrobenzenesulfonyl (DNBS) group. As expected, probe 1 could specifically detect biothiols (Cys, Hcy and GSH) through the dinitrobenzenesulfonyl group to form dye 2, which works as a signaling molecule for sensing biothiols in real samples. Surprisingly, probe 1 showed superior sensing characteristics and low-limit detection towards biothiols (36.0 nM for Cys, 39.0 nM for Hcy and 48.0 nM for GSH) with a large Stokes shift (134 nm). Additionally, the function of probe 1 as a platform for detecting biothiols was confirmed by confocal fluorescence imaging of biothiols in MCF-7 cells and zebrafish. More importantly, the capability of probe 1 in vivo has been further evaluated by imaging the overexpressed biothiols in tumor tissue. It is reasonable to believe that probe 1 can provide a valuable method to explore the relationship between biothiols and the genesis of tumor. Full article

Dual-initiation is a new orientation of many studies in the curing of unsaturated polyester resin and the manufacture of low-density unsaturated polyester resin (LDUPR) composite materials. In our research, two kinds of low-temperature (40–70 °C) initiators (cyclohexanone peroxide (CYHP) and methyl ethyl ketone peroxide (MEKP)), one kind of medium-temperature (70–130 °C) initiator (tert-butyl peroxy-2-ethylhexanoate (TBPO)), and three kinds of high-temperature (≥130 °C) initiators (tert-butyl benzoate peroxide (TBPB), tert-amyl carbonate peroxide-2-ethylhexanoate (TAEC), and tert-butyl carbonate peroxide-2-ethylhexanoate (TBEC)) were applied to constitute different dual-initiators. Those dual-initiators were a low-temperature dual-initiator (CYHP/MEKP), medium-low-temperature dual-initiators (CYHP/TBPO and MEKP/TBPO), and high-temperature dual-initiators (TAEC/TBPB, TAEC/TBEC, and TBEC/TBPB). In the low-temperature and medium-low-temperature ranges, the LDUPR sample displayed the highest specific compression strength (P_s) of 42.08 ± 0.26 MPa·g⁻¹·cm³ in the presence of the MEKP/TBPO dual-initiator. In the high-temperature range, the LDUPR sample exhibited the highest specific compression strength (P_s) of 43.32 ± 0.45 MPa·g⁻¹·cm³ for the existence of the TAEC/TBPB dual-initiator. It is pointed out that the dual-initiator released more active free radicals, accelerating the initial curing time and the peak time of UPR. More active free radicals caused both high-activity (short-chain) molecules and low-activity (long-chain or intertwined) molecules in resin to cross-link, prolonging UPR’s curing process by approximately two minutes and resulting in an improvement of UPR’s cross-linking. In the presence of a dual-initiator, the integrated and planar microstructure of LDUPR samples performed uniformly distributed dimples, dispersed external forces, and enhanced samples’ specific compressive strength. Full article

Organic peroxy radicals (RO₂) as key intermediates in tropospheric chemistry exert a controlling influence on the cycling of atmospheric reactive radicals and the production of secondary pollutants, such as ozone and secondary organic aerosols (SOA). Herein, we present a comprehensive study of the self-reaction of ethyl peroxy radicals (C₂H₅O₂) by using advanced vacuum ultraviolet (VUV) photoionization mass spectrometry in combination with theoretical calculations. A VUV discharge lamp in Hefei and synchrotron radiation at the Swiss Light Source (SLS) are employed as the photoionization light sources, combined with a microwave discharge fast flow reactor in Hefei and a laser photolysis reactor at the SLS. The dimeric product, C₂H₅OOC₂H₅, as well as other products, CH₃CHO, C₂H₅OH and C₂H₅O, formed from the self-reaction of C₂H₅O₂ are clearly observed in the photoionization mass spectra. Two kinds of kinetic experiments have been performed in Hefei by either changing the reaction time or the initial concentration of C₂H₅O₂ radicals to confirm the origins of the products and to validate the reaction mechanisms. Based on the fitting of the kinetic data with the theoretically calculated results and the peak area ratios in the photoionization mass spectra, a branching ratio of 10 ± 5% for the pathway leading to the dimeric product C₂H₅OOC₂H₅ is measured. In addition, the adiabatic ionization energy (AIE) of C₂H₅OOC₂H₅ is determined at 8.75 ± 0.05 eV in the photoionization spectrum with the aid of Franck-Condon calculations and its structure is revealed here for the first time. The potential energy surface of the C₂H₅O₂ self-reaction has also been theoretically calculated with a high-level of theory to understand the reaction processes in detail. This study provides a new insight into the direct measurement of the elusive dimeric product ROOR and demonstrates its non-negligible branching ratio in the self-reaction of small RO₂ radicals. Full article

The accurate identification of ozone (O₃) production sensitivity is central to developing O₃ pollution control policies. It is determined by the relative ratio of the radical loss to the total primary radical production. However, such radical losses in the traditional sensitivity analysis typically rely on nitrogen oxide (NO_x) sinks while ignoring particle uptake (collisions between compounds in the gas phase and condensed phases that result in irreversible uptake due to chemical reactions). Therefore, we combine NO_x and particle uptakes to optimize peroxy radical loss estimates and thus analyze the relative sensitivity. We also assess the absolute responses of precursor reduction to O₃ production. Such relative and absolute sensitivity analysis is applied to measurements in Chun’an, a county in China, where volatile organic compounds (VOCs) and NO_x are both rich. Consequently, the relative sensitivity analysis presents that the dominant precursor for O₃ production sensitivity shifts from volatile organic compounds (VOCs) in the morning and evening to NO_x in the afternoon, the main driver of which is related to NO depletion. In contrast, the absolute sensitivity analysis confirms that VOCs persistently determine the diurnal ozone production sensitivity. Moreover, they both show that particle uptake does not change the regime classification of O₃ production sensitivity (i.e., VOC- or NO_x-sensitive regime) but potentially has a strong inhibition on the sensitivity magnitude (within 16% and 38% for VOC- or NO_x-sensitive regimes, respectively). Our results partly explain more insensitive O₃ production measurements than those suggested by traditional sensitivity analyses, which has important implications for synergistic controls on O₃ and fine particulate matter pollution. Full article

Polyethylene is a model polyolefin, and a widely used material for the manufacture of many products, including cable sheaths. Understanding degradation mechanisms at the atomic scale leading to oxidation during aging is crucial for many long-term applications. The concentrations of radicals derived from oxidation and chain scission during radio-oxidation, as well as their ratio, are important parameters controlling the predominance of chain scission or crosslinking of the polymer. In this work, we propose a cryogenic EPR technique for measuring oxidation- and fragmentation-derived radicals as a less-destructive method for the evaluation of cable insulation aging and performance capability. We investigate the effect of the low-dose and high-dose radiation aging on the formation of free radicals in the polymer matrix that are both unprotected and protected by antioxidants. The stability of radicals after aging is a determinant of macroscopic processes and structural changes during aging. Under the conditions of the higher dose rate, the peroxy radical buildup is lower per dose. Peroxy radical buildup is followed by decay during aging, in accordance with POOH content. Our results allow the prediction of the capability of the antioxidant to protect the XLPE material in the function of dose and time. Full article

Even though there are many photocurable compositions that are cured by cationic photopolymerization mechanisms, UV curing generally consists of the formation of cross-linking covalent bonds between a resin and monomers via a photoinitiated free radical polymerization reaction, obtaining a three-dimensional polymer network. One of its many applications is in the refinish coatings market, where putties, primers and clear coats can be cured faster and more efficiently than with traditional curing. All these products contain the same essential components, which are resin, monomers and photoinitiators, the latter being the source of free radicals. They may also include additives used to achieve a certain consistency, but always taking into account the avoidance of damage to the UV curing—for example, by removing light from the innermost layers. Surface curing also has its challenges since it can be easily inhibited by oxygen, although this can be solved by adding scavengers such as amines or thiols, able to react with the otherwise inactive peroxy radicals and continue the propagation of the polymerization reaction. In this review article, we cover a broad analysis from the organic point of view to the industrial applications of this line of research, with a wide current and future range of uses. Full article

The detection of reactive oxygen species (ROS) and the analysis of oxidative stress are frequent applications of functional flow cytometry. Identifying and quantifying the ROS species generated during oxidative stress are crucial steps for the investigation of molecular mechanisms underlying stress responses. Currently, there is a wide availability of fluorogenic substrates for such purposes, but limitations in their specificity and sensitivity may affect the accuracy of the analysis. The aim of our work was to validate a new experimental model based in different strains of Escherichia coli B deficient in key genes for antioxidant defense, namely oxyR, sodA and sodB. We applied this model to systematically assess issues of specificity in fluorescent probes and the involvement of different ROS in a bacterial model of oxidative stress, as the probes can react with a variety of oxidants and free radical species. Our results confirm the higher sensitivity and specificity of the fluorescent probe mitochondrial peroxy yellow 1 (MitoPY1) for the detection of H₂O₂, and its very low capacity for organic hydroperoxides, thus extending MitoPY1′s specificity for H₂O₂ in mammalian cells to a bacterial model. On the contrary, the fluorescent probe 2′,7′-dichlorodihydrofluorescein diacetate (H₂DCF-DA) is more sensitive to organic peroxides than to H₂O₂, confirming the lack of selectivity of H₂DCF-DA to H₂O₂. Treatment with organic peroxides and H₂O₂ suggests a superoxide-independent oxidation of the fluorescent probe Hydroethidine (HE). We found a positive correlation between the lipophilicity of the peroxides and their toxicity to E. coli, suggesting greater quantitative importance of the peroxidative effects on the bacterial membrane and/or greater efficiency of the protection systems against the intracellular effects of H₂O₂ than against the membrane oxidative stress induced by organic peroxides. Altogether, our results may aid in preventing or minimizing experimental errors and providing recommendations for the proper design of cytometric studies of oxidative stress, in accordance with current recommendations and guidelines. Full article

The self-reaction of acetylperoxy radicals (CH₃C(O)O₂^•) (R1) as well as their reaction with methyl peroxy radicals (CH₃O₂^•) (R2) have been studied using laser photolysis coupled to a selective time resolved detection of three different radicals by cw-CRDS in the near-infrared range: CH₃C(O)O₂^• was detected in the Ã-$\tilde{X}$ electronic transition at 6497.94 cm⁻¹, HO₂^• was detected in the 2ν₁ vibrational overtone at 6638.2 cm⁻¹, and CH₃O₂^• radicals were detected in the Ã-$\tilde{X}$ electronic transition at 7489.16 cm⁻¹. Pulsed photolysis of different precursors at different wavelengths, always in the presence of O₂, was used to generate CH₃C(O)O₂^• and CH₃O₂^• radicals: acetaldehyde (CH₃CHO/Cl₂ mixture or biacetyle (CH₃C(O)C(O)CH₃) at 351 nm, and acetone (CH₃C(O)CH₃) or CH₃C(O)C(O)CH₃ at 248 nm. From photolysis experiments using CH₃C(O)C(O)CH₃ or CH₃C(O)CH₃ as precursor, the rate constant for the self-reaction was found with k₁ = (1.3 ± 0.3) × 10⁻¹¹ cm³s⁻¹, in good agreement with current recommendations, while the rate constant for the cross reaction with CH₃O₂^• was found to be k₂ = (2.0 ± 0.4) × 10⁻¹¹ cm³s⁻¹, which is nearly two times faster than current recommendations. The branching ratio of (R2) towards the radical products was found at 0.67, compared with 0.9 for the currently recommended value. Using the reaction of Cl^•-atoms with CH₃CHO as precursor resulted in radical profiles that were not reproducible by the model: secondary chemistry possibly involving Cl^• or Cl₂ might occur, but could not be identified. Full article

Heat-assisted plasma (HAP) treatment using He gas is known to improve the adhesive-bonding and adhesive-free adhesion properties of polytetrafluoroethylene (PTFE). In this study, we investigated the effects of He and Ar gaseous species on the HAP-treated PTFE surface. Epoxy (EP) adhesive-coated stainless steel (SUS304) and isobutylene–isoprene rubber (IIR) were used as adherents for the evaluation of the adhesive-bonding and adhesive-free adhesion properties of PTFE. In the case of adhesive bonding, the PTFE/EP-adhesive/SUS304 adhesion strength of the Ar-HAP-treated PTFE was the same as that of the He-HAP-treated PTFE. In the case of adhesive-free adhesion, the PTFE/IIR adhesion strength of the Ar-HAP-treated PTFE was seven times lower than that of the He-HAP-treated PTFE. The relation among gaseous species used in HAP treatment, adhesion properties, peroxy radical density ratio, surface chemical composition, surface modification depth, surface morphology, surface hardness, and the effect of irradiation with vacuum ultraviolet (VUV) and UV photons were investigated. The different adhesive-free adhesion properties obtained by the two treatments resulted from the changes in surface chemical composition, especially the ratios of oxygen-containing functional groups and C–C crosslinks. Full article