Secondary Radicals Research Articles

Investigation of the Mechanism of Oxidative Potential Increase in Atmospheric Particulate Matter during Photoaging: Important Role of Aromatic Nitrogenous Compounds.

Particulate matter (PM) undergoing various aging processes in the atmosphere changes its toxicity. However, the mechanism of toxicity evolution is not fully clarified currently. This study demonstrates that photoaging promotes an increase in the oxidative potential (OP) of atmospheric PM by about 30%, and the increased OP is mainly attributed to the production of secondary organic compounds, while water-soluble metal ions contribute only 11%. The OP of nonextractable matters (NEMs) of atmospheric PM was mostly increased after photoaging, followed by water-soluble matters (WSMs). NEM can produce quinone-like functional groups and secondary persistent free radicals during photoaging, which are most likely to produce reactive oxygen species (ROS). For WSM, the conversion of low-oxidation humic-like substances (HULIS) to high-oxidation HULIS is the main reason for the increase in OP. Quinones, nitrophenols, and N-containing heterocycles are the OP contributors produced during the conversion process. Among them, quinones are the main secondary oxidizing active compounds, while nitro-phenolic compounds and N-containing heterocyclic compounds may play a catalyst-like role, facilitating the production of oxidizing active compounds and ROS in the newly converted high-oxidation HULIS. This study clarifies the secondary OP generation mechanism and provides new insights into the uncertainty of PM toxicity during atmospheric aging.

Formation of active centers of polymer catalysts for radical-coordination polymerization

Chromatography–mass spectrometry of samples representing the interaction products of ferrocene, radical initiator and monomer taken in the molar ratio of 1:2:10 in toluene solution was used for experimental detection of products indicating the structure and mechanism of formation of metal complex active centers of radical-coordination polymerization. Structures similar to those proposed by the quantum-chemical modeling were demonstrated to be formed with the participation of secondary radicals.

Effective photocatalytic degradation of sulfamethoxazole using PAN/SrTiO3 nanofibers

Freshwater scarcity driven by pollution and climate change necessitates the development of effective water purification methods. There is an urgent need for innovative solutions that can efficiently remove contaminants from water sources. A effective material for the photocatalytic degradation of organic sulfonamide antibiotics from water was developed in this study. A composite of electrospun strontium titanate (SrTiO3) and carbon fibers polyacrylonitrile/strontium titanate (PAN/SrTiO3) was employed for the photocatalytic degradation of sulfamethoxazole (SMX). Scanning Electron Microscopy/Energy Dispersive Spectroscopy (SEM-EDS), Transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterise the composite. The fibers had a thickness of ~250 nm and uniformly dispersed PAN and SrTiO3 particles. A PAN/SrTiO3 composite with a 1:1 mass ratio (20 mg) demonstrated excellent performance, achieving over 90 % degradation at pH 7 and a contaminant concentration of 5 mg/L under ultraviolet (UV) light irradiation during 60 min. The composite was tested for the photodegradation of the major organic pollutant (SMX) in distilled and river water. In river water, the degradation efficiency exceeded 80 % at pH 7 because of the formation of secondary radicals involved in antibiotic degradation. SMX degradation was described using a pseudo-first order kinetic equation using the Langmuir-Hinshelwood model. These results underscore the novelty and significance of the PAN/SrTiO3 composite and demonstrate its high efficiency and potential for large-scale water purification applications.

Structure and Kinetics of Organic Acid Radicals Formed in Reaction with •OH Radicals.

The study investigated •OH-derived radicals from certain organic acids employed in nuclear fuel processing and separation using EPR spectroscopy and quantum chemistry methods. Hydroxyl radicals were generated through a Fenton-like reaction within the EPR resonator under both acidic and basic conditions, allowing for the detection of neutral and radical anions, respectively. The spectral assignment and analysis were conducted using a combination of literature data and quantum chemical calculations employing DFT theory with B3LYP or LPBE functionals and the L2a_3 basis set. The reaction of the •OH radical with lactic and glycolic acids yielded primary C-centered radicals through hydrogen abstraction from these acids. In contrast, the •OH radical exclusively generated secondary radicals from oxalic acid, whereas for citric acid, it resulted in both primary and secondary species induced by decarboxylation. The EPR spectrum of acetohydroxamic acid, upon reaction with the •OH radical, displayed a complex pattern featuring primary •N-type and N-O•-type radicals. The decay pathways of the generated radicals were primarily attributed to radical-radical reactions, with the extracted reaction rate constants generally falling within the typical range observed for such reactions. The EPR parameters calculated for potential radicals using B3LYP and LPBE functionals with L2a_3 basis set demonstrated good accuracy for neutral radicals, albeit requiring minor adjustments for radical anions.

Overlooked role of CO3·− reactivity with different dissociation forms of organic micropollutants in degradation kinetics modeling: A case study of fluoxetine degradation in a UV/peroxymonosulfate system

Selective oxidizing agent carbonate radical (CO3•–) is an important secondary radical in radical-based advanced oxidation technology for wastewater treatment. However, the role of CO3•– in removing ionizable organic micropollutants (OMs) under environmentally relevant conditions remains unclear. Herein we investigated CO3•– effect on degradation kinetics of fluoxetine in UV/peroxymonosulfate (PMS) system based on a built radical model considering CO3•– reactivity differences with its different dissociation forms. Results revealed that the model, which incorporated CO3•– selective reactivity (with determined second-order rate constants, ksrc,CO3·−, of 7.33 ×106 and 2.56 ×108 M–1s–1 for cationic and neutral fluoxetine, respectively) provided significantly more accurate predictions of fluoxetine degradation rates (k). A good linear correlation was observed between ksrc,CO3·− from experiments and literatures for 24 ionizable OMs and their molecular orbital energy gaps and oxidation potentials, suggesting the possible electron transfer reaction mechanism. Cl– slightly reduced the degradation rates of fluoxetine owing to rapid transformation of Cl• with HCO3− into CO3•–, which partially compensated for the quenching effects of Cl− on HO• and SO4•–. Dissolved organic matter significantly quenched reactive radicals. The constructed kinetic model successfully predicted fluoxetine degradation rates in real waters, with CO3•– being the dominant contributor (∼90 %) to this degradation process.

Alkoxide-Assisted Stereoselective Functionalization of 1,2-Bis-boronic Esters Under Photoredox Catalysis.

Site-specific functionalization of the secondary C-B bond of 1,2-bis-boronic esters has been proven to be an important method for the generation of 1,2-bis-functionalized compounds in a highly stereoselective manner. We have explored previously unknown secondary selective alkenylation, allylation, alkynylation and addition to aryl vinyl trifluoromethane, which proceeds via a novel reaction mechanism: alkoxide-mediated photoredox activation to generate secondary radicals over the primary one.

Cu-Electrocatalysis Enables Vicinal Bis(difluoromethylation) of Alkenes: Unraveling Dichotomous Role of Zn(CF2H)2(DMPU)2 as Both Radical and Anion Source.

The difluoromethyl group (CF2H) serves as an essential bioisostere in drug discovery campaigns according to Lipinski's Rule of 5 due to its advantageous combination of lipophilicity and hydrogen bonding ability, thereby improving the ADME properties. However, despite the high prevalence and importance of vicinal hydrogen bond donors in pharmaceutical agents, a general synthetic method for doubly difluoromethylated compounds in the vicinal position is absent. Here we describe a copper-electrocatalyzed strategy that enables the vicinal bis(difluoromethylation) of alkenes. By leveraging electrochemistry to oxidize Zn(CF2H)2(DMPU)2-a conventionally utilized anionic transmetalating source, we paved a way to utilize it as a CF2H radical source to deliver the CF2H group in the terminal position of alkenes. Mechanistic studies revealed that the interception of the resultant secondary radical by a copper catalyst and subsequent reductive elimination is facilitated by invoking the Cu(III) intermediate, enabling the second installation of the CF2H group in the internal position. The utility of this electrocatalytic 1,2-bis(difluoromethylation) strategy has been highlighted through the late-stage bioisosteric replacement of pharmaceutical agents such as sotalol and dipivefrine.

Unveiling the Role of Direct Electron Transfer and Secondary Radicals in Electrooxidation of Tetrabromobisphenol A: Identification of Intermediates and Density Functional Theory Insights

Unveiling the Role of Direct Electron Transfer and Secondary Radicals in Electrooxidation of Tetrabromobisphenol A: Identification of Intermediates and Density Functional Theory Insights

The comparison of the efficacy of 185/254 nm and 172 nm photolysis for the removal of sulfonamides and trimethoprim from aqueous solutions

The VUV (λ < 200 nm) photolysis can be used to eliminate organic substances without the addition of oxidant due to the efficient generation of OH from water. Two VUV light sources are commercially available: the low-pressure mercury vapor (LPM) and the Xe-excimer lamp, which emit 185/254 nm and 172 nm photons, respectively. This study compares the efficiency of the UV/VUV185nm and VUV172nm photolysis in removing four sulfonamides (SAs) and trimethoprim (TRIM) antibiotics. For the LPM lamp, 254 nm UV radiation ((4.21 ± 0.08) × 10−6 molphoton s−1) can contribute to the transformation of target substances besides the OH generated by the 185 nm VUV light. The VUV photon flux (1.02 × 10−5 molphoton s−1) of the Xe-excimer lamp significantly exceeded that of the LPM lamp (3.97 × 10−7 molphoton s−1); as H2O2 formation in pure water reflected, however, the efficiency of the transformation rate of the target substances was just slightly faster. For the LPM lamp, in addition to the direct UV photolysis of SAs, the 254 nm light enhances the OH formation via H2O2 photolysis, thereby partially compensating for the low VUV185nm photon flux. The high VUV172nm photon flux was primarily manifested in mineralization efficiency and not in the transformation rate of target compounds. The short penetration depth of 172 nm light favors the recombination of primary radicals and decreases the efficiency. The effect of the matrix and matrix components is complex; they act as a radical scavenger or (V)UV filter. The change of radical set and the role of the formed secondary radicals (Cl, Cl2−, and CO3−) in transformation must be considered.

Characterization of a secondary carbon-centred radical

Characterization of a secondary carbon-centred radical

Stereoselective amino acid synthesis by photobiocatalytic oxidative coupling.

Photobiocatalysis-where light is used to expand the reactivity of an enzyme-has recently emerged as a powerful strategy to develop chemistries that are new to nature. These systems have shown potential in asymmetric radical reactions that have long eluded small-molecule catalysts1. So far, unnatural photobiocatalytic reactions are limited to overall reductive and redox-neutral processes2-9. Here we report photobiocatalytic asymmetric sp3-sp3 oxidative cross-coupling between organoboron reagents and amino acids. This reaction requires the cooperative use of engineered pyridoxal biocatalysts, photoredox catalysts and an oxidizing agent. We repurpose a family of pyridoxal-5'-phosphate-dependent enzymes, threonine aldolases10-12, for the α-C-H functionalization of glycine and α-branched amino acid substrates by a radical mechanism, giving rise to a range of α-tri- and tetrasubstituted non-canonical amino acids 13-15 possessing up to two contiguous stereocentres. Directed evolution of pyridoxal radical enzymes allowed primary and secondary radical precursors, including benzyl, allyl and alkylboron reagents, to be coupled in an enantio- and diastereocontrolled fashion. Cooperative photoredox-pyridoxal biocatalysis provides a platform for sp3-sp3 oxidative coupling16, permitting the stereoselective, intermolecular free-radical transformations that are unknown to chemistry or biology.

Elucidating the enhanced role of carbonate radical in propranolol degradation by UV/peroxymonosulfate system

Carbonate radical (CO3•−) has been proved to be an important secondary radical in advanced oxidation processes due to various radical reactions involved HCO3−/CO32−. However, the roles and contributions of CO3•− in organic micropollutant degradation have not been explored systematically. Here, we quantified the impact of CO3•− on the degradation kinetics of propranolol, a representative pollutant in the UV/peroxymonosulfate (PMS) system, by constructing a steady-state radical model. Substantially, the measured values were coincident with the predictive values, and the contributions of CO3•− on propranolol degradation were the water matrix-dependent. Propranolol degradation increased by 130% in UV/PMS system containing 10 mM HCO3−, and the contribution of CO3•− was as high as 58%. Relatively high pH values are beneficial for propranolol degradation in pure water containing HCO3−, and the contributions of CO3•− also enhanced, while an inverse phenomenon was shown for the effects of propranolol concentrations. Dissolved organic matter exhibited significant scavenging effects on HO•, SO4•−, and CO3•−, substantially retarding the elimination process. The developed model successfully predicted oxidation degradation kinetics of propranolol in actual sewage, and CO3•− contribution was up to 93%, which in indicative of the important role of CO3•− in organic micropollutant removal via AOPs treatment.

Plasma Activated Water for wine barrels disinfection

Barrel aging is crucial for the production of high-quality wines, with barrel reuse playing a key role in this process. Therefore, disinfecting and cleaning barrels are vital to prevent health and safety issues, being B. bruxellensis one of the most extended problems. In this study, naturally contaminated oak barrels with B. bruxellensis were immersed during 3 h in four Plasma Activated Water (PAW) generated for 1.5 min, 5 min, 15 min and 30 min. The presence of secondary radicals (OH•, NO•, NO2•) was observed after HPLC and spectrometry analysis. The results suggested that those reactive species played an important role in the inactivation of B. bruxellensis. PAW_5 (generated during 5 min), which achieved a reduction of 3.49 ± 0.83 logarithmic units in B. bruxellensis population, was chosen as the best one in terms of economic and time consumption. Thus, an ecofriendly, sustainable and inexpensive solution was presented to inactivate B. bruxellensis from wine barrels.

Хемилюминесцентные характеристики периферической крови при облучении in vitro в диапазоне доз 100–500 мГр

Abstract. Nowadays a lot of examinations are dedicated to determination of radiobiological effects under low doses of ionising radiation. It is known that ionising radiation in the cells of an organism increases generation of reactive oxygen species (ROS). The purpose of the work is to determine basic parameters of chemiluminescent kinetics of ROS in peripheral blood under in vitro radiation in the range of 100–500 mGy doses. The research will extend the knowledge of the impact degree of ionising radiation in low doses on organism tissue of farm animals. Scientific novelty is that the results of the research will allow to predict radiobiological effects of low doses in a multicellular organism. The research is included in practical and fundamental directions of radiobiology. Research methods. In vitro radiation of blood samples in the range of 100–500 mGy doses. The kinetics of generation of ROS is registered on 36-channel chemiluminometer 3604-PC. Results. The doses in the range of 100–300 mGy accelerated the time of the first peak of spontaneous and activated generation of radicals, under 500 mGy dose the formation of the first peak of spontaneous and activated generation of primary ROS decelerated. Under the impact of low absorbed doses maximum intensity of primary and secondary radicals generation decreased. The inhibition of primary radicals spontaneous production occurred under 100–300 mGy doses, the inhibition of antigen activated generation of primary ROS was under 400 mGy. The reduction of the amount of spontaneous secondary ROS was registered under 100 mGy dose. The decrease of antigen activated secondary radicals production occurred under 100–300 mGy doses. 500 mGy dose inhibited a reaction ability of blood cells to generate primary radicals. The external in vitro gamma radiation in the range of 100–500 mGy had a negative impact on peripheral blood cells showing an acceleration of chemiluminescent reaction as well as decrease of maximum intensity of the first peak of spontaneous and antigen activated primary and secondary radicals production. As a consequence, a decrease of the amount of primary and secondary radicals production was revealed.

Development of a Five-Chemical-Probe Method to Determine Multiple Radicals Simultaneously in Hydroxyl and Sulfate Radical-Mediated Advanced Oxidation Processes.

Advanced oxidation processes (AOPs), such as hydroxyl radical (HO•)- and sulfate radical (SO4•-)-mediated oxidation, are attractive technologies used in water and wastewater treatments. To evaluate the treatment efficiencies of AOPs, monitoring the primary radicals (HO• and SO4•-) as well as the secondary radicals generated from the reaction of HO•/SO4•- with water matrices is necessary. Therefore, we developed a novel chemical probe method to examine five key radicals simultaneously, including HO•, SO4•-, Cl•, Cl2•-, and CO3•-. Five probes, including nitrobenzene, para-chlorobenzoic acid, benzoic acid, 2,4,6-trimethylbenzoic acid, and 2,4,6-trimethylphenol, were selected in this study. Their bimolecular reaction rate constants with diverse radicals were first calibrated under the same conditions to minimize systematic errors. Three typical AOPs (UV/H2O2, UV/S2O82-, and UV/HSO5-) were tested to obtain the radical steady-state concentrations. The effects of dissolved organic matter, Br-, and the probe concentration were inspected. Our results suggest that the five-probe method can accurately measure radicals in the HO•- and SO4•--mediated AOPs when the concentration of Br- and DOM are less than 4.0 μM and 15 mgC L-1, respectively. Overall, the five-probe method is a practical and easily accessible method to determine multiple radicals simultaneously.

Alkene dialkylation by triple radical sorting.

The development of bimolecular homolytic substitution (SH2) catalysis has expanded cross-coupling chemistries by enabling the selective combination of any primary radical with any secondary or tertiary radical through a radical sorting mechanism1-8. Biomimetic9,10 SH2 catalysis can be used to merge common feedstock chemicals-such as alcohols, acids and halides-in various permutations for the construction of a single C(sp3)-C(sp3) bond. The ability to sort these two distinct radicals across commercially available alkenes in a three-component manner would enable the simultaneous construction of two C(sp3)-C(sp3) bonds, greatly accelerating access to complex molecules and drug-like chemical space11. However, the simultaneous in situ formation of electrophilic and primary nucleophilic radicals in the presence of unactivated alkenes is problematic, typically leading to statistical radical recombination, hydrogen atom transfer, disproportionation and other deleterious pathways12,13. Here we report the use of bimolecular homolytic substitution catalysis to sort an electrophilic radical and a nucleophilic radical across an unactivated alkene. This reaction involves the in situ formation of three distinct radical species, which are then differentiated by size and electronics, allowing for regioselective formation of the desired dialkylated products. This work accelerates access to pharmaceutically relevant C(sp3)-rich molecules and defines a distinct mechanistic approach for alkene dialkylation.

Digital cholangioscopy-assisted, direct visualization-guided, radiation-free, endoscopic retrograde intervention for cholelithiasis: technical feasibility, efficacy, and safety.

Nonradiation, digital cholangioscope (DCS)-assisted endoscopic intervention for cholelithiasis has not been widely performed. For this study, we aimed to report the feasibility, efficacy, and safety of an established DCS-guided lithotomy procedure. Data relating to biliary exploration, stone clearance, adverse events, and follow-up were obtained from 289 patients. The choledocholithiasis-related outcomes via the DCS-guided procedure were subsequently compared to those via conventional endoscopic retrograde cholangiopancreatography (ERCP). Biliary access was achieved in 285 patients. The technical success rate for the exploration of the common bile duct, the cystic stump, the hilar ducts, and secondary radicals was 100%. Moreover, the success rates were 98.4%, 61.7%, and 20.7%, for the exploration of the cystic duct, complete cystic duct, and gallbladder, respectively. Suspicious or confirmed suppurative cholecystitis, cholesterol polyps, and hyperplastic polyps were detected in 42, 23, and 5 patients, respectively. Stone clearance was achieved in one session in 285 (100%), 11 (100%), 13 (100%), 7 (100%), 6 (100%), and 3 (14.3%) patients with choledocholithiasis and hepatolithiasis, cystic duct stump stones, nondiffuse located intrahepatic lithiasis, a single cystic duct stone, a single gallbladder stone, and diffuse located intrahepatic lithiasis, respectively. Complete stone clearance for diffuse intrahepatic lithiasis was achieved in 19 (90.5%) patients, and fractioned re-lithotomy was performed in 16 (76.2%) patients. One patient developed mild acute cholangitis, and 12 developed mild pancreatitis. Stones recurred in one patient. Compared with conventional ERCP, DCS-guided lithotomy has the advantages of clearing difficult-to-treat choledocholithiasis and revealing concomitant biliary lesions, and this technique has fewer complications and a decreased risk of stone recurrence. The technical profile, efficacy, and safety of nonradiation-guided and DCS-guided lithotomy are shown in this study. We provide a feasible modality for the endoscopic removal of cholelithiasis.

Cost-effective approach for atmospheric accretion reactions: a case of peroxy radical addition to isoprene.

We present an accurate and cost-effective method for investigating the accretion reactions between unsaturated hydrocarbons and oxidized organic radicals. We use accretion between isoprene and primary, secondary and tertiary alkyl peroxy radicals as model reactions. We show that a systematic semiempirical transition state search can lead to better transition state structures than relaxed scanning with density functional theory with a significant gain in computational efficiency. Additionally, we suggest accurate and effective quantum chemical methods to study accretion reactions between large unsaturated hydrocarbons and oxidized organic radicals. Furthermore, we examine the atmospheric relevance of these types of reactions by calculating the bimolecular reaction rate coefficients and formation rates under atmospheric conditions from the quantum chemical reaction energy barriers.

Photoexcitation of (diarylmethylene)amino benziodoxolones for alkylamination of styrene derivatives with carboxylic acids.

The alkylamination of alkenes using pristine carboxylic acids was achieved by the photoexcitation of (diarylmethylene)amino benziodoxolones (DABXs), which serve as both an oxidant and an aminating reagent (an iminyl radical precursor). The developed method is a simple photochemical reaction without the need for external photosensitizers and shows a broad substrate scope for aliphatic carboxylic acids leading to the formation of primary, secondary, and tertiary alkyl radicals, thus enabling the facile synthesis of various structurally complex amines. Mechanistic investigations including transient absorption spectroscopy measurements using a laser flash photolysis (LFP) method disclosed the unique photochemical reactivity of DABXs, which undergoes homolysis of their I-N bonds to give an iminyl radical and ortho-iodobenzoyloxy radical, the latter of which participates in the single-electron oxidation of carboxylates.

Synthesis of a trivalent copper complex for efficient degradation of antibiotic ofloxacin

Copper-based catalysts have been widely used in heterogeneous advanced oxidation processes (AOPs) to degrade emerging contaminants, with trivalent copper species (Cu(III)) often identified as crucial intermediates. However, the current understanding of the reactivity and potential oxidation mechanism associated with such reactive species remains quite limited. In the present study, a stable Cu(III) complex was synthesized, and its reactivity towards a typical fluoroquinolone antibiotic, ofloxacin (OFX), was comprehensively investigated. The results revealed that Cu(III) itself functioned as the primary oxidizing agent instead of secondary hydroxyl radicals generated during OFX decomposition, which exhibited high reactivity over a wide pH range (3.0–9.0) with molar ratio of Cu(III) to OFX between 1:2 and 3:1. Interestingly, prevalent constituents of natural water, including (bi)carbonate (0–10 mM), chloride (0–10 mM), nitrate (0–10 mM) and humic acid (0–30 mg/L), displayed minimal influence on the oxidation efficiency of Cu(III). Piperazine moiety was identified as the primary reaction site, and three different pathways including tertiary amine oxidation, hydroxylation, and N-demethylation process were proposed. The detailed oxidation mechanisms were further illustrated by density functional theory (DFT) calculations. This study contributes to the theoretical foundation for investigating the mechanism of Cu(III)-mediated oxidation of antibiotics.