Peroxidation Products Research Articles

Ferritin with methylglyoxal produces reactive oxygen species but remains functional

Iron is necessary for life, but the simultaneous iron-catalyzed formation of reactive oxygen species (ROS) is involved in pathogenesis of many diseases. One of them is diabetes mellitus, a widespread disease with severe long-term complications, including neuropathy, retinopathy, and nephropathy. Much evidence points to methylglyoxal, a potent glycating agent, as the key mediator of diabetic complications. In diabetes, there is also a peculiar dysregulation of iron homeostasis, leading to an expansion of redox-active iron. This in vitro study focuses on the interaction of methylglyoxal with ferritin, which is the main cellular protein for iron storage. Methylglyoxal effectively liberates iron from horse spleen ferritin, as well as synthetic iron cores; in both cases, it is partially mediated by superoxide. The interaction of methylglyoxal with ferritin increases the production of hydrogen peroxide, much above the generation of peroxide by methylglyoxal alone, in an iron-dependent manner. Glycation with methylglyoxal results in structural changes in ferritin. All of these findings can be demonstrated with pathophysiologically relevant (submillimolar) methylglyoxal concentrations. However, the rate of iron release by ascorbate, the ferroxidase activity, or the diameter of gated pores even in intensely glycated ferritin is not altered. In conclusion, although the functional features of ferritin resist alterations due to glycation, the interaction of methylglyoxal with ferritin liberates iron and markedly increases ROS production, both of which could enhance oxidative stress in vivo. Our findings may have implications for the pathogenesis of long-term diabetic complications, as well as for the use of ferritin as a nanocarrier in chemotherapy.

Indium Oxide Layer Dual Functional Modified Bismuth Vanadate Photoanode Promotes Photoelectrochemical Oxidation of Water to Hydrogen Peroxide.

The photoelectrochemical (PEC) dual-electron pathway for water oxidation to produce hydrogen peroxide (H2O2) shows promising prospects. However, the dominance of the four-electron pathway leading to O2 evolution competes with this reaction, severely limiting the efficiency of H2O2 production. Here, we report a In2O3 passivator-coated BiVO4 (BVO) photoanode, which effectively enhances the selectivity and yield of H2O2 production via PEC water oxidation. Based on XPS spectra and DFT calculations, a heterojunction is formed between In2O3 and BVO, promoting the effective separation of interface and surface charges. More importantly, Mott-Schottky analysis and open-circuit potential measurements demonstrate that the In2O3 passivation layer on the BVO photoanode shifts the hole quasi-Fermi level towards the anodic direction, enhancing the oxidation level of holes. Additionally, the widening of the depletion layer and the flattening of the band bending on the In2O3-coated BVO photoanode favor the generation of H2O2 while suppressing the competitive O2 evolution reaction. In addition, the coating of In2O3 can also inhibit the decomposition of H2O2 and improve the stability of the photoanode. This work provides new perspectives on regulating PEC two/four-electron transfer for selective H2O2 production via water oxidation.

Fluorine-Doped Graphene Oxide-Modified Graphite Felt Cathode for Hydrogen Peroxide Generation

Electrochemical oxygen reduction via the two-electron pathway (2e-ORR) is an emerging method for producing H2O2. It is cleaner, safer, and more convenient compared to the anthraquinone process. Graphite felt is one of the cathode candidates for large-scale cells due to its excellent mechanical properties. However, commercial graphite felt often fails to achieve the desired hydrogen-peroxide yield because of its low catalytic selectivity for the 2e-ORR pathway. Fluorine-doped carbon materials are expected to enhance 2e-ORR selectivity. This is because the electronic structure of carbon atoms adjacent to fluorine atoms may facilitate the production of hydrogen peroxide while hindering its further reduction. In this study, fluorine-doped graphene oxide (FGO) was prepared by the hydrothermal method. Subsequently, graphite felt modified with FGO was fabricated and used as the cathode for H2O2 production. The results indicated that in alkaline media, the graphite felt modified with FGO achieved a catalytic selectivity of 93% and a generation rate of 8.91 mg cm⁻2 h⁻¹. In comparison, commercial graphite felt had a catalytic selectivity of 75% and a generation rate of 2.10 mg cm⁻2 h⁻¹. Moreover, graphite felt modified by FGO also exhibited excellent electrocatalytic performance for H2O2 generation in neutral media. This research provides a fundamental study to promote the application of graphite felt in the environmentally friendly electrocatalytic production of hydrogen peroxide in industries.

Pyrene‐4,5,9,10‐Tetraone‐Based Porous Aromatic Frameworks for Photocatalytic Production of Hydrogen Peroxide

AbstractThree pyrene‐4,5,9,10‐tetraone‐based porous aromatic frameworks (PT‐PAFs) are synthesized and their photocatalytic properties for H2O2 production are studied. It is found that the combination of pyrene‐4,5,9,10‐tetraone with anthraquinone affords an efficient PT‐PAF photocatalyst (PAF‐371) for H2O2 production, which achieves production rates of 3791 µmol g−1 h−1 (with sacrificial reagent) and 923 µmol g−1 h−1 (without sacrificial reagent) from water and oxygen under visible light irradiation. This work demonstrates that pyrene‐4,5,9,10‐tetraone molecule could be introduced into PAF materials to construct efficient organic semiconductor photocatalysts for H2O2 production.

Bi2Te3/Carbon Nanotube Hybrid Nanomaterials as Catalysts for Thermoelectric Hydrogen Peroxide Generation

Harnessing waste heat from environmental or industrial sources presents a promising approach to eco-friendly and sustainable chemical synthesis. In this study, we introduce a thermoelectrocatalytic (TECatal) system capable of utilizing even small amounts of heat for hydrogen peroxide (H2O2) production. We developed a nanohybrid structure, combining carbon nanotubes (CNTs) and Bi2Te3 nanoflakes (Bi2Te3/CNTs), through a one-pot synthesis method. Bi2Te3, as a thermoelectric (TE) material, generates charge carriers under a temperature gradient via the Seebeck effect, enabling them to participate in surface redox reactions. However, the rapid recombination of these charge carriers greatly limits the TECatal activity. In the Bi2Te3/CNTs nanohybrid system, the introduction of CNTs substantially enhances the efficiency of H2O2 production, as the strong bonding between CNTs and Bi2Te3, along with the excellent conductivity of CNTs, facilitates charge carrier separation and transport, as confirmed by TE electrochemical tests. This study underscores the significant potential of thermoelectric nanomaterials for converting waste heat into green chemical synthesis.

Membrane-free Electrolysis Production of Hydrogen Peroxide on Low-Cost Metal-Free Electrocatalysts for Dye Degradation.

The efficient production of hydrogen peroxide (H2O2) solution was achieved by combining cathodic two-electron oxygen reduction (2e- ORR) and anodic two-electron water oxidation (2e- WOR) in two half-reaction cells. h-BN loaded on carbon fibers (h-BN@C) is prepared and employed as an anode material to catalyze 2e- WOR, while sulfonated commercial BP-2000 carbons (BP-2000-SO3H) were prepared as the cathode materials for 2e- ORR. In a 2 M KHCO3 solution, an overall Faradaic efficiency of 97% and a total H2O2 production rate of 1872 mmol g-1 h-1 over metal-free electrodes were accomplished in a membrane-free flow cell. The dilute H2O2 solution could be directly used to degrade cationic Rhodamine B or methyl orange and anionic methylene blue dyes in water. This work proved low-cost production of dilute H2O2 solution in simple membrane-free flow cells with single electrolyte and on-site utilization for efficient dye degradation.

A Multi-Enzyme Nanocascade to Target Disease-Relevant Metabolites.

Metabolic processes in living organisms depend on the synergistic actions of enzymes working in proximity and in concert, catalyzing reactions effectively while regulating the formation of metabolites. This enzyme synergy offers promising therapeutic application for diseases such as alcohol intoxication, cancer, and hyperinflammation. Despite their potential, the clinical translation of enzyme cascades is restricted by challenges including poor enzyme stability, short half-life, and a lack of delivery strategies that maintain enzyme proximity. In this study, multi-enzyme nanocascades synthesized are developed through in situ atom transfer radical polymerization using a zwitterionic monomer. This method markedly enhances enzyme stability and proximity, thereby prolonging their circulation half-life after systemic administration. It is demonstrated that the nanocascades of uricase and catalase effectively reduce uric acid levels without excessive hydrogen peroxide production, providing a potential antidote for hyperuricemia. Moreover, in a murine breast cancer model, the nanocascades of glucose oxidase and catalase inhibited tumor progression and enhanced the therapeutic efficacy of doxorubicin. The prolonged circulation and promoted reaction efficacy of these nanocascades underscore their substantial potential in enzyme replacement therapy and the treatment of various diseases.

Bacteria-Mediated Tumor-Targeting Delivery of Multienzyme-Mimicking Covalent Organic Frameworks Promoting Pyroptosis for Combinatorial Sono-Catalytic Immunotherapy.

Pyroptosis, an inflammatory cell death, has attracted great attention for potentiating a strong immune response against tumor cells. However, developing powerful pyroptosis inducers and then activating specific pyroptosis still remains challenging. Herein, a PEG-CuP-COF@∆St nanosystem is rationally designed, consisting of PEG-CuP-COF nanozyme pyroptosis inducers and tumor-targeting bacteria of the Salmonella Typhimurium strain VNP20009 (ΔSt), with an affinity for the tumor hypoxic microenvironment. The PEG-CuP-COF nanozymes possessed excellent sonodynamic performance and multienzyme-mimicking activities to generate reactive oxygen species (ROS) and then induce potent pyroptosis. The superoxide dismutase- and peroxidase-mimicking activities of PEG-CuP-COF catalytically produced hydrogen peroxide (H2O2) and hydroxyl radicals (•OH) which have important value in triggering acute inflammatory responses and pyroptosis. Moreover, PEG-CuP-COF showed outstanding glutathione peroxidase-mimicking activities, impairing the antioxidant defense in tumor cells and enhancing sonodynamic efficiency by making them more vulnerable to ROS-induced damage. During in vivo studies, PEG-CuP-COF@∆St nanosystem with its self-driven property exhibited impressive tumor-targeting capability and activated Caspase-3/gasdermin E-dependent pyroptosis to inhibit tumor growth. More importantly, it induced a powerful immune memory effect to prevent bone metastasis. In summary, this study introduces an innovative approach for combinatorial sono-catalytic immunotherapy using bacteria-mediated tumor-targeting delivery of nanozymes as specific pyroptosis inducers.

The role of ACSL4 in stroke: mechanisms and potential therapeutic target.

Stroke, as a neurological disorder with a poor overall prognosis, has long plagued the patients. Current stroke therapy lacks effective treatments. Ferroptosis has emerged as a prominent subject of discourse across various maladies in recent years. As an emerging therapeutic target, notwithstanding its initial identification in tumor cells associated with brain diseases, it has lately been recognized as a pivotal factor in the pathological progression of stroke. Acyl-CoA synthetase long-chain family member 4 (ACSL4) is a potential target and biomarker of catalytic unsaturated fatty acids mediating ferroptosis in stroke. Specifically, the upregulation of ACSL4 leads to heightened accumulation of lipid peroxidation products and reactive oxygen species (ROS), thereby exacerbating the progression of ferroptosis in neuronal cells. ACSL4 is present in various tissues and involved in multiple pathways of ferroptosis. At present, the pharmacological mechanisms of targeting ACSL4 to inhibit ferroptosis have been found in many drugs, but the molecular mechanisms of targeting ACSL4 are still in the exploratory stage. This paper introduces the physiopathological mechanism of ACSL4 and the current status of the research involved in ferroptosis crosstalk and epigenetics, and summarizes the application status of ACSL4 in modern pharmacology research, and discusses the potential application value of ACSL4 in the field of stroke.

Genome-Wide Analysis of the Serine Carboxypeptidase-like (SCPL) Protein Family of Bitter Gourd and Functional Validation of McSCPL22 in Fusarium oxysporum f. sp. Momordicae (FOM) Resistance

Bitter gourd is increasingly being recognized for its value as a vegetable and medicinal use, but the molecular mechanisms of pathogen resistance remain relatively poorly understood. The serine carboxypeptidase-like (SCPL) protein family plays a key role in plant growth, pathogen defense, and so on. However, a comprehensive identification and functional characterization of the SCPL gene family has yet to be conducted in bitter melon. In this study, 32 SCPL genes were identified in bitter gourd and divided into three classes. The number of SCPL genes contained in the three clusters was 7, 7, and 18, respectively. Most SCPL gene promoters contain cis-acting elements with light, hormone, and stress responses. The RNA sequencing data showed that the expression of several SCPL genes changed significantly after pathogen infection. In particular, expression of the McSCPL4, 10, 17, 22, and 25 genes increased substantially in the resistant varieties after infection, and their expression levels were higher than those in the susceptible varieties. These results suggested that genes such as McSCPL4, 10, 17, 22, and 25 may play a significant role in conferring resistance to fungal infections. Moreover, the expression levels of the McSCPL10, 17, 22, 23, and 25 genes were likewise significantly changed after being induced by salicylic acid (SA) and jasmonic acid (JA). In situ hybridization showed that McSCPL22 was expressed in the vascular tissues of infected plants, which largely overlapped with the location of Fusarium oxysporum f. sp. Momordicae (FOM) infection and the site of hydrogen peroxide production. Our results showed that McSCPL22 may be involved in the regulation of the SA and JA pathways and enhance resistance to FOM in bitter gourd plants. This is the first study to perform SCPL gene family analysis in bitter gourd. McSCPL22 may have the potential to enhance FOM resistance in bitter gourd, and further investigation into its function is warranted. The results of this study may enhance the yield and molecular breeding of bitter gourd.

Sustainable photocatalytic hydrogen peroxide production over octonary high-entropy oxide

The direct utilization of solar energy for the artificial photosynthesis of hydrogen peroxide (H2O2) provides a reliable approach for producing this high-value green oxidant. Here we report on the utility of high-entropy oxide (HEO) semiconductor as an all-in-one photocatalyst for visible light-driven H2O2 production directly from H2O and atmospheric O2 without the need of any additional cocatalysts or sacrificial agents. This high-entropy photocatalyst contains eight earth-abundant metal elements (Ti/V/Cr/Nb/Mo/W/Al/Cu) homogeneously arranged within a single rutile phase, and the intrinsic chemical complexity along with the presence of a high density of oxygen vacancies endow high-entropy photocatalyst with distinct broadband light harvesting capability. An efficient H2O2 production rate with an apparent quantum yield of 38.8% at 550 nm can be achieved. The high-entropy photocatalyst can be readily assembled into floating artificial leaves for sustained on-site production of H2O2 from open water resources under natural sunlight irradiation.

Neuroprotective Effect of Natural Indole and β-carboline Alkaloids against Parkinson's Disease: An Overview.

Parkinson's disease (PD) is a devastating neurodegenerative condition that mostly damages dopaminergic neurons in the substantia nigra and impairs human motor function. Males are more likely than females to have PD. There are two main pathways associated with PD: one involves the misfolding of α-synuclein, which causes neurodegeneration, and the other is the catalytic oxidation of dopamine via MAO-B, which produces hydrogen peroxide that can cause mitochondrial damage. Parkin (PRKN), α-synuclein (SNCA), heat shock protein (HSP), and leucine-rich repeat kinase-2 (LRRK2) are some of the target areas for genetic alterations that cause neurodegeneration in Parkinson's disease (PD). Under the impact of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP), which is also important in Parkinson's disease (PD), inhibition of mitochondrial complex 1 results in enhanced ROS generation in neuronal cells. Natural products are still a superior option in the age of synthetic pharmaceuticals because of their lower toxicity and moderate side effects. A promising treatment for PD has been discovered using beta-carboline (also known as " β-carboline") and indole alkaloids. However, there are not many studies done on this particular topic. In the herbs containing β-carbolines and indoles, the secondary metabolites and alkaloids, β-carbolines and indoles, have shown neuroprotective and cognitive-enhancing properties. In this review, we have presented results from 18 years of research on the effects of indole and β-carboline alkaloids against oxidative stress and MAO inhibition, two key targets in PD. In the SAR analysis, the activity has been correlated with their unique structural characteristics. This study will undoubtedly aid researchers in looking for new PD treatment options.

Assessment of clinical and laboratory parameters of oral сavity in patients with orthodontic systems

equipment (braces) on the biochemical parameters of oral fluid. Materials and methods. The study involved patients aged 18 to 22 years who are undergoing orthodontic treatment with a bracket system. Thegroup of examined persons was 25 people. The control group included 15 practically healthy people without braces. All patients underwent dental status assessment (Green – Vermillion hygiene index – simplified IG-Y; PMA inflammation index), laboratory examination of oral fluid before and after controlled oral hygiene. The biochemical analysis included determination of the acid-base balance in the oral fluid using a pH meter, assessment of free radical oxidation by chemiluminogram parameters by biochemiluminescence and by levels of molecular products of lipid peroxidation (diene and triene conjugates, Schiff bases), activity of the enzyme alkaline phosphatase, concentrations of total protein and lactate. Results and discussions. In patients undergoing orthodontic treatment with a bracket system, an insufficient level of oral hygiene and inflammatory manifestations in the gums of moderate severity were revealed. The level of the acid-base balance of the oral fluid before controlled hygiene was equal to 6.8±0.19, that is, below the range of normal pH values in the oral cavity. After hygiene, the pH of the oral fluid returned to the norm of 7.1±0.2. In patients with braces, activation of free radical oxidation and an increase in lipoperoxidation parameters – triene conjugates and Schiff bases, increased activity of alkaline phosphatase, total protein and lactate levels took place.Cоnclusion. After hygienic treatment of the oral cavity, the biochemical parameters did not differ statistically significantly from the control data.

CuO/Cu(OH)2@g-C3N4 derived from CuBTC/g-C3N4 for two channel photocatalytic hydrogen peroxide production

CuO/Cu(OH)2@g-C3N4 derived from CuBTC/g-C3N4 for two channel photocatalytic hydrogen peroxide production

Demyelination in cuprizone mice is ameliorated by Calycosin mediated through astrocyte Nrf2 signaling pathway

Oxidative stress plays a pivotal role in multiple sclerosis (MS), triggering demyelination predominantly through excessive peroxide production and the depletion of antioxidants. The accumulation of oxidative damage can be caused by dysregulation of astrocytes, which are the brain's main regulators of oxidative homeostasis. Calycosin, an essential bioactive component extracted from Astragalus, is recognized for its neuroprotective properties. Although recent research has highlighted calycosin's neuroprotective capabilities, its role in demyelinating conditions like MS remains unclear. In this work, we examined the possible molecular mechanism of calycosin's neuroprotective effect on cuprizone (CPZ)-induced demylination in mice. According to our research, calycosin successfully reduced demyelination and behavioral dysfuction in CPZ mice. Calycosin also decreased the production of oxidative stress and enhanced the expression of antioxidants in CPZ mice and in astrocytes induced by hydrogen peroxide (H2O2). Furthermore, both in vivo and in vitro experiments demonstrated that calycosin promoted the nuclear translocation of nuclear factor erythroid 2-related factor 2 (Nrf2) along with the upregulation of heme oxygenase 1 (HO-1), NAD(P)H quinone dehydrogenase 1 (NQO1), and superoxide dismutase (SOD). Importantly, the application of all-trans retinoic acid (ATRA), a specific inhibitor of Nrf2, effectively reversed the myelin-protective and antioxidant effects conferred by calycosin. This study suggested that calycosin might exert neuroprotection by inhibiting oxidative stress and reducing demyelination via the activation of astrocyte Nrf2 signaling. These findings indicated that calycosin might be a potential candidate for treating MS.

Influenza and non-influenza ARVI in children. A relationship between cytokine profile, parameters of the “lipid peroxidation – antioxidant defense system” as well as clinical and laboratory indicators

Influenza and acute respiratory viral infections (ARVI) impose a substantial damage to the population health in the Russian Federation due to their seasonal circulation and predominantly affect young children. A very few data on the cytokine profile, the nonspecific LPO — AOD system and their relationships with clinical characteristics in such diseases in preschool children are available. The aim of this study was to assess the cytokine profile, LPO — AOD system parameters and their relationship with the clinical and laboratory characteristics of diseases in preschool children with influenza and other ARVI. 86 preschool children (3–6 years old) were examined: with an established diagnosis of influenza (n = 31), non-influenza ARVI (n = 28), apparently healthy children (control group (n = 27). All pediatric samples were analyzed by enzyme-linked immunosorbent assay assessing blood serum concentrations of C-reactive protein and cytokines IL-1β, IL-4, IL-6, IL-8, TNFα, IFNα, IFNγ. Spectrophotometric, fluorometric and enzyme immunoassay methods to assess the state of the “LPO — AOD” system were used. In the group of children with influenza vs other ARVI, a higher incidence of intoxication syndrome was revealed. Cytokine profile in children from both clinical groups compared with control cohort was featured with higher indicators of both pro-inflammatory and anti-inflammatory origin. Children with non-influenza ARVI, had increased magnitude of LPO final products in the nonspecific LPO — AOD system along with lowered concentration of fat-soluble vitamins, general antioxidant activity, GSH level, and SOD activity. In the group with influenza, the level of primary and final lipid peroxidation products was increased, whereas that of for retinol,α-tocopherol, and total antioxidant activity was decreased paralleled with higher GSSG and SOD levels. Numerous correlations were noted in the group of children with ARVI: IL-1β/ketones, IL-6/ketones, IL-8/ketones, TNFα/ketones, IL-4/ketones, IFNg/shortness of breath, IFNα/cough, double bonds/fever, double bonds/AST, SO/intoxication, retinol/fever, GSSG/cough. The influenza group differed in the following relationships: IL-4/ketones, IL-4/fever, IFNα/ketones, CDs/AST. It can be concluded that in preschool children with ARVI and influenza, changes in the cytokine profile are accompanied by increased pro- and anti-inflammatory cytokine levels, increased intensity of lipid peroxidation reactions along with reduced magnitude of antioxidant factors. In the group with ARVI, there was a relationship between the final toxic products of lipid peroxidation — Schiff bases — and the intoxication index, as well as the presence of protective mechanisms in the form of connections between interferons and disease clinical manifestations. The group with influenza was distinguished by the presence of protective relations, which may have a beneficial effect in the context of developing pathological process. The data obtained will help expand the understanding of the pathogenetic mechanisms related to immune reactivity and nonspecific lipid peroxidation reactions in preschool patients and formulate appropriate measures for correction.

Modulating Core Polarity in Metal-free Covalent Organic Frameworks for Selective Electrocatalytic Hydrogen Peroxide Production.

Tuning the charge density at the active site to balance the adsorption ability and reactivity of oxygen is extremely significant for driving a two-electron oxygen reduction reaction (ORR) to produce hydrogen peroxide (H2O2). Herein, we have highlighted the influence of intermolecular polarity in covalent organic frameworks (COFs) on the efficiency and selectivity of electrochemical H2O2 production. Different C3 symmetric building blocks have been utilized to regulate the charge density at the active sites. The benzene-cored COF, which exhibits reduced polarity than the triazine-cored COF, displayed enhanced performance in H2O2 production, achieving 93.1% selectivity for H₂O₂ at 0.4 V with almost two-electron transfer and a faradaic efficiency of 90.5%. In-situ electrochemical Raman spectroscopy and scanning electrochemical microscopy (SECM) were employed to confirm H₂O₂ generation and analyze spatial reactivity patterns. These techniques provided detailed insights into localized catalytic behavior, emphasizing the influence of core polarity.

Modulating Core Polarity in Metal‐free Covalent Organic Frameworks for Selective Electrocatalytic Hydrogen Peroxide Production

Tuning the charge density at the active site to balance the adsorption ability and reactivity of oxygen is extremely significant for driving a two‐electron oxygen reduction reaction (ORR) to produce hydrogen peroxide (H2O2). Herein, we have highlighted the influence of intermolecular polarity in covalent organic frameworks (COFs) on the efficiency and selectivity of electrochemical H2O2 production. Different C3 symmetric building blocks have been utilized to regulate the charge density at the active sites. The benzene‐cored COF, which exhibits reduced polarity than the triazine‐cored COF, displayed enhanced performance in H2O2 production, achieving 93.1% selectivity for H₂O₂ at 0.4 V with almost two‐electron transfer and a faradaic efficiency of 90.5%. In‐situ electrochemical Raman spectroscopy and scanning electrochemical microscopy (SECM) were employed to confirm H₂O₂ generation and analyze spatial reactivity patterns. These techniques provided detailed insights into localized catalytic behavior, emphasizing the influence of core polarity.

Regulation of Exciton Effects in Functionalized Conjugated Polymers by B‐N Lewis Pairs for Visible‐Light Photocatalysis

Strong excitonic effects are common in organic conjugated polymer semiconductors, severely hindering the generation of free charge carriers for conducting photocatalysis. Therefore, exploring new channels to modulate exciton dissociation in polymers is far‐reaching in facilitating photocatalysis. A series of B‐N Lewis pair functionalized conjugated polymers have been developed to minimize exciton effects by modulating charge transfer pathways. Theoretical studies have shown that introducing B‐N Lewis pairs can dramatically increase the distance of charge transfer (D index) and the amount of electron transfer and reduce the Coulomb attraction energy (EC), which contributes to breaking the equilibrium of the coexistence of excitons and charge carriers. Further experimental results show that the singlet excitons are efficiently dissociated into more free‐charge carriers under photoexcitation to participate in surface reactions. The optimized polymer PyPBM shows an exponential increase in photocatalytic hydrogen and hydrogen peroxide production performance by visible light illumination.

Regulation of Exciton Effects in Functionalized Conjugated Polymers by B-N Lewis Pairs for Visible-Light Photocatalysis.

Strong excitonic effects are common in organic conjugated polymer semiconductors, severely hindering the generation of free charge carriers for conducting photocatalysis. Therefore, exploring new channels to modulate exciton dissociation in polymers is far-reaching in facilitating photocatalysis. A series of B-N Lewis pair functionalized conjugated polymers have been developed to minimize exciton effects by modulating charge transfer pathways. Theoretical studies have shown that introducing B-N Lewis pairs can dramatically increase the distance of charge transfer (D index) and the amount of electron transfer and reduce the Coulomb attraction energy (EC), which contributes to breaking the equilibrium of the coexistence of excitons and charge carriers. Further experimental results show that the singlet excitons are efficiently dissociated into more free-charge carriers under photoexcitation to participate in surface reactions. The optimized polymer PyPBM shows an exponential increase in photocatalytic hydrogen and hydrogen peroxide production performance by visible light illumination.