Free Radical Chain Research Articles

Mechanism of methyl elaidate on the thermal oxidation behavior

The effects of cis–trans isomerization on the oxidation products of oleic acid (composites and structure characterization) were investigated. The reduction of thermal oxidation reaction of methyl elaidate (ME) was 6.72 % lower than that of methyl oleate (MO), and the oxidation products (core aldehydes) first increased and then decreased with the prolongation of thermal oxidation time. ME exhibited better oxidation stability than MO in free radicals, hydroperoxides, double bonds, aldehydes, and glycerides. The oxidation products were mainly 11-oxo-9-undecenoate (initial stage) and methyl 9-oxononanoate (later stage), following the free radical chain reaction mechanism. The H8 in double bond was more easily dehydrogenated in the chain initiation stage than H11, followed by the formation of core aldehyde through three intermediates and two transition states each pathway. ME required a higher energy barrier (1.3–13.6 kJ/mol) than MO reaction, making it more difficult for ME to undergo thermal oxidation reaction. The transition state 4 and 5 were rate determining steps of chain initiation reaction and proliferation reaction, respectively. This study was of great significance to further control the formation of these trans fats and their oxidation products.

Lignin‐based nitrogen and phosphorus‐containing polylactic acid with flame‐retardant performances

AbstractPolylactic acid (PLA) is a new type of biodegradable material that has been applied in many fields such as extrusion, injection molding, film drawing, and spinning. In contrary, it does not have flame retardancy. In this paper, N‐PCDL was synthesized by amidation reaction between COOH of PCDL and NH2 of tetraethylenepentamine (TEPA), followed by an Atherton‐Todd reaction of unreacted NH2 at the other end of TEPA with PH of DOPO to prepare a novel lignin‐based flame retardant containing nitrogen and phosphorus (NP‐PCDL). The Fourier transform infrared spectroscopy (FT‐IR) and nuclear magnetic hydrogen spectroscopy (1H NMR) analysis results showed that proton peaks of CONH, PN, and NH appeared in the NP‐PCDL spectrum, while the characteristic absorption peak of PH bond disappeared in DOPO, the X‐ray photoelectron spectroscopy (XPS) results showed that the degraded lignin consisted of elements C and O, while NP‐PCDL consisted of elements C, O, N and P. The above results indicated that NP‐PCDL was successfully prepared. NP‐PCDL accounted for 3% (mass percentage, the same below), 5% and 10% of PLA, then lignin based flame‐retardant PLA composites were prepared by internal mixing and injection molding. Thermogravimetric analysis (TGA) showed that the residual carbon of PLA/3% NP‐PCDL, PLA/5% NP‐PCDL and PLA/10% NP‐PCDL at 800°C were higher than that of pure PLA, with the increase of 56.56%, 97.54%, and 301.64%, respectively; The analysis of SEM, XPS, and Raman showed that PLA/NP‐PCDL formed dense, regular and highly graphitized residual carbon with phosphorus nitrogen structure during the combustion process. At the same time, NH3, H2O and PO˙ free radicals were released, which could dilute combustible gases, destroy free radical chain reaction, isolate combustible gases and heat, so as to play a flame‐retardant role.

Hydrogen therapy from the initiation to its practical applications

Molecular hydrogen (H2) has emerged as a therapeutic and prophylactic agent devoid of adverse effects. H2 demonstrates multifaceted functionality across diverse cell types and organs, attributable to its interaction with oxidized hemes as a fundamental molecular mechanism. Given the abundance of various heme types both intracellularly and extracellularly, the broad-ranging effects of H2 are comprehensible. Subsequent Pathways are mediated by end-or modified- products of lipid peroxide followed by free radical chain reactions. Notably, H2 confers benefits not only to patients afflicted with diseases but also to individuals seeking to enhance health and wellness. The mission of hydrogen medicine encompasses addressing unresolved medical challenges, including cerebral infarction, post-cardiac arrest syndrome, advanced cancer, metabolic syndrome, and dementia. Transitioning from animal experiments to clinical studies is imperative to confront these formidable diseases effectively.

Revealing the Intrinsic Correlation between Cu Scales and Free Radical Chain Reactions in the Regulation of Catalytic Behaviour.

Defining the copper-based catalysts that are responsible for the catalytic behaviour of oil-paper insulation systems and implementing effective regulation are of great significance. Accelerated ageing experiments were conducted to reveal variations in copper scales and deterioration in insulation properties. As ageing progressed, TEM images demonstrated that copper species were adsorbed and aggregated on the fibre surface in the form of nanoparticles (NPs). The scale of NPs exhibited a continuous increase, from 27.06 nm to 94.19 nm. Cu(I) and Cu(II) species were identified as the active sites for inducing intense free radical reactions, which significantly reduced the activation energy, making the insulating oil more susceptible to oxidation. The role of the antioxidant di-tert-butyl-p-cresol (DBPC) in extending the insulation life was regulated by determining the optimal addition time based on variations in the interfacial tension. After the second addition of DBPC, the ageing rates of the dissipation factor, acidity, micro-water and breakdown voltage in the Cu+DBPC group decreased by 28.8%, 43.2%, 52.9% and 46.7%, respectively, compared to the Cu group. This finding not only demonstrates the crucial role of DBPC in preventing the copper-based catalyst-induced oxidation of insulating oil, but also furnishes a vital foundation for enhancing the long-term stability of transformer insulation systems.

Research Progress on the Intervention of Traditional Chinese Medicine in Signal Pathways Related to Acute Cerebral Infarction

Acute cerebral infarction is a disease with high incidence, mortality, and disability rates. Its etiology is complex, and the exact pathogenesis is not yet fully understood. Current studies often involve inflammatory responses, apoptosis, oxidative stress, atherosclerosis, excitotoxicity, and free radical chain reactions. Signal pathways play a crucial role in the occurrence and development of this condition. Traditional Chinese medicine can improve the condition of patients with acute cerebral infarction by intervening in multiple signal pathways. This paper systematically reviews recent literature, identifying 11 key signal pathways, including NLRP3, TLR4/NF-κB, Nrf2/ARE, CD40/CD40L, JAK/STAT, PI3K/AKT, JNK/p38 MAPK, Wnt, Notch, RhoA/ROCK, and ERK1/2. The aim is to provide some reference for the research on traditional Chinese medicine treatments for acute cerebral infarction.

Research on the Potential of Persistent Free Radicals Triggering Open-Pit Coal Oxidation and Spontaneous Combustion

ABSTRACT This study attempts to reveal the triggering pathways of open-pit coal oxidation and spontaneous combustion from the perspective of persistent free radicals (PFRs). To this end, electron spin resonance technology, spin trap technology, and quantum chemical calculations were combined to study the occurrence characteristics of PFRs in coal and their photoreaction characteristics. Based on typical coal molecular fragments, the mechanism of PFRs triggering open-pit coal oxidation was further revealed. The results indicate that coal contains abundant PFRs, which produce reactive oxygen species (ROS) after exposure to sunlight, mainly including hydroxyl radicals (•OH) and superoxide anion radicals (O2 •−). Among them, the higher the initial content of PFRs or the longer the time of sunlight exposure, the more favorable it is for the production of •OH, the concentration of photoinduced •OH remains at the level of 1011 spin/mm3. Compared to O2 in the air, these photoinduced •OH have stronger oxidizing properties and can trigger free radical chain reactions of coal oxidation at room temperature (activation energies ＜ 40 kJ/mol), releasing reaction heat (average enthalpy change is −65.53 kJ/mol). As a common oxidant in coal spontaneous combustion (CSC) process, O2 does not possess these abilities (activation energies greater than 190 KJ/mol and enthalpy change greater than 160 KJ/mol). From the perspectives of thermodynamics and kinetics, PFRs in coal have the potential to indirectly trigger open-pit coal oxidation and spontaneous combustion. Therefore, the efficient quenching of PFRs or inhibiting the production of •OH will be beneficial for preventing the oxidation and spontaneous combustion of open-pit coal. This study provides a new perspective on revealing the mechanism of CSC and developing new inhibitors.

Polycyclic aromatic compounds surface modulation of TiO2@SiO2 nanoparticles enhances the insulation performance of polypropylene film

Polypropylene (PP) film is an important component of metallized film capacitors. However, the insulation issues of polypropylene film significantly affect the safe and stable operation of capacitors. In this study, polycyclic aromatic compounds (PAC) were introduced to the surface of TiO2@SiO2 nanoparticles via chemical grafting, preparing Ti@Si-PAC nanofillers, to achieve modulation of the nanoparticle/PP interface. The experimental and simulation results indicate that Ti@Si-PAC/PP exhibits excellent insulation performance. The study indicates that the surface modulation of nanoparticles by PAC introduces a ‘soft interface’ between the nanoparticles and the polypropylene matrix. The ‘soft interface’ enhances the interfacial interaction, reduces dielectric loss, and introduces deep traps, exhibiting a significant inhibitory effect on carrier migration. Additionally, the introduction of PAC enhances the electron trapping capability in the interface region, which plays a positive role in quenching free radical chain reactions and reducing the damage of high-energy electrons to polypropylene molecular segments. This study provides an effective method for enhancing the insulation performance of polypropylene.

A step to microplastic formation: Microcracking and associated surface transformations of recycled LDPE, LLDPE, HDPE, and PP plastics exposed to UV radiation

Plastics when exposed to UV radiation start to degrade via photooxidative aging including free radical formation, oxidation, chain scission and/or crosslinking reactions. These chemical changes can cause loss in mechanical strength, surface embrittlement, and eventually surface erosion. The eroded particles are microplastics (MPs), which have been identified as a potentially serious threat to the environment and its inhabitants. In general, photodegradation of virgin plastics has been studied extensively, but there is not much literature on the degradation of recycled plastics. The goal of the study was to investigate the changes caused by photodegradation in recycled plastics and assess the potential risks of MPs formation. And eventually, knowing the chemical and physical transformations occurring on the surface understand the mechanism behind surface microcracking, which is the first step of MPs formation. Pellets of five industrially recycled plastics (low-density polyethylene (rLDPE), linear low-density polyethylene (rLLDPE), high-density polyethylene (rHDPE), and two polypropylenes (rPP)) from different waste sources were analysed. UV irradiation was performed in an accelerated weathering chamber for milled (< 400 µm) plastic powder to ensure homogeneous changes throughout the sample. The properties were investigated by ATR-FTIR, HT-SEC, XPS and DSC. Formation of microcracks was studied on plastic pellets by SEM. The results showed that the degradation significantly differed between the recycled plastics, and the waste source was more important than the plastic type. rLDPE and one of the rPP samples showed a significant increase in carbonyl index as well as decrease in molar mass during the first 500 h of UV exposure. The other rPP and rHDPE samples showed first considerable signs of degradation only after 1000 h of UV exposure. Minor changes were observed for the rLLDPE sample during the whole test. The SEM revealed microcracking on the surface of all samples, which also had noticeable degradation identified by other methods. These recycled plastics can be considered the ones with the highest potential of MPs formation. From the chemical and physical transformations identified on the surface, the mechanism leading to microcracking, which is the first step in the formation of MPs, is proposed.

DFT-based computational analysis of 2,4-dimethyl-6-tert-butylphenol (DTBP) as an antioxidant in aviation fuels

Antioxidants are indispensable additives for ensuring the long-term stability, performance, and reliability of aviation fuels. They prevent the formation of gum and other insoluble deposits in the fuel which clog fuel systems, leading to engine problems. This is achieved by inhibiting free radical chain reactions involved in the oxidation of hydrocarbons in the fuel. The compound 2,4-Dimethyl-6-tert-butyl phenol (DTBP) is one of the widely used antioxidants in aviation fuels. In this report, the radical scavenging done by DTBP is analysed computationally by density functional theory (DFT) with the model chemistry X/6-31+G(d,p), where X represents certain Minnesota functionals such as MN15, M05-2X, M06-2X, M08-HX, and M11. Among the well-known modes of radical scavenging, namely HAT, SETPT, and SPLET, the HAT mode is preferred in the gaseous phase, while SPLET operates in non-polar solvents, as computations indicate. Fukui indices, global reactivity descriptors, electronic spectra, and natural bond orbitals (NBOs) are also generated to explain the results. Understanding the mechanism of radical scavenging is important in designing powerful and efficient antioxidants for aviation fuels such as jet fuel, aviation gasoline, Jet B, and bio-kerosene.

Photoelectrochemical synthesis of chloroprocaine from procaine coupled with hydrogen generation

AbstractChloroprocaine is favored in anesthesia for its effectiveness and safety but is produced through complex, environmentally harmful processes. There is a growing interest in developing greener, more cost‐effective methods for producing chloroprocaine. Here, we establish a green and cost‐effective photoelectrochemical (PEC) approach for synthesizing chloroprocaine from procaine using a WO3 photoanode with oxygen vacancies. Achieving a high yield of 18.8 μmol cm−2 h−1 with selectivity of 92% and FE of 99%, this method leverages a free radical chain mechanism initiated by Cl· radicals formed over the WO3. The incorporation of oxygen vacancies enhances light absorption and charge separation, facilitating Cl· and Cl2 generation critical for its synthesis. We successfully produced 37.4 mg of chloroprocaine and 5.4 mL of hydrogen using a self‐powered PEC device, demonstrating the method effectiveness and environmental friendliness for chloroprocaine synthesis and hydrogen production.

Alwyn George Davies. 13 May 1926—1 September 2023

Alwyn Davies was one of the last surviving members of Christopher Ingold (FRS)'s research group, a set of chemists who together transformed our understanding of mechanistic organic chemistry and laid the foundation for modern teaching of the subject. His early independent research on organic peroxides led into organometallic peroxides and thence into organometallic chemistry. His monographs Organic peroxides (1961, Butterworths) and Organotin chemistry (1997, 2004, Wiley) helped to promote the rapid growth of these topics. One route to organometallic peroxides was the reaction of organometallic compounds with dioxygen, and Alwyn Davies showed that these reactions occurred by a free radical chain reaction. Perhaps his greatest contribution was to establish that radical reactions would often occur at the metal centres in main group organometallic compounds, sometimes a million times faster than at hydrogen. He used electron spin resonance (ESR) spectroscopy to monitor the products and rates of these reactions, and to study the properties of the organic radicals that were produced. The theme of metals behaving as hydrogen surrogates permeated much of the work. In his later career, he developed improved methods for generating organic radical cations, and he recorded and analysed their unusual ESR spectra.

Potential of Oyster Mushroom (Pleurotus ostreatus) secondary metabolites on KRAS protein in-silico liver cancer

Liver Cell Carcinoma (KSH) currently ranks as the fourth most common cause of death due to cancer worldwide and is the sixth most common cancer in the world. HCC (Hepatocellular Carcinoma) is caused by environmental factors, viral infections, and certain genetic changes. Ras is a very important oncogene and is hypermutated in various types of cancer, including HCC. The doxorubicin compound is a curative agent that is widely used for chemotherapy treatment of various types of cancer, however, administration of the kura agent with high cytotoxic activity can cause several side effects. Secondary metabolite compounds have anti-oxidant capabilities including breaking free radical chains and chelating redox-active metal ions which cause lipid peroxidation. These properties also help prevent cancer. Pleurotus otstreatus bioactive compounds that have antioxidant potential, flavonol. Due to the potential cytotoxic activity of these secondary metabolites, a bioinformatics approach is needed in this research to determine the results of predicting the interaction activity of flavonol compounds on the KRAS protein in silico and to determine the amino acids and bonds involved in the interaction. between these compounds and the KRAS protein, as a reference for future HCC drugs. The method used is using the PyRx device, Biovia Discovery Studio, Autodock for the docking process and validating the docking results. The results of this research are that flavonol compounds have a docking value of -7.1 kcal/mol. This compound has the potential as a candidate compound that can be used in liver cancer therapy, because it’s have high values ​​and close to the positive control value, namely doxorubicin, of -7.6 kcal/mol.

System-wide coordination and communication of lipid metabolism atlas revealed cytotoxicity of epoxy triglyceride in deep-frying oil

The epoxy triglycerides generated by oxidation, cyclization, and free radical chain reaction of unsaturated dietary oils during deep-frying are demonstrated to have cytotoxicity and can induce lipid metabolism related diseases. Metabolic diseases are usually characterized by metabolic abnormalities in different tissues, however, the relationship between changes in intratissue coordination and communication induced by epoxy triglycerides and specific pathogenic mechanisms remains largely unknown. We conducted lipid metabolomics analysis across six different tissues in C57BL/6J mice, including the medial prefrontal cortex, interscapular brown adipose tissue, epididymal white adipose tissue, liver, intestine, and heart. Normal diet intake demonstrated a high degree of association between lipid metabolites, indicative of cross-communication and cooperation among various tissues and organs, while, a global correlation that was disrupted and restructured by epoxy triglycerides intake. Examination of blood samples revealed that epoxy triglycerides enhanced bacterial translocation from the gut to the systemic circulation, consequently stimulating the TLR4/CD36/NF-κB pathway. In summary, this study found that epoxy triglyceride upsets the comprehensive coordination and information exchange of lipid metabolism, providing a fresh perspective for future research on the systemic metabolic network and identifying metabolic disease markers and associated mechanisms induced by deep-frying oil.

A multifunctional tannic acid binder for 5.0 V LiNi0.5Mn1.5O4 electrodes and its interfacial characterization

Due to the higher working voltage of spinel LiNi0.5Mn1.5O4 (LNMO), the electrolyte degrades at high potentials, leading to the generation of numerous alkyl radicals.The transition metals will dissolve under high-voltage reactions, resulting in an unstable LNMO/electrolyte interface, ultimately deteriorating the battery’s cycling performance. In this study, a PAALi-TAc composite binder was obtained through the crosslinking of polyphenolic hydroxides Tannic acid (TAc) with PAALi. The electrode fabricated using this binder achieved a maximum capacity of 132.6 mAh g−1 at a 1 C rate. After 100 cycles, the capacity remained at 130.3 mAh g−1, with a retention rate of 98.2%. Even after 400 cycles, the capacity was maintained at 113.2 mAh g−1, with a retention rate of 85.3%. During the 400 cycles of high-current fast charge and discharge at 5 and 10 C, the capacity retention rates were 89.3% and 88.0%, respectively. The PAALi-TAc binder played a crucial role in establishing a compatible electrolyte interface by terminating the free radical chain reactions and chelating the excess dissolved metals in high-voltage LNMO//Li batteries, and this led to improved cycling and rate performance.

Synergistic effects of organosilicon flame retardant and DOPO-based reactive compatibilizer for high performance PC/PBT composites

PC/PBT alloy is flammable resulting in fire safety hazards in practical applications and the existing flame retardants have a great influence on the mechanical properties, which limits its application range. Therefore, it is an urgent problem to improve the flame retardancy of PC/PBT alloy while taking its mechanical properties into account. Herein, a novel flame retardant and reactive compatibilizer was synthesized by grafting 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO) onto ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA), named as DOPO-EG, to improve the flame retardancy and mechanical properties of PC/PBT alloy simultaneously. Additionally, based on the effective synergistic effect of enhancing the charring and flame retardancy between silicon and phosphorus, the organosilicon flame retardant (RMSi) is introduced and compounded with DOPO-EG to prepare excellent flame retardancy PC/PBT/DOPO-EG/RMSi composites. The results showed that the PC/PBT/DOPO-EG/RMSi composites with 10 wt% DOPO-EG and 8 wt% RMSi (CBE10P10Si8) reached UL-94 V-0 rating and the peak of heat release rate (PHRR) and total heat release rate (THR) of CBE10P10Si8 decreased by 42% and 16% respectively. This is due to the fact that DOPO is cracked into phosphorus radicals to capture and eliminate the active H and OH radicals, inhibiting the chain free radical reaction, and RMSi is enriched on the surface of CBE10P10Si8 to form an inorganic oxygen insulation protective layer during combustion. The impact strength of CBE10P10Si8 increased from 5.8 kJ/m2 to 11.9 kJ/m2. The improvement of impact strength is owing to the existence of DOPO-EG which promotes the formation of the interface layer between PC and PBT phases, resulting in the transfer of stress between the two phases. This work provides a new method for the preparation of PC/PBT alloy with excellent flame retardancy and mechanical properties, and also provides a certain reference value for the research of flame retardancy and toughening modification of polymer composites.

Sustainable cycling and mechanism of Co(II)/Co(IV)/Co(III) with S(IV) highly triggered by Co(IV) in E/Co(II)/S(IV) for enhanced removal of reactive brilliant red X-3B

The massive discharge and inadequate treatment of dye wastewater have led to the extensive accumulation of azo dyes in natural water bodies, which is a severe threat to human health. In this study, a novel homogeneous electrochemical system, denoted E/Co(II)/S(IV), was developed by the incorporation of an electric field and cobalt/sulfite. Notably, the decontamination efficiency of the E/Co(II)/S(IV) system for reactive brilliant red X-3B (X-3B) was 95.14 % within 10 min, which was accomplished by utilizing only a trace amount of Co(II). The entire process exhibited an exceptionally low energy consumption of only 0.331 kWh/m3. Single-factor experiments were conducted to explore the influence of various operational parameters and water matrix components on the system decontamination efficiency. By combining the chelator EDTA and chemical probe PMSO, the presence of Co(III) and Co(IV) was detected. The results showed that Co(IV) mainly triggered the chain reaction. The activation products of S(IV), including SO3•−, SO4•−, SO5•− and HO∙, played a dominant role in the degradation of X-3B, with SO4•− having the most substantial contribution. Under anodic oxidation, Co(II) underwent double-electron transfer, leading to the conversion of Co(II) into Co(IV). Subsequently, Co(IV) activated S(IV) via a single-electron transfer mechanism, initiating a free radical chain reaction. During the reaction, Co(IV) transformed into Co(III) and Co(II), thus achieving the Co(II)/Co(IV)/Co(III) cycle. The generation of oxygen as a result of the electrochemical process offers a viable solution for addressing the issue of hypoxia stemming from the rapid activation of S(IV). The active sites in the X-3B molecule were elucidated through density functional theory predictions, and three degradation pathways for X-3B were identified via mass spectrometry analysis. The toxicological characteristics of both X-3B and its degradation products were comprehensively assessed using toxicity estimation software tool and algal culture experiments. This research offers valuable insights into the refinement of cobalt/sulfite systems and introduces innovative concepts for electrochemical applications, which have broad-reaching implications for dye wastewater purification.

Augmented degradation performance of dielectric barrier discharge plasma via optimized hydroxyl radical generation

Dielectric barrier discharge (DBD) plasma demonstrates significant potential for eliminating chlorinated aromatic compounds (CACs), while its commercial application has been hampered by inadequate generation and diffusion of active species. In response, this work introduced iron-biochar composites (Fe/BC) into DBD system to enhance the generation of highly oxidative hydroxyl radicals (OH) from underutilized O3 and H2O2, thereby reducing the diffusion of OH and accelerating the degradation of CACs. The results indicated that, in just 15 min, the combined system achieved remarkable degradation rates exceeding 95% for six diverse CACs, with the degradation rate constant increasing up to 4.27 times when compared to DBD alone. Moreover, the varied response of pollutants implied that the enhanced degradation efficiency was primarily facilitated by the reduced mass transfer distance between pollutants and formed OH. The activation of O3 on Lewis acidic sites not only directly promoted the generation of OH through free radical chain reactions but also indirectly induced more conversion of H2O2 into OH by facilitating the Fe3+/Fe2+ cycle. The identification of intermediates and toxicity analysis substantiated its environmental sustainability. This study offers a viable technical pathway and theoretical foundation for enhancing the efficiency of plasma-based treatment of organic wastewater.

Effect of mechanical energy input during mechanical crushing on the macrokinetics of the coal–oxygen reaction: A laboratory–scale study

Underground mining is usually simplified as a process of coal crushing and pulverization. However, this process is not purely physical. The mechanical energy input to this process also induces a mechanochemical effect. The specific impact of this effect on the macrokinetics of the coal–oxygen reaction (COR) has not been independently investigated, which motivates this work. Thermal analysis tests showed that mechanical energy input contributed to the strength of the COR and exhibited regularities in its impact on COR's kinetic parameters. Explanations for this were given based on mechanochemistry, free radicals chain reaction and quantum chemistry theories. A coal macromolecule model, influenced by mechanical energy input, was developed based on the typical Wiser model, and subsequent quantum mechanical calculations were conducted. It was found that mechanical energy input facilitated the breaking of specific chemical bonds in coal, redistributing the electrostatic potential and increasing the number of active sites within the coal molecule. Moreover, both the free radicals from bonds breaking and the remaining active structural sites exhibited an increasing trend in their electrified capacities. Different from the traditional physical pathway, this work refined the mechanism by which mechanical forces affect COR through the mechanochemical pathway.

Photocatalytic fuel cell assisted by Fenton-like reaction for p-Chloronitrobenzen degradation and electricity production through S-scheme heterojunction C3N5 modified TNAs photoanode: Performance, DFT calculation and mechanism

Photocatalytic fuel cell (PFC) is a promising technology to recover usable energy from wastewater through the degradation of pollutants, whereas the complex preparation procedures and high photogenerated carrier recombination efficiency of photoanode remains an urgent challenge to improve the PFC performance. Herein, PFC with S-scheme heterojunction C3N5/TNAs photoanode assisted by Fenton-like reaction (C3N5/TNAs-PFC-Fenton) system was built for p-Chloronitrobenzene degradation and electricity production. The working function confirmed the band bending of C3N5 and TNAs, and density functional theory calculations indicated the formation of internal electric field at heterojunction interface of C3N5 and TNAs, which promoted visible-light absorption capacity and charge transfer property of C3N5/TNAs photoanode. The incorporation of Fenton-like reaction into C3N5/TNAs-PFC-Fenton system could effectively enhance p-Chloronitrobenzene degradation and electricity production by participating in free radical chain reaction and stimulating electron transfer. The radical trapping experiments confirmed that •OH and photogenerated electron were main reactive species, and photogenerated hole, •O2− and 1O2 were also participated in p-Chloronitrobenzene degradation. The p-Chloronitrobenzene degradation pathway was interpreted and the overall toxicity of p-Chloronitrobenzene was relieved after treatment in C3N5/TNAs-PFC-Fenton system. The C3N5/TNAs-PFC-Fenton system exhibited fine universality for degradation of organic pollutants and electricity production.

Surface modification of iron-zinc ions incorporated calcium phosphate biocomposite flexible films for biomedical applications

In this work, the poly(methyl methacrylate) (PMMA)-Iron (Fe)-Zinc (Zn) ions incorporated hydroxyapatite nanocomposite films were developed by solvent evaporation technique and exposed to nitrogen 7+ ions implantation on different fluences viz., 1 × 1015, 5 × 1015, and 1 × 1016 ions/cm2 are denoted as PFZH115, PFZH515, and PFZH116 respectively. The N7+ ion implantation modified the surface properties but did not affect the bulk properties of the films. The ion beam implantation leads to the polymer chain scission and free radical formation due to the production of localized heating. The bombardment of the low-energy ions removed the oxygen in the composite matrix resulting in the replacement of nitrogen ions. The ion-induced surface diffusion results in the orientation of polarized dipoles and the reduction of wettability. All the samples are hemocompatible. The formation of craters is due to the continuous impingement of the ion beams that paved the way for the leaching of zinc ions from the hydroxyapatite matrix leading to the increased antimicrobial activity of the films. The surface engineering led to the proliferation of fibroblast cells by 10% which made the ion beam implantation a potential way to fabricate novel bone/dental filling materials in the biomedical field.