A comprehensive exploration of hydrogel applications in multi-stage skin wound healing.

Hydrogels, as an emerging biomaterial, have found extensive use in the healing of wounds due to their distinctive physicochemical structure and functional properties. Moreover, hydrogels can be made to match a range of therapeutic requirements for materials used in wound healing through specific functional modifications. This review provides a step-by-step explanation of the processes involved in cutaneous wound healing, including hemostasis, inflammation, proliferation, and reconstitution, along with an investigation of the factors that impact these processes. Furthermore, a thorough analysis is conducted on the various stages of the wound healing process at which functional hydrogels are implemented, including hemostasis, anti-infection measures, encouraging regeneration, scar reduction, and wound monitoring. Next, the latest progress of multifunctional hydrogels for wound healing and the methods to achieve these functions are discussed in depth and categorized for elucidation. Finally, perspectives and challenges associated with the clinical applications of multifunctional hydrogels are discussed.

Unravelling the removal mechanisms of trivalent arsenic by sulfidated nanoscale zero-valent iron: The crucial role of reactive oxygen species and the multiple effects of citric acid.

The remediation of arsenic-contaminated groundwater by sulfidated nanoscale zero-valent iron (S-nZVI) has raised considerable attention. However, the role of trivalent arsenic (As(III)) oxidation by S-nZVI in oxic conditions (S-nZVI/O2) remains controversial, and the comprehensive effect of citric acid (CA) prevalent in groundwater on As(III) removal by S-nZVI remains unclear. Herein, the mechanisms of reactive oxygen species (ROS) generation and multiple effects of CA on As(III) removal by S-nZVI/O2 were systematically explored. Results indicated that the removal efficiency of As(III) by S-nZVI/O2 (97.81 %) was prominently higher than that by S-nZVI (66.71 %), resulting from the significant production of ROS (mainly H2O2 and OH) under oxic conditions, which played a crucial role in promoting the As(III) oxidation. Additionally, CA had multiple effects on As(III) removal by S-nZVI/O2 system: (i) CA impeded the diffusion of As(III) towards S-nZVI and increased the secondary risk of immobilized As(III) re-releasing into the environment due to the Fe dissolution from S-nZVI; (ii) CA could significantly enhance the yields of OH from 25.29 to 133.00 µM via accelerating the redox cycle of Fe(II)/Fe(III) and increasing the oriented conversion rate of H2O2 to OH; (iii) CA could also enrich the types of ROS (such as O2- and 1O2) in favor of further As(III) oxidation. This study contributed novel findings regarding the control of As(III) contaminated groundwater using S-nZVI technologies.

Activation of periodate by N-doped iron-based porous carbon for degradation of sulfisoxazole: Significance of catalyst-mediated electron transfer mechanism.

Periodate (PI) has recently been studied as an excellent oxidant in advanced oxidation processes, and its reported mechanism is mainly the formation of reactive oxygen species (ROS). This work presents an efficient approach using N-doped iron-based porous carbon (Fe@N-C) to activate periodate for the degradation of sulfisoxazole (SIZ). Characterization results indicated the catalyst has high catalytic activity, stable structure, and high electron transfer activity. In terms of degradation mechanism, it is pointed out that the non-radical pathway is the dominant mechanism. In order to prove this mechanism, we have carried out scavenging experiments, electron paramagnetic resonance (EPR) analysis, salt bridge experiments and electrochemical experiments, which demonstrate the occurrence of mediated electron transfer mechanism. Fe@N-C could mediate the electron transfer from organic contaminant molecules to PI, thus improving the efficiency of PI utilization, rather than simply inducing the activation of PI through Fe@N-C. The overall results of this study provided a new understanding into the application of Fe@N-C activated PI in wastewater treatment.

Activation of peroxymonosulfate for degrading ibuprofen via single atom Cu anchored by carbon skeleton and chlorine atom: The radical and non-radical pathways.

Single atomic Cu catalysts (SACs Cu@C) anchored by carbon skeleton and chlorine atom was synthesized by hydrolyzing Cu-MOFs and then pickled by aqua-regia to remove Cu nanoparticles (NPs Cu). Comparative characterizations revealed that SACs Cu@C was a hierarchically porous nanostructure and Cu dispersed uniformly throughout the carbon skeletons. With less active components, SACs Cu@C behaved better in activating PMS over NPs Cu@C on ibuprofen removal (91.3 % versus 30.2 % in 30 min). Two Cu coordination environments were found by EXAF and DFT calculation, including four-coordinated Cu with 4C atoms and six-coordinated Cu with 4Cu and 2Cl atoms. The obvious interfacial electron delivery between PMS and SACs Cu@C was found, which was enhanced by Cl atom. Cu(I)/Cu(II) redox cycle would donate electron to peroxy bond of PMS for generating OH, SO4- and O2-. But electron transferred in opposite direction when PMS bonded to Cu atom through its terminal oxygen atom in sulfate, which formed 1O2. IBP degradation proceeded through both radical and non-radical route. IBP degradation was inhibited with the presence of TBA, methanol and furfuryl alcohol but accelerated by p-BQ, which could accelerate OH generation. Two degradation pathways were deducted. This study provided a new insight into catalysts designed for PMS activation.

A comprehensive review on metal based active sites and their interaction with O3 during heterogeneous catalytic ozonation process: Types, regulation and authentication.

Heterogeneous catalytic ozonation (HCO) was a promising water purification technology. Designing novel metal-based catalysts and exploring their structural-activity relationship continued to be a hot topic in HCO. Herein, we reviewed the recent development of metal-based catalysts (including monometallic and polymetallic catalysts) in HCO. Regulation of metal based active sites (surface hydroxyl groups, Lewis acid sites, metal redox cycle and surface defect) and their key roles in activating O3 were explored. Advantage and disadvantage of conventional characterization techniques on monitoring metal active sites were claimed. In situ electrochemical characterization and DFT simulation were recommended as supplement to reveal the metal active species. Though the ambiguous interfacial behaviors of O3 at these active sites, the existence of interfacial electron migration was beyond doubt. The reported metal-based catalysts mainly served as electron donator for O3, which resulted in the accumulation of oxidized metal and reduced their activity. Design of polymetallic catalysts could accelerate the interfacial electron migration, but they still faced with the dilemma of sluggish Me(n+m)+/Men+ redox cycle. Alternative strategies like coupling active metal species with mesoporous silicon materials, regulating surface hydrophobic/hydrophilic properties, polaring surface electron distribution, coupling HCO process with photocatalysis and H2O2 were proposed for future research.

Enhanced oxidation of organic contaminants by Mn(VII) in water.

Studies that promote chemical oxidation by permanganate (MnO4-; Mn(VII)) as a viable technology for water treatment and environmental purification have been quickly accumulating over the past decades. Various methods to activate Mn(VII) have been proposed and their efficacy in destructing a wide range of emerging organic contaminants has been demonstrated. This article aims to present a state-of-art review on the development of Mn(VII) activation methods, including photoactivation, electrical activation, the addition of redox mediators, carbonaceous materials, and other chemical agents, with a particular focus on the potential activation mechanism and critical influencing factors. Different reaction mechanisms are involved in activated Mn(VII) oxidation processes, including the generation of reactive intermediates derived from Mn(VII) (e.g., Mn(III), Mn(V), and Mn(VI)) or activators (e.g., intermediates of redox mediators and Ru catalysts), reactive oxygen species (ROS) (e.g., •OH, O2•-, and 1O2), as well as electron transfer from organics to Mn(VII) via catalysts as the electron mediator. Except •OH that is generated as one of co-oxidants in UV/Mn(VII) process, other reactive species are relatively mild oxidants, which are more selective toward organic substrates and highly tolerant toward various water matrices (e.g., inorganic ions and natural organic matter) compared to strongly oxidizing radical species. Therefore, activated Mn(VII) oxidation processes show a good prospect for efficient removal of target contaminants in natural and complex environmental matrices. However, there are some disputes about the dominant reactive species generated in these processes, and their identification methods may be not appropriate, causing serious confusion in the mechanistic understanding. So, further efforts are still needed to fill the knowledge gap and also to address the application challenges of these technologies.

Functional bacterial consortium responses to biochar and implications for BDE-47 transformation: Performance, metabolism, community assembly and microbial interaction.

The influence of biochar on the biodegradation of persistent organic pollutants (POPs) has been extensively studied. However, the underlying mechanisms behind the response of functional microbial consortia to biochar remain poorly understood. Herein, we systematically explored the effect of biochar on 2,2',4,4'-tetrabrominated ether (BDE-47) biodegradation, and investigated the interaction and assembly mechanism of the functional bacterial consortium QY2. The results revealed that the biodegradation efficiency of QY2 for BDE-47 increased from 53.85% to 94.11% after the addition of biochar. Fluorescence excitation-emission matrix and electrochemical analysis showed that biochar-attached biofilms were rich in redox-active extracellular polymeric substances (EPS, 3.03-fold higher than free cell), whose strong interaction with biochar facilitated the electron transfer of the biofilm, thus enhancing the debromination degradation of BDE-47. Meanwhile, the assembly model and molecular ecological networks analysis indicated that bacterial community assembly in biofilms was more driven by deterministic processes (environmental selection >75.00%) upon biochar stimulation and exhibited closer interspecific cooperative interactions, leading to higher biodiversity and broader habitat niche breadth for QY2 in response to BDE-47 disturbance. Potential degraders (Methylobacterium, Sphingomonas, Microbacterium) and electrochemical bacteria (Ochrobactrum) were selectively enriched, whose role as keystone bacteria may be participated in biofilm formation and redox-active EPS secretion (r > 0.5, P < 0.05). These findings deepen the understanding of the mechanisms by which biochar promotes microbial degradation of PBDEs and provided a theoretical basis for better regulation of functional bacterial communities during environmental remediation.

Promotion of the biodegradation of phenanthrene adsorbed on microplastics by the functional bacterial consortium QY1 in the presence of humic acid: Bioavailability and toxicity evaluation.

The adsorption of hydrophobic organic compounds (HOCs) by microplastics (MPs) has attracted great attention in recent years. However, the ultimate environmental fate of the HOCs sorbed on MPs (HOCs-MPs) is poorly understood. In this work, we investigated the potential influence of the biotransformation process on the environmental fate of phenanthrene (PHE, a model HOC) sorbed on MPs (PHE-MPs) under the existence of humic acid (HA, the main ingredient of dissolved organic matter (DOM)) in the aquatic environment. The results indicated that the adsorption behavior of PHE on MPs decreased its bioavailability and thus inhibited its biotransformation efficiency. However, HA significantly promoted the biodegradation rate and percentage of PHE-MPs. This was probably because HA improved the desorption of PHE from MPs, which promoted the acquisition of PHE by bacteria from the aqueous phase. Further, HA dramatically increased the bacterial community diversity and richness and altered the community composition. The richness of some PHE-degrading bacteria, such as Methylobacillus and Sphingomonas, significantly increased, which may also be an important factor for promoting PHE biodegradation. Molecular ecological network analysis implied that HA enhanced the modularity and complexity of bacterial interaction networks, which was beneficial to maintaining the functional stability of the consortium QY1. Besides, HA decreased the cytotoxicity of functional microbes induced by HOCs-MPs. This work broadens our knowledge of the environmental fate of HOCs-MPs and interactions of MPs, HOCs, DOMs and functional microbial consortiums in aqueous environments.

Bisulfite activated permanganate for oxidative water decontamination.

Recently, bisulfite-activated permanganate (MnO4-; Mn(VII)) process has attracted considerable attention as a novel class of advanced oxidation technology for destruction of organic contaminants in water. However, disputes over the underlying activation mechanism as well as reactive species generated in the Mn(VII)/bisulfite system remain for a long period due to the fairly complex chemistry involved in this system. This article aims to present a critical review on scientific development of the Mn(VII)/bisulfite system, with particular focus on the generation and contribution of various reactive intermediates. Both reactive manganese species (RMnS) (i.e., soluble Mn(III), Mn(V), and Mn(VI)) and radical species (primarily SO4•-) are identified as the oxidizing components responsible for enhanced degradation of organic contaminants by the Mn(VII)/bisulfite system. Bisulfite plays a dual role of being an activating agent for reactive intermediates generation and acting as a complexing agent to stabilize RMnS. Solution chemistry (e.g., the [Mn(VII)]/[bisulfite] molar ratio, solution pH, the type of contaminants, ligands, and water matrix components) greatly impacts the generation and consumption of RMnS and radicals, thus influencing the degradation kinetics and pathways of organics. Particularly, dissolved oxygen (DO) is a vital factor for driving the oxidation of organics since the absence of DO can block the generation of SO4•- and meantime causes the consumption of RMnS by excess SO3•- as a strong reductant. Interestingly, ferrate (FeO42-, Fe(VI)) and hexavalent chromium (CrO42-/HCrO4-, Cr(VI)) that are high-valent metal oxyanions analogous to Mn(VII) can be activated by bisulfite via a similar pathway (i.e. both high-valent metal-oxo intermediates and reactive radicals are involved). Furthermore, key knowledge gaps are identified and future research needs are proposed to address the potential challenges encountered in practical application of the Mn(VII)/bisulfite oxidation technology.

Synergistic removal of Cr(VI) by S-nZVI and organic acids: The enhanced electron selectivity and pH-dependent promotion mechanisms.

The effects of organic acids on hexavalent chromium (Cr(VI)) removal by reduced iron-based materials have been extensively studied. Nevertheless, the promotion mechanism from the perspective of the electron transfer process is still unclear. Herein, sulfidated nanoscale zero-valent iron (S-nZVI) and the selected organic acids, citric acid (containing both -OH and -COOH groups) and oxalic acid (containing only -COOH groups), showed significant synergistic promotion effects in Cr(VI) removal. The FeS and FeS2 on S-nZVI surface could enhance the Cr(VI) reduction as the reductive entity and electron conductor. Furthermore, even though the reactivity of FeS with Cr(VI) is higher than that with FeS2, the Cr(VI) removal efficiency by FeS2 was much higher than that by FeS with organic acids. Under neutral and alkaline conditions (pH 6.0-8.0), organic acids promoted the diffusion, adsorption and complexation of Cr(VI) on S-nZVI surface, thus enhancing the electron selectivity towards Cr(VI). However, when the solution pH changed to acidic conditions (pH 4.0), organic acids facilitated the dissolution of Fe(II) ions from S-nZVI and enhanced the electron utilization towards Cr(VI) via the fast Fe(III) reduction process. This study provided a new insight into the Cr(VI) removal, which was beneficial to understand the application boundaries of S-nZVI for Cr(VI) remediation.

Environmental contamination and human exposure of polychlorinated biphenyls (PCBs) in China: A review.

Polychlorinated biphenyls (PCBs), together with 11 other organic compounds, were initially listed as persistent organic pollutants (POPs) by the Stockholm Convention because of their potential threat to ecosystems and humans. In China, many monitoring studies have been undertaken to reveal the level of PCBs in environment since 2005 due to the introduced stricter environmental regulations. However, there are still significant gaps in understanding the overall spatial and temporal distributions of PCBs in China. This review systematically discusses the occurrence and distribution of PCBs in environmental matrices, organisms, and humans in China. Results showed that PCB contamination in northern and southern China was not significantly different, but the PCB levels in East China were commonly higher than those in West China, which might have been due to the widespread consumption of PCBs and intensive human activities in East China. Serious PCB contamination was found in e-waste disassembling areas (e.g., Taizhou of Zhejiang Province and Qingyuan and Guiyu of Guangdong Province). Higher PCB concentrations were also chronicled in megalopolises and industrial clusters. The unintentionally produced PCBs (UP-PCBs) formed during industrial thermal processes may play an increasingly significant role in PCB pollution in China. Low PCB levels were recorded in rural and underdeveloped districts, particularly in remote and high-altitude localities such as the Tibetan Plateau and the South China Sea. However, these data are limited. Human exposure to PCBs is closely related to the characteristics of environmental pollution. This review also discusses existing issues and future research prospects on PCBs in China. For instance, the accumulation characteristics and migration regularities of PCBs in food webs should be further studied. More investigations should be undertaken to assess the quantitative relationship between external and internal exposure to PCBs. For example, bioaccessibility and bioavailability studies should be supplemented to evaluate human health risks more accurately.

Effects of methanol on the performance of a novel BDE-47 degrading bacterial consortium QY2 in the co-metabolism process.

2,2',4,4'-tetrabrominated diphenyl ether (BDE-47), frequently detected in the environment, is arduous to be removed by conventional biological treatments due to its persistence and toxicity. Herein effects of methanol as a co-metabolic substrate on the biodegradation of BDE-47 was systematically studied by a functional bacterial consortium QY2, constructed through long-term and successive acclimation from indigenous microorganisms. The results revealed that BDE-47 (0.25 mg/L) was completely removed within 7 days in the 2.5 mM methanol treatment group, and its degradation efficiency was 3.26 times higher than that without methanol treatment. The addition of methanol dramatically accelerated the debromination, hydroxylation and phenyl ether bond breakage of BDE-47 by QY2. However, excessive methanol (>5 mM) combined with BDE-47 had strong stress on microbial cells, including significant (p < 0.05) increase of reactive oxygen species level, superoxide dismutase activity, catalase activity and malondialdehyde content, even causing 20.65% cell apoptosis and 11.27% death. It was worth noting that the changes of QY2 community structure remained relatively stable after adding methanol, presumably attributed to the important role of the genus Methylobacterium in maintaining the functional and structural stability of QY2. This study deepened our understanding of how methanol as co-metabolite substances stimulated the biodegradation of BDE-47 by microbial consortium.

Removal of heavy metal ions and polybrominated biphenyl ethers by sulfurized nanoscale zerovalent iron: Compound effects and removal mechanism.

Sulfurized nanoscale zerovalent iron (S-nZVI) has been widely reported to be able to quickly remove heavy metals/persistent organic pollutants, but the limited understanding of the complicated removal process of heavy metals-organic combined pollutants restricts the application of S-nZVI. Here, we demonstrate that there is significant difference in the effectiveness of S-nZVI for removing single pollutant and complex pollutants. The removal kinetic constant (kobs) of heavy metals by S-nZVI followed a sequence of Cr(VI)>Pb(II)>Ni(II)>Cd(II) with or without polybrominated diphenyl ethers (PBDEs). While the capacity of co-existing cations increasing the kobs of PBDEs followed the order: Ni(II)>Pb(II)>Cd(II), and the co-existence of Cr(VI) anion inhibited the reduction of PBDE by S-nZVI because the generated Cr-Fe precipitate hindered the electron transfer. The de-passivation process on S-nZVI surface by Cd(II) ions slightly accelerated the transformation rate of electron. Nevertheless, the co-existing Pb(II) significantly accelerated the transformation of BDE-209 via the galvanic effect from the generated Pb0/Fe0 bimetal. Interestingly, the kobs of BDE-47 in Ni(II)/S-nZVI system was 5.51 times higher than that of Pb(II)/S-nZVI system, implying that an atomic hydrogen mechanism dominated the reduction of BDE-47 by Ni(II)/S-nZVI. In conclusion, the results provided a deep comprehending of removal mechanism of heavy metal-organic complex pollutants by S-nZVI.

Removal of triphenyl phosphate by nanoscale zerovalent iron (nZVI) activated bisulfite: Performance, surface reaction mechanism and sulfate radical-mediated degradation pathway.

Recently, sulfate radical-based advanced oxidation processes (SR-AOPs) have been studied extensively for the removal of pollutants, however, few researches focused on the activation of bisulfite by nanoscale zerovalent iron (nZVI), especially, surface reaction mechanism and sulfate radical-mediated degradation pathway have not been elucidated in detail. In this study, influencing factors, the kinetics, transformation pathway and mechanism of triphenyl phosphate (TPHP) degradation in the nZVI/bisulfite system were systematically discussed. Compared with Fe2+, nZVI was found to be a more efficient and long-lasting activator of bisulfite via gradual generation of iron ions. The optimal degradation efficiency of TPHP (98.2%) and pseudo-first-order kinetics rate constant (kobs = 0.2784 min-1) were obtained by using 0.5 mM nZVI and 2.0 mM bisulfite at the initial pH 3.0. Both Cl- and NO3- inhibited the degradation of TPHP and the inhibitory effect of Cl- was stronger than that of NO3- due to the higher reaction rate of Cl- with •SO4-. Furthermore, SEM, XRD and XPS characterization revealed that a thin passivation layer (Fe2O3, Fe3O4, FeOOH) deposited on the surface of fresh nZVI and a few iron corrosion products generated and assembled on the surface of reacted nZVI. Radical quenching tests identified that •SO4- was the dominant reactive oxidative species (ROS) for TPHP removal. Based on HRMS analysis, six degradation products were determined and a sulfate radical-mediated degradation pathway was proposed. In a word, this study revealed that the nZVI/bisulfite system had a great potential for the TPHP elimination in waterbody.

Reductive debromination of decabromodiphenyl ether by iron sulfide-coated nanoscale zerovalent iron: mechanistic insights from Fe(II) dissolution and solvent kinetic isotope effects.

The mechanism that iron sulfide-coated nanoscale zero valent iron (S-nZVI) has better reduction activity towards organic pollutants than nanoscale zero-valent iron (nZVI) has long been debated. In this work, a systematic study was investigated to compare differences of main influences, BDE-209 degradation pathway, degradation kinetics and reduction mechanism of BDE-209 between nZVI and S-nZVI systems. The observed transformation rate of BDE-209 (kobs) by S-nZVI was 58.3 and 7.1 times greater than that by S2- and nZVI, respectively. The valence change of Fe and S on S-nZVI surface before and after BDE-209 degradation process based on XPS characterization confirmed that both Fe0 and iron sulfide were the reduction entity of the surface-mediated reaction. The presence of tetrahydrofuran (THF) promoted the surface contact of BDE-209 with S-nZVI, thus accelerating the BDE-209 degradation process. Compared with nZVI, the iron sulfide coated on the Fe0 core surface could not only greatly reduce unnecessary electron loss via Fe0 corrosion with water, but also accelerate the transmission of electrons from Fe0 core to organic pollutants according to Fe(II) dissolution and solvent kinetic isotope effects investigations. These findings help to clarify the synergistic degradation mechanism between Fe0 core and iron sulfide shell layer.

Magnetite/Fe-Al-montmorillonite as a Fenton catalyst with efficient degradation of phenol.

A Fe-Al-MPM material assembled from nanosized magnetite and Fe-Al-pillared montmorillonite (Fe-Al-Mt) was characterized by XRD, XPS, BET, SEM and TEM. Fe-Al-Mt was proven to be capable of facilitating the dispersion of magnetite nanoparticles and inhibiting their aggregation. The coupling of Fe-Al-Mt with magnetite in Fe-Al-MPM improved its Fenton catalytic activity. Complete conversion of phenol within 80min with a high TOC removal rate (>78%) was achieved using Fe-Al-MPM as a heterogeneous Fenton catalyst under optimized conditions. The Fenton process first underwent a slow induction reaction, followed by the rapid oxidative decomposition of phenol. The existence of the induction reaction period was attributed to the need for activation of the iron species on the catalyst surfaces, and the duration depended on the solution temperature, pH and catalyst's nature. More importantly, Fe-Al-MPM showed high stability, with a low iron-release even after it was recycled 5 times. The minimal iron-leaching from Fe-Al-MPM was ascribed to the competitive adsorption of the incorporated aluminum and all the iron species for the residual (low ecotoxicity) organic ligands. These organic acids were among the main products that remained at the end of the Fenton process. Also important was the ease of separation of Fe-Al-MPM under a magnetic field.

Efficient degradation of phenol using iron-montmorillonite as a Fenton catalyst: Importance of visible light irradiation and intermediates.

Iron-montmorillonite (Fe-Mt) with delaminated structures was synthesized via the introduction of iron oxides into Na-montmorillonite. Fe-Mt showed significant increases in the available iron content, surface area and pore volume, along with a slight increase in the basal spacing from d001=1.26 (Na-Mt) to 1.53nm (Fe-Mt). The Fenton process was efficient for phenol removal using Fe-Mt as a catalyst under visible light irradiation, and the process had two-stage pseudo-first order kinetics. The overall reaction had a higher degradation rate even when it was only irradiated with visible light for the first 40min period. Further investigation confirmed that the irradiation increased the presence of certain intermediates. Among them, 1,4-benzoquinone, hydroquinone, and catechol all enhanced the Fenton reaction rates. Either catechol or hydroquinone was added to the Fenton system with Fe-Mt/H2O2 with or without visible light irradiation, and they both accelerated phenol degradation because catechol and hydroquinone are capable of reductively and effectively transforming Fe(III) into Fe(II). The concentrations of dissolved total Fe increased with the increase in the oxalic acid concentration, which can strongly chelate Fe(III). Hence, iron was released from Fe-Mt, and reductive transformation played an important role in promoting the Fenton reaction process for phenol removal.