Electron Transfer Process Research Articles

A novel fluorescent probe for formaldehyde based on hydrazone formation for real food samples detection and bioimaging

Formaldehyde (FA) is an active carbonyl structure that is widely used in people's daily life, such as preservatives and fixatives. Furthermore, formaldehyde is highly toxic and has been listed as one of the three major indoor pollutants. Therefore, the development of highly sensitive and selective fluorescent probes is of great biological importance. In this article, probe X is designed to identify formaldehyde by a light-induced electron transfer (PET) process between the naphthalimide derivative and the hydrazine group based on hydrazone formation. Moreover, the probe has good optical response and excellent linearity over a wide range of formaldehyde concentrations, ensuring that formaldehyde concentration values in real complex food samples can be quantitatively recorded. In addition, the probe can monitor the changes of formaldehyde levels in living cells with good biocompatibility and image resolution.

ERCAD: A Parametric Reactor Design Tool That Enables Rapid Prototyping and Optimization of Electrochemical Reactors through 3D Printing.

The reactors are an essential component of electrosynthetic reactions. As the electron transfer processes are heterogeneous, the reactors have a significant impact on reaction outcomes. This has resulted in reaction reproducibility being problematic, which commercial reactors alleviate somewhat but are expensive and cannot be optimized or iterated upon. Using 3D printing, rapid prototyping of bespoke reactors should facilitate investigation of the sensitivity of key reactor parameters, enable reactor optimization, and improved reproducibility through sharing of the print files. However, the bottleneck to this approach is the Computer Aided Design (CAD) of the reactors, which typically requires specialist knowledge and training to do. This has resulted in 3D printing not being typically used in the field of electrosynthesis. Herein, we showcase the development and application of a user-friendly, open-source software tool that can be used to produce Electrochemical Reactor CAD (ERCAD) designs simply and easily by nonexperts. We demonstrate its use to design and print reactors for the analysis, optimization, screening, and scaleup of electrosynthetic reactions. Using this parametric design tool, chemists with no design experience or skills can now easily create, print, test, and share their reactors.

Biology-Based Synthesis of Nickel Single Atoms on the Surface of Geobacter sulfurreducens as an Efficient Electrocatalyst for Alkaline Water Electrolysis.

Single-atom metal catalysts are promising electrocatalysts for water electrolysis. Nickel-based electrocatalysts have shown attractive application prospects for water electrolysis. However, synthesizing stable Ni single atoms using chemical and physical approaches remains a practical challenge. Here, a facile and precise method for synthesizing stable nickel single atoms on the surface of Geobacter sulfurreducens using a microbial-mediated extracellular electron transfer (EET) process is demonstrated. It is shown that G. sulfurreducens can effectively anchor nickel single atoms on their surface. X-ray absorption near-edge structure and Fourier-transformed extended X-ray absorption fine structure spectroscopy confirm that the nickel single atom is coordinated to nitrogen in the cytochromes. The as-synthesized nickel single atoms on G. sulfurreducens exhibit excellent bifunctional catalytic properties for alkaline water electrolysis with low overpotential (η) to achieve current density (10mAcm-2) for both hydrogen evolution reactions (η = 80mV) and oxygen evolution reaction (η = 330mV) with minimal catalyst loading of 0.0015mgNicm-2. The nickel single-atom catalyst shows long-term stability at a constant electrode potential. This synthesis method based on the EET capability of electroactive bacteria provides a simple and scalable approach for producing low-cost and highly efficient nonnoble transition metal single-atom catalysts for practical applications.

Enhanced electrochemical performance of ZrTe-Mn2O3 nanocomposite electrocatalyst for HER and OER in alkaline medium

Electrochemical energy conversion in renewable-energy technologies relies on the OER and HER towards next-generation fuels. Herein, we have coupled zirconia telluride (ZrTe) and manganese oxide (Mn2O3) nanosheets heterointerfaces by a facile hydrothermal method, which are engineered on stainless steel substrate (ZrTe-Mn2O3/SS). The physical properties, including crystallinity, phase purity, morphology, conductivity, and chemical interacted states of the developed composite, are systematically investigated by XRD, HRTEM, I-V, and XPS. The XPS observation showed unique redox properties of hydrogen peroxide species on the ZrTe-Mn2O3 catalyst and the oxidation state of Zr and Mn that was more easily changed in the ZrTe-Mn2O3 electrocatalyst compared with the pristine catalysts. The very decent electrochemical performance of the catalyst activation step (Mn3+→Mn4+ and Zr2+→Zr4+ oxidations) observed from electrochemical cyclic voltammetry (CV) and linear sweep voltammetry (LSV) studies that are tested in the alkaline environment. Concerning higher bifunctional activity for ZrTe-Mn2O3, the current density of 10 mA cm−2 is revealed only at a lower overpotential of 244 mV and Tafel slope of 48 mV/dec toward better OER. At the same time, composite material also exhibited a minimal overpotential of 61 mV toward HER to attain 100 mA/cm2. It was also found that introducing a connection of ZrTe with Mn2O3 improves the precise surface area and exposes more multi-active sites for easy transfer of electrons. In addition, it maintains excellent long-term stability for almost 110 hrs through chronoamperometry, which leads to no activity loss and further represents higher OER/HER activity in industrial applications. We conclusively demonstrate that the first-time reported research provides valuable insights attributed to the defective structure, porous nature, and covalently bridging between atomic-level heterogeneous interfaces, favouring rapid electron transfer process activation for continuously produced O2 and H2 gas bubbles.

Impact of biocatalytic behavior of Shewanella sp. through electron transfer processes on effective treatment of beer brewing wastewater in a microbial fuel cell and power generation

AbstractThis study examines the performance of a microbial fuel cell (MFC) utilizing Shewanella bacteria through electrochemical impedance spectroscopy (EIS). Exo‐electrogen bacteria are key agents in an MFC. Shewanella sp. as a common exo‐electrogen bacteria can transfer electrons from the cell surface through different electron transfer mechanisms. In this work, EIS was used to probe the effects of biofilms of Shewanella sp. and the solution of 10% V/V Shewanella on the MFC performance. This research investigates the effects of both microbial biofilms and Shewanella bacterial solutions on MFC efficacy. Findings revealed that biofilm formation on the anode surface significantly reduces anode charge transfer resistance, thereby enhancing power generation. Notably, a 10% Shewanella solution resulted in a 25% higher power density compared to the biofilm. Furthermore, the MFC demonstrated up to 80% chemical oxygen demand removal efficiency in treating brewery wastewater. The study underscores the viability of Shewanella bacterial solutions as an efficient alternative to biofilms, emphasizing their role in improving MFC performance and wastewater treatment efficiency.

Photosynthetic biohybrid systems for solar fuels catalysis.

Photosynthetic reaction center (RC) proteins are finely tuned molecular systems optimized for solar energy conversion. RCs effectively capture and convert sunlight with near unity quantum efficiency utilizing light-induced directional electron transfer through a series of molecular cofactors embedded within the protein core to generate a long-lived charge separated state with a useable electrochemical potential. Of current interest are new strategies that couple RC chemistry to the direct synthesis of energy-rich compounds. This Feature Article highlights recent work from our lab on RC and RC-inspired hybrid systems that capture the Sun's energy and convert it to chemical energy in the form of H2, a carbon-neutral energy source derived from water. Biohybrids made from the Photosystem I (PSI) RC are among the best photocatalytic H2-producing protein hybrids to date. Targeted self-assembly strategies that couple abiotic catalysts to PSI translate to catalyst incorporation at intrinsic PSI sites within thylakoid membranes to achieve complete solar water-splitting systems. RC-inspired biohybrids interface synthetic photosensitizers and molecular catalysts with small proteins to create photocatalytic systems and enable the spectroscopic discernment of the structural features and electron transfer processes that underpin solar-driven proton reduction. In total, these studies showcase the incredible scientific opportunities photosynthetic biohybrid research provides for harnessing the optimal qualities of both artificial and natural photosynthetic systems and developing materials that capture, convert, and store solar energy as a fuel.

Impact of surface hydrophilicity on the ordering and transport properties of bicontinuous microemulsions.

Microemulsions (MEs) have many industrial applications, where recent developments have shown that MEs can be utilized for electrochemical applications, including potentially in redox flow batteries. However, understanding the structure and dynamics of these systems, including at a surface, is needed to direct and rationally control their electrochemical behavior. While bulk solution measurements have provided insight into their structure, their assembly at an interface also impacts the electron (to the electrode) and ion (across the surfactant) charge transfer processes in the system. To address this shortcoming, neutron reflectivity experiments and molecular simulations have been completed that document the near surface structure of a series of deuterated water (D2O)/polysorbate-20/toluene MEs on hydrophilic and amphiphilic surfaces. These results show that the microemulsions form complex layered structures near a hard electrode surface, where most layers are not purely one component. Decreasing the D2O concentration in the ME increases the number of and purity of the layers established on the solid surface. These lamellar-type layers transition from the surface to the bulk microemulsion as a series of mixed layers (i.e., containing oil, water, and surfactant) that are consistent with perforated lamellae. Additionally, these mixed lamellae appear to become more perforated with oil and water pathways on an amphiphilic surface. The purity and thickness of these layers will influence the accessibility of an electrode by redox active species, as well as ion transport required to satisfy the electroneutrality condition.

Electron transfer mechanism mediated MOF-derived nanoflowers catalyst for promoting peroxymonosulfate activation and ciprofloxacin degradation

Three MOF-derived nanoparticles were synthesized by manganese doping and calcination of ZIF-67 precursor. The surface physicochemical properties of these materials were compared using SEM, TEM, XRD, FTIR and BET analyses. Among them, cobalt-manganese oxide nanoflowers (CoMn2O4-NFs) exhibited excellent catalytic performance in the degradation of ciprofloxacin (CIP) by activated peroxymonosulfate (PMS), achieving 100 % removal within 30 minutes with a rate constant (kobs) of 0.2960 min−1. The catalytic mechanism was elucidated by quenching experiments, EPR, electrochemical analysis and X-ray photoelectron spectroscopy (XPS). The results show that the non-radical oxidation process was initiated mainly by direct electron transfer and 1O2 (∼80 %), with a small contribution from the radical SO4·- (∼20 %). The nano-confined structure on the surface of CoMn2O4-NFs makes it easy to combine with PMS to form CoMn2O4-NFs/PMS* complexes, which directly capture electrons from CIP to complete the degradation process. The double redox cycle of cobalt-manganese ions and oxygen vacancies on CoMn2O4-NFs could accelerate the electron transfer process. CoMn2O4-NFs maintained high removal efficiency (>99 %) over a wide pH range (3−11), with minimal interference from most environmental anions, demonstrating strong stability and interference resistance. This study provides insights into using metal-based materials for oxidative degradation of organic pollutants via non-radical pathways.

Facilitating Intracellular Electron Bifurcation by Mediating Flavin-Based Extracellular and Transmembrane Electron Transfer: A Novel Role of Pyrogenic Carbon in Dark Fermentation for Hydrogen Production.

Pyrogenic carbon is considered an enhancer to H2-yielding dark fermentation (DF), but little is known about how it regulates extracellular electron transfer (EET) and influences transmembrane respiratory chains and intracellular metabolisms. This study addressed these knowledge gaps and demonstrated that wood waste pyrogenic carbon (biochar) could significantly improve the DF performance; e.g., addition of pyrogenic carbon produced by pyrolysis at 800 °C (PC800) increased H2 yield by 369.7%. Biochemical quantification, electrochemical analysis, and electron respiratory chain inhibition tests revealed that PC800 promoted the extracellular flavin-based electron transfer process and further activated the acceleration of the transmembrane electron transfer. Comparative metagenome/metatranscriptome analyses indicated that the flavin-containing Rnf complex was the potential transmembrane respiratory enzyme associated with PC800-mediated EET. Based on NADH/NAD+ circulation, the promoted Rnf complex could stimulate the functions of the electron bifurcating Etf/Bcd complex and startup of glycolysis. The promoted Etf/Bcd could further contribute to balance the NADH/NAD+ level for glycolytic reactions and meanwhile provide reduced ferredoxin for group A1 [FeFe]-hydrogenases. This proton-energy-linked mechanism could achieve coupling production of ATP and H2. This study verified the important roles of pyrogenic carbon in mediating EET and transmembrane/intracellular pathways and revealed the crucial roles of electron bifurcation in DF for hydrogen production.

Facile synthesis and tunable fluorescent properties of a new D-π-A isocoumarin: Applications in encryption and OLED technology

A facile synthesis of a new D-π-A isocoumarin (ICP-NH2) with only two steps under mild conditions through O-acylation/Wittig/reduction reaction has been established. The readily accessible phosphonium salt precursor 1 and 4-nitrobenzoyl chloride 2 produced intermediate ICP-NO2 in the presence of triethylamine. Subsequently, ICP-NO2 underwent conversion to ICP-NH2 through the reduction of stannous dichloride. ICP-NH2 exhibits enhanced fluorescence overcoming the photo-induced electron transfer (PET) process in ICP-NO2. ICP-NH2 demonstrates a significant change in fluorescence from blue to green in various polar solvents, and DFT analysis confirmed that its solvatochromism is attributed to intramolecular charge transfer (ICT) effect. ICP-NH2 undergoes noticeable acidochromism based on reversible protonation and deprotonation reactions with TFA and TEA, leading to periodic changes in fluorescence from green to dark blue. This phenomenon can be utilized in designing reusable encryption technology. Additionally, ICP-NH2 can be employed in the fabrication of a cyan green OLED device.

Exploring the reaction mechanistic pathway for the sensing of G-Series nerve agent with Kemp's triacid derivative: A computational study

Kemp's triacid derivative have been reported as a candidate for sensing of nerve agents employing the photoinduced electron transfer (PET) processes. The sensor probe molecules were prepared with primary alcohol in very close proximity to a tertiary amine to acylate the alcohol with rapid intramolecular N-alkylation to produce quaternary ammonium salt. The reaction pathways for the formation of quaternary ammonium salt and isomethyl propyl phosphonate remain unexplored. In this report, the mechanistic pathways of G-series nerve agents sarin and its simulant diethylcholorophosphate (DCP) with Kemp's triacid derivatives has been explored computationally. The calculations performed with B3LYP-D3/6-311+G(d,p) level of theory in DCM solvent revealed that the reaction proceeds via intermolecular and intramolecular SN2 pathways. The probe molecule is sterically hindered, therefore, the frontside and backside SN2 reaction pathways have been examined. The computed results suggest that the first intermolecular SN2 reaction of Kemp's triacid derivatives (I &II) with sarin for the backside attack is energetically favored compared to the frontside attack and the following intramolecular SN2 reaction is a barrierless process. The calculations performed with simulant diethylcholorophosphate (DCP) and Kemp's triacid derivatives (I &II) show that the reactions are energetically more facile compared to the nerve agent sarin molecule. The Distortion-Interaction model and ΔNBOSteric analysis showed that the back side is energetically favored over the front side attack in such SN2 reactions. The designed Kemp's triacid derivative (II) with phosphorus center for sensing sarin and (DCP) suggests that the size of the hetero centers are important to facilitate the reaction in the probe molecule.

Important role of cellulose and lignin in controlling the crystal structure of iron-carbon composite: Fe3C surpassing Fe0 in activating peroxymonosulfate

The mechanism of producing iron-carbon composites with different crystal structures by varied wood-based biomass remains unclear. Herein, cellulose and lignin as the important components of wood-based biomass were used to investigate the influence on the crystal structure of iron-carbon composites. Results showed that Fe3C could only be produced in cellulose-containing pyrolysis processes, while the pyrolysis of lignin could reduce the iron salt to Fe0. Additionally, prolonging pyrolysis time and increasing the ratio of cellulose to Fe also favored the production of Fe3C. When applied to activate peroxymonosulfate (PMS), the Fe@Cel0.5-4 typically dominated by Fe3C showed better performance than Fe@Ln1.0-4 which was dominated by Fe0 in the aspects of adsorption, electron transfer, retaining the iron species, sustainability, adaptability to complex water conditions, and the catalytic capability to degrade diclofenac (DCF). Quenching experiments and electron spin resonance results indicated the presence of free radicals (OH, SO4−, SO5− and O2−) and non-radical (1O2 and electron transfer process) pathways in both processes. However, the degradation of DCF in Fe@Cel0.5-4/PMS process was mainly dominated by 1O2 and electron transfer while was contributed by radical and nonradical pathways almost equally in Fe@Ln1.0-4/PMS process. This study may cast some light on the development of iron-carbon composites using wood-based biomass as the carbon source to synthesize the highly efficient catalyst for PMS activation.

Advancing anaerobic digestion with MnO2-modified biochar: Insights into performance and mechanisms

The use of bio-based composites to enhance the methane production in anaerobic digestion has attracted considerable attention. Nevertheless, the study of electron transfer mechanisms and the applications of biochar/MnO2 (MBC) in complex systems remains largely unexplored. Biochar composited with MnO2 at 10:1 mass ratio (MBC10) increased the content of volatile fatty acids by 9.09 % during acidogenic phase. During the methanogenic experiments using acetate, cumulative methane production (CMP) rose by 5.83 %, and in the methanogenic experiments using food waste, CMP increased by 24.32 %. Microbial community analysis indicated an enrichment of Syntrophomonas, Bacilli, and Methanosaetaceae in the MBC10 group. This enrichment occurred mainly due to the redox capability of MnO2 enhancing MBC capacitance, thereby facilitating microbial electron transfer processes. Additionally, under 2 g/L ammonia nitrogen concentration and 30 g/L organic load, the CMP of MBC10 increased by 12.74 % and 9.44 %, respectively, compared to the BC600 group. This study illuminates MBC's electron transfer mechanisms and applications, facilitating its wider practical adoption and fostering future innovations.

Near-Infrared Fluorescent Turn-On Probe for Selective Detection of Hypochlorite in Aqueous Medium and Live Cell Imaging.

Hypochlorite, as an important reactive oxygen species (ROS), plays a vital role in many physiological and pathological processes, but an excess concentration of hypochlorite (ClO-) may become toxic to humans and cause disease. Hence, the selective and rapid detection of hypochlorite (ClO-) is necessary for human safety. Here, we report a novel near-infrared (NIR) fluorescence "turn-on" and highly selective benzophenoxazinium chloride-based fluorescent probe, BPH (benzophenoxazinium dihydroxy benzaldehyde), for hypochlorite detection. Due to hypochlorite-induced vicinal diol oxidation to the corresponding ortho benzoquinone derivative, the photoinduced electron transfer (PET) process, which was operating from vicinal diol to the benzophenoxazinium chloride receptor moiety, was suddenly inhibited, as a result of which strong NIR fluorescence "turn-on" emission was observed. The detection limit of BPH was found to be 2.39 × 10-10 M, or 0.23 nM. BPH was successfully applied for exogenous and endogenous hypochlorite detection in live MDA-MB 231 cells.

Bidentate Substrate Binding Mode in Oxalate Decarboxylase.

Oxalate decarboxylase is an Mn- and O2-dependent enzyme in the bicupin superfamily that catalyzes the redox-neutral disproportionation of the oxalate monoanion to form carbon dioxide and formate. Its best-studied isozyme is from Bacillus subtilis where it is stress-induced under low pH conditions. Current mechanistic schemes assume a monodentate binding mode of the substrate to the N-terminal active site Mn ion to make space for a presumed O2 molecule, despite the fact that oxalate generally prefers to bind bidentate to Mn. We report on X-band 13C-electron nuclear double resonance (ENDOR) experiments on 13C-labeled oxalate bound to the active-site Mn(II) in wild-type oxalate decarboxylase at high pH, the catalytically impaired W96F mutant enzyme at low pH, and Mn(II) in aqueous solution. The ENDOR spectra of these samples are practically identical, which shows that the substrate binds bidentate (κO, κO') to the active site Mn(II) ion. Domain-based local pair natural orbital coupled cluster singles and doubles (DLPNO-CCSD) calculations of the expected 13C hyperfine coupling constants for bidentate bound oxalate predict ENDOR spectra in good agreement with the experiment, supporting bidentate bound substrate. Geometry optimization of a substrate-bound minimal active site model by density functional theory shows two possible substrate coordination geometries, bidentate and monodentate. The bidentate structure is energetically preferred by ~4.7 kcal/mol. Our results revise a long-standing hypothesis regarding substrate binding in the enzyme and suggest that dioxygen does not bind to the active site Mn ion after substrate binds. The results are in agreement with our recent mechanistic hypothesis of substrate activation via a long-range electron transfer process involving the C-terminal Mn ion.

Methane oxidation coupling with heavy metal and microplastic transformations for biochar-mediated landfill cover soil

The impact of co-occurring heavy metal (HM) and microplastic (MP) pollution on methane (CH4) oxidation by methanotrophs (MOB) in landfill cover soil (LCS) and the role of biochar in mediating these collaborative transformations remains unclear. This study conducted batch-scale experiments using LCS treated with individual or combined HMs and MPs, with or without biochar amendment. Differentiation in methanotrophic activities, HM transformations, MP aging, soil properties, microbial communities, and functional genes across the groups were analyzed. Biochar proved essential in sustaining efficient CH4 oxidation under HM and MP stress, mainly by diversifying MOB, and enhancing polysaccharide secretion to mitigate environmental stress. While low levels of HMs slightly inhibited CH4 oxidation, high HM concentration enhanced methanotrophic activities by promoting electron transfer process. MPs consistently stimulated CH4 oxidation, exerting a stronger influence than HMs. Notably, the simultaneous presence of low levels of HMs and MPs synergistically boosted CH4 oxidation, linked to distinct microbial evolution and adaptation. Methanotrophic activities were demonstrated to affect the fate of HMs and MPs. Complete passivation of Cu was readily achieved, whereas Zn stabilization was negatively influenced by biochar and MPs. The aging of MPs was also partially suppressed by biochar and HM adsorption.

Schottky Interface Enabled Electrospun Rhodium Oxide Doped Gold for Both pH Sensing and Glucose Measurements in Neutral Buffer and Human Serum.

This study has focused on adjusting sensing environment from basic to neutral pH and improve sensing performance by doping electrodeposited gold (Au) with metal oxide for nonenzymatic glucose measurements in forming a Schottky interface for superior glucose sensing with detailed analysis for the sensing mechanism. The prepared sensor also holds the ability to measure pH with the identical electrospun metal oxide-electrodeposited Au, which composed a dual sensor (glucose and pH sensor) through applying chronoamperometry and open circuit potential methods. The rhodium oxide nanocoral structure was fabricated with an electrospinning precursor solution, followed by a calcination process, and it was mixed with electrodeposited nanocoral gold to form the Schottky interface by constructing a p-n type heterogeneous junction for improved sensitivity in glucose detection. The prepared materials were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectrometry (XPS), etc. The prepared materials were used for both pH responsive testing and amperometric glucose measurements. The rhodium oxide nanocoral doped gold demonstrated a sensitivity of 3.52 μA mM-1 cm-2 and limit of detection of 20 μM with linear range up to 3 mM glucose concentration compared to solely electrodeposited gold for a sensitivity of 0.46 μA mM-1 cm-2 and a limit of detection of 450 μM. The Mott-Schottky method was used for the analysis of an electron transfer process from noble metal to metal oxide to electrolyte in demonstrating the improved sensitivity at neutral pH for glucose measurements due to the Schottky barrier adjustment mechanism at an applied flat band potential of 0.3 V. This work opens a new venue in illustrating the metal oxide/metal materials in the glucose neutral response mechanism. In the end, human serum samples were tested against current commercial glucose meter to certify the accuracy of the proposed sensor.

Genome-centric metagenomic analysis reveals mechanisms of quorum sensing promoting anaerobic digestion under sulfide stress: Syntrophic metabolism and microbial self-adaptation

Sulfide stress is a common inhibition factor in anaerobic digestion systems with sulfur-rich feedstocks. Quorum sensing (QS) signaling molecule N-acyl-homoserine lactones (AHLs) possess positive effect on promoting anaerobic digestion. However, the micro-biological mechanisms of AHLs affecting syntrophic metabolism and microbial self-adaptation have not yet been deciphered in anaerobic digestion under sulfide stress. In this study, the CH4 production increased by 21.34 % at 20 μM AHLs addition in anaerobic digestion under sulfide stress. AHLs contributed to establishing potential syntrophic relationship between acidifying bacteria (unclassified_o__Bacteroidales, Lentimicrobium, Acetoanaerobium, Longilinea, and Sphaerochaetaa) and Methanothrix. AHLs promoted syntrophic metabolism by boosting microbial metabolic activity and interspecies electron transfer (IET) process under sulfide stress. For microbial metabolic activity, AHLs promoted the key enzyme synthesis in acidogenesis and methanogenesis. For IET process, AHLs promoted the assembly and synthesis of conductive pili, and synthesis and secretion of riboflavin. Furthermore, AHLs promoted microbial self-adaptation including two component system, lipopolysaccharide biosynthesis, and DNA repair, which were important evidences that microbial resistance to sulfide stress was enhanced by AHLs. Microbial self-adaptation provided favorable foundation and safeguard for syntrophic metabolisms under sulfide stress. These findings deciphered the micro-biological mechanisms of AHLs enhancing anaerobic digestion under sulfide stress.

Molecular–level insights into the synergistic activation of peracetic acid by ultraviolet and ferrous ions for the degradation of sedimentation sludge water in drinking water treatment plants based on Fourier transform-ion cyclotron resonance mass spectrometry

Sedimentation sludge water (SSW) from sedimentation tanks in drinking water treatment plants contains significant amounts of dissolved organic matter (DOM) and precursors of disinfection byproducts, raising increasing concerns about the safety of finished water following SSW recycling. This study explores the alterations in bulk properties and molecular characteristics of DOM in SSW treated with ultraviolet (UV)/ferrous ions (Fe2+) and peracetic acid (PAA) using fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT–ICR MS). The primary reactive species, hydroxyl radicals (·OH) and acylperoxy radicals (CH3C(O)OO·) achieved degradation rates of up to 82.0%, eliminating 84.5% of total fluorescent components and reducing molecular intensity and apparent molecular count by 90.9% and 69.8%, respectively. This treatment significantly reduced the aromaticity of DOM, leading to the formation of more oxidized and stable compounds. Reaction mechanisms indicate that ·OH and CH3C(O)OO· primarily facilitate oxygen addition and dehydrogenation, while CH3C(O)OO· promotes decarboxylation through weak electron transfer processes. The treatment preferentially removes complex DOM containing nitrogen and sulfur heteroatoms, which are key precursors of disinfection byproducts. These findings enhance our understanding of DOM transformations during UV/Fe2+/PAA treatment and provide valuable insights into the safe recycling of SSW.

On-site monitoring of L-adrenaline neurotransmitter in biological samples by chitosan oligosaccharide derived carbon dots

Carbon quantum dots (CDs) are fascinating fluorescent nanomaterial for spectrofluorimetry sensor applications, owing to the fact of its strong chemical stability, high quantum yield and high photostability. At this instance, we have developed the fluorescent sensing technique to detect the L-adrenaline (L-Adr) by nitrogen-doped carbon quantum dots as a sensing probe. The nitrogen-doped carbon dots was synthesized using chitosan oligosaccharide by hydrothermal method. The synthesized chitosan oligosaccharide derived CDs (COL-CDs) exhibits blue fluorescence under UV light and the size of the carbon quantum dots is 3.39 ± 0.08 nm calculated from HR-TEM image. The hormone called L-Adr found in the human body is crucial for controlling visceral processes. Utilizing the process of photo-induced electron transfer (PET), the previously mentioned COL-CDs have applied to sense the L-Adr. The sensing mechanism have explained clearly using Rehm-Weller equation by calculating ΔG. Tap water, blood serum, urine and adrenaline drug samples employed as real sample for the sensing L-Adr. A reagent free paper-based kit established for the purpose of on-site monitoring L-Adr. The smartphone’s colour picker software used to measure the RGB intensity from the paper-based kit.