Changes In Redox Potential Research Articles

Restored saltmarshes have low beta diversity due to limited topographic variation, but this can be countered by management

Abstract Spatial heterogeneity of species (beta diversity) is an important attribute of ecological communities, but is less frequently considered when assessing restoration success than other aspects of diversity (gamma and alpha). Differences in beta diversity between restored and natural sites may arise due to differences in environmental heterogeneity. We used a nested sampling design to survey plant communities and environmental conditions (elevation, redox potential and metrics of topography) on four pairs of restored and natural saltmarshes. We assessed whether there were differences in both alpha and beta diversity between natural and restored sites and analysed their environmental drivers. Topography was an important driver of plant alpha diversity and beta diversity on saltmarshes. The effects of topography were partly indirect, mediated though changes in redox potential, but topography also influenced plant communities independently of both elevation and redox. Restored saltmarshes were less heterogeneous in topography than natural marshes. This reduced topography was reflected in lower beta diversity; plant communities 1 m apart in natural marshes were as dissimilar as those found 20 m apart in restored marshes. Large‐scale topographic manipulation carried out at one site a decade after initial restoration successfully increased topographic heterogeneity and increased beta diversity when surveyed 3 years after manipulation. These changes were still evident when resurveyed after a further 2 years. Synthesis and applications. Increasing environmental heterogeneity can improve restoration outcomes by increasing beta diversity on restored sites. The effect of environmental heterogeneity is likely to be particularly strong within intertidal habitats such as saltmarshes, where small changes in topography can determine whether a species can occur at a given location. Topographic manipulation is a feasible post‐restoration technique that can be applied to ensure restored saltmarshes better meet policy targets of biological, physical and functional equivalence with natural marshes.

Anaerobic Digestion Combined with Electrolysis of Poultry Manure and Activated Sludge Inoculum

The aim of the work was to study the effect of electrolysis on the process of anaerobic digestion in the example of poultry manure with an inoculum of activated sludge from a municipal wastewater treatment plant. The set aim was achieved by solving the following tasks: microcopiing of anaerobic activated sludge during the digestion of poultry manure under the influence of electrolysis treatment; studying the dynamics of biogas yield and its component composition under electrolysis treatment; studying the change in pH values and redox potential (ORP) in experiments with a combination of a bioreactor with electrolysis treatment and without treatment. Evaluation of the effect of stimulating the metabolic activity of microorganisms during treatment in the bioreactor-electrolyser was the most significant result. In addition, improved biodegradability of complex organic components of poultry manure was substantiated. Thus, methane yield on the 28th day was 640.5 ml from the total volume of 1525 ml of biogas, and under conventional conditions, methane yield was 33.4 ml from 50 ml of total volume. The decrease of H2S content in biogas under the influence of electrolysis was determined. A low ORP value of - 495 mV was achieved in the control experiment (without electrolysis treatment). ORP gradually increased in the bioreactor-electrolyser at all stages of digestion and reached -53 mV on day 28. pH stabilized at a neutral level. The positive effect of combining anaerobic digestion with electrolysis on the intensification of biogas production with a large volume of methane has been experimentally confirmed.

Transcriptional Response of Two Brassica napus Cultivars to Short-Term Hypoxia in the Root Zone.

Waterlogging is one major stress for crops and causes multiple problems for plants, for example low gas diffusion, changes in redox potential and accumulation of toxic metabolites. Brassica napus is an important oil crop with high waterlogging sensitivity, which may cause severe yield losses. Its reactions to the stress are not fully understood. In this work the transcriptional response of rapeseed to one aspect of waterlogging, hypoxia in the root zone, was analyzed by RNAseq, including two rapeseed cultivars from different origin, Avatar from Europe and Zhongshuang 9 from Asia. Both cultivars showed a high number of differentially expressed genes in roots after 4 and 24 h of hypoxia. The response included many well-known hypoxia-induced genes such as genes coding for glycolytic and fermentative enzymes, and strongly resembled the hypoxia response of the model organism Arabidopsis thaliana. The carbohydrate status of roots, however, was minimally affected by root hypoxia, with a tendency of carbohydrate accumulation rather than a carbon starvation. Leaves did not respond to the root stress after a 24-h treatment. In agreement with the gene expression data, subsequent experiments with soil waterlogging for up to 14 days revealed no differences in response or tolerance to waterlogging between the two genotypes used in this study. Interestingly, using a 0.1% starch solution for waterlogging, which caused a lowered soil redox potential, resulted in much stronger effects of the stress treatment than using pure water suggesting a new screening method for rapeseed cultivars in future experiments.

A partial least squares-path model of causality among environmental deterioration indicators in the dry period of Paraopeba River after the rupture of B1 tailings dam in Brumadinho (Minas Gerais, Brazil)

This study investigated the collapse of B1 mine-tailings dam that occurred in 25 January 2019 and severely affected the Brumadinho region (Minas Gerais state, Brazil) socially, economically and environmentally. As regards water resources, the event impacted the Paraopeba River in the first 155.3 km counted from the dam site, meaning nearly half the main water course downstream of B1. In the impacted sector, high concentrations of tailings-related Al, Fe, Mn, P in river sediment-tailings mixtures and water were detected, as well as changes to the reflectance of riparian forests. In the river water, the metal concentrations raised significantly above safe levels. For caution, the water management authorities declared immediate suspension of Paraopeba River as drinking water source to the Metropolitan Region of Belo Horizonte (6 million people), irrespective of representing nearly 30% of all supply. In this study, the main purpose was to assess potential links between tailings distribution, river water composition and reflectance of forest vegetation, which worked out as latent variables in regression models. The latent variables were represented by numerous physical and chemical parameters, measured 4 times in 22 sites during the dry period of 2019. The modeling results suggested the release of aluminum and phosphorus from sand fractions in the mine tailings as major cause of water contamination. The NDVI changes were interpreted as environmental deterioration. Changes in redox potential may have raised manganese concentrations in surface water further affecting the forest NDVI. Distance from the B1 dam and dissolved calcium appear to attenuate deterioration. Overall, the regressions allowed robust prognoses of environmental deterioration in the Paraopeba River under low flow conditions. More importantly, they can be transposed to similar dam ruptures helping environmental authorities to decide upon measures that can bring the affected rivers to pre-rupture conditions.

Redox-sensitive fluorescent biosensors detect Sinorhizobium meliloti intracellular redox changes under free-living and symbiotic lifestyles

Reactive oxygen species such as hydrogen peroxide (H2O2) are key signaling molecules that control the setup and functioning of Rhizobium-legume symbiosis. This interaction results in the formation of a new organ, the root nodule, in which bacteria enter the host cells and differentiate into nitrogen (N2)-fixing bacteroids. The interaction between Sinorhizobium meliloti and Medicago truncatula is a genetic model to study N2-fixing symbiosis. In previous work, S. meliloti mutants impaired in the antioxidant defense, showed altered symbiotic properties, emphasizing the importance of redox-based regulation in the bacterial partner. However, direct measurements of S. meliloti intracellular redox state have never been performed. Here, we measured dynamic changes of intracellular H2O2 and glutathione redox potential by expressing roGFP2-Orp1 and Grx1-roGFP2 biosensors in S. meliloti. Kinetic analyses of redox changes under free-living conditions showed that these biosensors are suitable to monitor the bacterial redox state in real-time, after H2O2 challenge and in different genetic backgrounds. In planta, flow cytometry and confocal imaging experiments allowed the determination of sensor oxidation state in nodule bacteria. These cellular studies establish the existence of an oxidative shift in the redox status of S. meliloti during bacteroid differentiation. Our findings open up new possibilities for in vivo studies of redox dynamics during N2-fixing symbiosis.

Comprehensive Effect of Oxidant Addition in an FGD Slurry on the Removal and Distribution of Selenium: A Field Study.

Flue gas desulfurization (FGD) scrubbers capture selenium in coal-fired power plants, leading to a high concentration of selenium in the slurry. This research proves that SO32- is preferentially oxidized compared to SeO32- by S2O82-. With the increase in the oxidation-reduction potential (ORP) caused by S2O82- addition, the conversion rate of SO32- increased and the size of gypsum grains grew from 31.2 to 34.6 μm. SeO32- migrates into gypsum grains during the growth of CaSO4·2H2O, leading to selenium fixation in gypsum. In a field study of a 350 MW unit, the ORP increased from 142 to 450 mV when Na2S2O8 was fed into the FGD slurry. With the addition of the oxidant, 65.1% of selenium in the liquid phase migrated into gypsum. The concentration of selenium in the leachate of gypsum after oxidant addition decreased by 68.0%. A 2.34% increase in the selenium removal rate was observed in the scrubber. This study focuses on the migration and conversion of selenium in an actual FGD slurry via a field test. The results found in the 350 MW unit are consistent with laboratory results. The change in ORP has been proven to be effective in adjusting the selenium distribution in the FGD slurry.

Single and Multiple Stimuli-Responsive Polymer Particles for Controlled Drug Delivery.

Polymers that can change their properties in response to an external or internal stimulus have become an interesting platform for drug delivery systems. Polymeric nanoparticles can be used to decrease the toxicity of drugs, improve the circulation of hydrophobic drugs, and increase a drug’s efficacy. Furthermore, polymers that are sensitive to specific stimuli can be used to achieve controlled release of drugs into specific areas of the body. This review discusses the different stimuli that can be used for controlled drug delivery based on internal and external stimuli. Internal stimuli have been defined as events that evoke changes in different characteristics, inside the body, such as changes in pH, redox potential, and temperature. External stimuli have been defined as the use of an external source such as light and ultrasound to implement such changes. Special attention has been paid to the particular chemical structures that need to be incorporated into polymers to achieve the desired stimuli response. A current trend in this field is the incorporation of several stimuli in a single polymer to achieve higher specificity. Therefore, to access the most recent advances in stimuli-responsive polymers, the focus of this review is to combine several stimuli. The combination of different stimuli is discussed along with the chemical structures that can produce it.

Nanogel Crosslinking-Based Belousov-Zhabotinsky Self-Oscillating Polyacrylamide Gel with Improved Mechanical Properties and Fast Oscillatory Response.

The Belousov-Zhabotinsky (BZ) self-oscillating gel is a unique actuator suited for studying the behavior of intelligent soft robots. However, the traditional BZ self-oscillating polyacrylamide (PAAm) gel is easily broken and is slow to response to stimuli, which limits its practical application. Therefore, the preparation of BZ gels with sensitive responses to external stimuli and desirable, robust mechanical properties remains a challenge. In this work, PAAm-activated nanogels with unpolymerized double bonds are used as nanocrosslinkers to synthesize a nanogel crosslinking-based BZ (NCBZ) self-oscillating PAAm gel, whose mechanical properties, for example, antipuncture, cutting, and tensile properties, are superior to those of traditional PAAm BZ-self-oscillating gels. The oscillatory period of the traditional gel is much longer than that of the corresponding homogeneous BZ system, resulting from the slow response of the gel to changes in redox potential, whereas large, interconnected pores inside the NCBZ gel provide efficient channels for rapid species transport, supporting fast response of the gel, which results in almost the same period of chemomechanical oscillations as the homogeneous system under the same conditions. Scanning electron microscopy results show that the NCBZ gel is more stable than the traditional BZ PAAm gel after 7 h of oscillation. Our results make it possible to prepare robust gel motors and provide promising application prospects for smart soft robots, actuators, sensors, tissue engineering, and other applications.

Inflammation-Triggered Supramolecular Nanoplatform for Local Dynamic Dependent Imaging-Guided Therapy of Rheumatoid Arthritis.

The aging of population has resulted in a significant increase in the prevalence of rheumatoid arthritis (RA), which is a persistent and recurrent synovial inflammation caused by abnormal immune activation. Herein, the authors designed an inflammation‐triggered disassembly (ITD) nanoplatform by a supramolecular assembly method, which controls the decomposition and drug release through changes in cytokine concentrations and redox potentials during the onset of arthritis, and its dual‐targeted synergistic effect on collagen‐induced arthritis (CIA) rats resulted in higher cell death rate and immunosuppressive rate. Meanwhile, they propose the local dynamic dependent imaging (LDDI) technology to diagnose the disease status, which may produce corresponding changes with the fluctuation of inflammatory activity and improve the accuracy of dual‐target therapy by monitoring the synovial changes through in situ photoactivation of the second near infrared light (NIR‐II). Very importantly, histological analysis shows that ITD strategy relieved joint destruction and cartilage degeneration and its clinical score is similar to that of the healthy group. Their work provides an effective strategy for the early diagnosis and treatment of acute and chronic inflammation diseases, which can interfere to abnormal immune activation, rather than affecting the normal function of immune system.

Detecting Redox Potentials Using Porous Boron Nitride/ATP-DNA Aptamer/Methylene Blue Biosensor to Monitor Microbial Activities

Microbial activity has gained attention because of its impact on the environment and the quality of people’s lives. Most of today’s methods, which include genome sequencing and electrochemistry, are costly and difficult to manage. Our group proposed a method using the redox potential change to detect microbial activity, which is rooted in the concept that metabolic activity can change the redox potential of a microbial community. The redox potential change was captured by a biosensor consisting of porous boron nitride, ATP-DNA aptamer, and methylene blue as the fluorophore. This assembly can switch on or off when there is a redox potential change, and this change leads to a fluorescence change that can be examined using a multipurpose microplate reader. The results show that this biosensor can detect microbial community changes when its composition is changed or toxic metals are ingested.

Cross-Linked Ionic Polysaccharides: Insights from the Structure to Stimuli-Sensitive Drug Delivery System Applications

The review provides an insight regarding the state of the art of cross-linked ionic polysaccharides, which are a part of common drug delivery systems, which are involved in the regulation of release of drug in specific required sites. The changes in pH, ion concentration, wavelength, redox potential, temperature, electric and magnetic field intensity are the stimuli sensitive functions, which play a major roles. Due to their high reproducibility and better characterization from natural resources, the polysaccharides remains as a point of interest for compiling many stimuli-responsive drug delivery systems. The hydrogel networks are formed from ready cross-linking of ionic polysaccharides, subject to control of internal and external variables. These hydrogel networks become operative for drug release on-off through complex mechanisms. The polysaccharide-based drug delivery systems are now responsive to different hybrids, composites and grafted polymers with a broad range of stimuli functions.

Supramolecular Polymerization Powered by Escherichia coli : Fabricating a Near-Infrared Photothermal Antibacterial Agent in Situ

Supramolecular Polymerization Powered by <i>Escherichia coli</i> : Fabricating a Near-Infrared Photothermal Antibacterial Agent in Situ

Vertical differentiation of pedogenic iron forms – a key of hydromorphic soil profile development

This paper focuses on the vertical distribution and characterisation of pedogenic iron forms in a Gleysol- Histosol transect developed in a marshy area in the Danube-Tisza Interfluve, Hungary. Four soil profiles were investigated along a series of increasing waterlogging and spatial and temporal patterns of hydromorphic pedofeatures (characteristics of pedogenic iron forms) were recorded. Frequent and wide-range redox potential (Eh) changes caused the emergence of many types of redoximorphic iron features, including mottles, plaques and nodules. The forms of these features depended on the micro-environments determined by the vertical position in the soil profile and the presence of plant roots. The greatest iron enrichment occurred in the zone of most intensive and widest-range redox fluctuations. Increasing water saturation resulted the extension of gleyic pattern due to the existence of permanent reduction. Most of the features also showed annual variations during the varying periods of water saturation and aeration.

Application of polyaniline nanofibers for the construction of nitrate all-solid-state ion-selective electrodes

The application of polyaniline nanofibers doped with chloride and nitrate ions (PANINFs-Cl and PANINFs-NO3) in potentiometry was described. Both kinds of nanofibers were used as an ion-to-electron transducer in ion-selective electrodes with solid contact (SCISEs). Extensive research on the properties of the nanofibers themselves (SEM, UV–Vis spectroscopy, FTIR) and the constructed electrodes (potentiometric methods, electrochemical impedance spectroscopy) has been carried out. Basic analytical parameters of electrodes containing various nanofibers contents in the ion-selective membrane and with nanofibers as an intermediate layer were determined. It was found that application of PANI nanofibers resulted in improvement of electrode performance (among others, better stability and reversibility of the electrode potential). The obtained sensors were characterized by a high slope of the calibration curve, a wide measuring range and a fast response time. Moreover, they were insensitive to change of redox potential, as well as light and the presence of oxygen in the solution, what is important from a practical point of view. They were also successfully used for nitrate determination in real environmental samples.

The Crystal Structure of Cysteamine Dioxygenase Reveals the Origin of the Large Substrate Scope of This Vital Mammalian Enzyme.

We report the crystal structure of the mammalian non-heme iron enzyme cysteamine dioxygenase (ADO) at 1.9 Å resolution, which shows an Fe and three-histidine (3-His) active site situated at the end of a wide substrate access channel. The open approach to the active site is consistent with the recent discovery that ADO catalyzes not only the conversion of cysteamine to hypotaurine but also the oxidation of N-terminal cysteine (Nt-Cys) peptides to their corresponding sulfinic acids as part of the eukaryotic N-degron pathway. Whole-protein models of ADO in complex with either cysteamine or an Nt-Cys peptide, generated using molecular dynamics and quantum mechanics/molecular mechanics calculations, suggest occlusion of access to the active site by peptide substrate binding. This finding highlights the importance of a small tunnel that leads from the opposite face of the enzyme into the active site, providing a path through which co-substrate O2 could access the Fe center. Intriguingly, the entrance to this tunnel is guarded by two Cys residues that may form a disulfide bond to regulate O2 delivery in response to changes in the intracellular redox potential. Notably, the Cys and tyrosine residues shown to be capable of forming a cross-link in human ADO reside ∼7 Å from the iron center. As such, cross-link formation may not be structurally or functionally significant in ADO.

Chitin as a Sorbent Superior to Other Biopolymers: Features and Applications in Environmental Research, Energy Conversion, and Understanding Evolution of Animals

Chitin is an effective sorbent which can be used in environmental monitoring, beyond obvious applications in withholding metal-containing pollutants from wastewater- or nuclear fuel reprocessing flows, since background levels in (purified) chitin are very low except for a few metals (Fe, Cu, Al, Ti, and Zn). Since retention of Mx+ and their complexes on chitin depend on an oxidation state, and to a lesser extent the presence of possible ligands or co-ligands, partition between chitin samples exposed to sediment and those exposed to water can be changed by environmental factors such as local biota producing or absorbing/metabolizing effective ligands such as citrate or oxalate and by changes of redox potential. Thermodynamics are studied via log P, using calibration functions log P vs. 1/r or log P vs. Σσ (sum of Hammett parameters of ligand donor groups) for di- and trivalent elements not involved in biochemical activity (not even indirectly) and thus measuring “deviations” from expected values. These “deviations” can be due to input as a pollutant, biochemical use of certain elements, precipitation or (bio-induced reduction of SO42− or CO2) dissolution of solids in sediment. Biochemical processes which occur deep in sediment can be detected due to this effect. Data from grafted chitin (saturation within ≤ 10 min) and from outer surfaces of arthropods caught at the same site do agree well. Log P is more telling than total amounts retrieved. Future applications of these features of chitin are outlined.

2-((E)-1-((E)-(2-methoxybenzylidene)hydrazono)ethyl)phenol based cost-effective sensor for the selective detection of Eu3+ ions

The detection of lanthanides has emerged as an attractive field of research due to potential applications in biomedical sciences. Here we design a simple and cost-effective ligand 2-((E)-1-((E)-(2-methoxybenzylidene)hydrazono)ethyl)phenol (MHEP) that acts as a rapid selective sensor for Eu3+ ions with a blue shift in UV–visible, ratiometric enhancement in fluorescence intensity and significant redox potential changes in cyclic voltammetric graph among various metal ions in the CH3OH:H2O (1:1, v/v) solvent system. The UV–visible titrations are used to determine the limit of detection 1.2 × 10−7 M, the limit of quantitation 41 × 10−7 M and linear range 22 × 10−6 M−1 to 124 × 10−6 M−1 are determined. The binding stoichiometry is determined by Job’s plot, mole ratio method and Benesi-Hildebrand plot that is found 1:1 (MHEP:Eu3+) with association constant 2.360 × 105 M−1. The IR spectroscopy reveals the role of imine functionalities for the Eu3+ ions detection.

Electrochemical biotesting technique as applied to comparative assessment of antimicrobial properties of essential oils

A biotesting technique is described that provides for periodic (every 2 hours) recording of changes in pH, redox potential, and electrical conductivity of a liquid culture medium incubated in the presence and in the absence of viable test microorganisms (TM) and test samples (TS). The results of a comparative analysis using this technique of antibiotic activity against Staphylococcus aureus of different concentrations of «essential oils» obtained from 10 types of plant raw materials are presented. Based on this, we can conclude the following. Using the presented methodology, it is possible to assess the effect on the dynamics of the vital activity of TM of samples of various pharmaceutical, cosmetic, food, feed and other products, much more quickly, objectively and informatively than using standard visual methods of microbiological testing. The initial antibiotic activity of TS in most cases was greater than their prolonged antibiotic activity. At the same time, the mid-term (in terms of the time of interaction of TS with TM) antibiotic activity of TS was usually intermediate in value between their initial and prolonged biological activity.

Effect of Leptolyngbya sp. Biofilm and Vallisneria natans Growth on Nutrient Release from Sediment

AbstractNutrients supplied by sediment of lakes and light are likely important factors determining the growth balance between Leptolyngbya sp. biofilm and Vallisneria natans. Therefore, experiments with varying light are conducted to compare the effect of nutrient release from surface sediment on their growth. The results show that changes in pH, dissolved oxygen (DO) and redox potential (Eh) are significantly correlated with the changes in nitrogen(N) and phosphorus (P) concentrations in the water (p &lt; 0.05). The optimum light intensity for the growth of Leptolyngbya sp. and V. natans is different. The biomass of Leptolyngbya sp. biofilm is higher at 2–27 µmol m−2·s−1, but the biomass of V. natans is positively correlated with light intensity (2–54 µmol m−2·s−1) (p &lt; 0.05). The Leptolyngbya sp. biofilm and V. natans can retain P from sediment and significantly remove N in the overlying water. The total P amounts retained by V. natans are significantly higher than that of Leptolyngbya sp. biofilm in all treatments, and the potential for P retention of V. natans increases with the increase of light intensity. The retention of P amounts in the Leptolyngbya sp. biofilm mainly formed 47.8% Fe‐bound P, but 57% NH4CI‐bound P in the V. natans.

Trace Element Mobility during Corg-Enhanced Denitrification in Two Different Aquifers

Nitrate (NO3−)-polluted groundwater treatment by enhanced denitrification is becoming increasingly important due to rising NO3− concentrations and decreasing degradation capacities in aquifers. Besides evaluating the efficacy of substrates added to trigger denitrification, secondary reactions must be closely monitored. Biodenitrification by applied organic carbon (Corg) can lead to considerable changes in redox potential (Eh) and pH, two decisive parameters for trace element mobility. In this study, two geologically and hydrogeochemically different groundwater catchments important for drinking water production were investigated and compared. Sediments were analyzed for trace elements as well as sulfur (S) and carbon (C) contents. Ongoing hydrogeochemical reactions were evaluated with depth-specific isotope characterization, and the potential for trace element mobilization by Corg addition was determined in column experiments. Results for enhanced denitrification showed up to 3.8 times lower reaction rates with respect to comparable studies, probably due to incomplete formation of the necessary denitrifying bacteria. Concentrations of trace elements such as nickel (Ni) must also be considered when evaluating enhanced denitrification, as these can negatively affect microorganisms. Added ethanol led to Ni concentrations dropping from 0.013 mg/L to below the detection limit. Thus, Corg addition may not only induce denitrification, but also lead to the immobilization of previously released trace elements.