The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution gr...The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.展开更多
It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced ...It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced into the lattice of hexagonal ZnIn_(2)S_(4) nanosheets(Ni/ZnIn_(2)S_(4))via directionalsubstituting Zn atom with the facile hydrothermal method.The electronic structure calculations indicate that the introduction of Ni atom effectively extracts more electrons and acts as active site for subsequent reduction reaction.Besides the optimized light absorption range,the elevation of Efand ECBendows Ni/ZnIn_(2)S_(4) photocatalyst with the increased electron concentration and the enhanced reduction ability for surface reaction.Moreover,ultrafast transient absorption spectroscopy,as well as a series of electrochemical tests,demonstrates that Ni/ZnIn_(2)S_(4) possesses 2.15 times longer lifetime of the excited charge carriers and an order of magnitude increase for carrier mobility and separation efficiency compared with pristine ZnIn_(2)S_(4).These efficient kinetics performances of charge carriers and enhanced redox capacity synergistically boost photocatalytic activity,in which a 3-times higher conversion efficiency of nitrobenzene reduction was achieved upon Ni/ZnIn_(2)S_(4).Our study not only provides in-depth insights into the effect of atomic directional-substitution on the kinetic behavior of photogenerated charges,but also opens an avenue to the synchronous optimization of redox capacity and carrier-kinetics performance for efficient solar energy conversion.展开更多
The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2+ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different condition...The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2+ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe(III) to Fe(II) in the solutions containing synthetic extracellular polymeric substances (EPS).When the solution potential is lower than 650 mV (vs SHE),the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe(III) ions is up to 20 g/L but increases with increasing the concentration of Fe(III) ions;jarosites formed by bio-oxidized Fe3+ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2+ ions inside and outside EPS space into Fe^3+ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.展开更多
The sediment redox potential was raised in the laboratory to estimate reduction of internal available phosphorus loads,such as soluble reactive phosphorus(SRP)and total phosphorus(TP),as well as the main elements of s...The sediment redox potential was raised in the laboratory to estimate reduction of internal available phosphorus loads,such as soluble reactive phosphorus(SRP)and total phosphorus(TP),as well as the main elements of sediment extracts in Dianchi Lake.Several strongly reducing substances in sediments,which mainly originated from anaerobic decomposition of primary producer residues,were responsible for the lower redox potential.In a range of -400 to 200 mV raising the redox potential of sediments decreased TP and SRP in interstitial water.Redox potentials exceeding 320 mV caused increases in TP,whereas SRP maintained a relatively constant minimum level.The concentrations of Al,Fe, Ca^(2+),Mg^(2+),K^+,Na^+ and S in interstitial water were also related to the redox potential of sediments,suggesting that the mechanism for redox potential to regulate the concentration of phosphorus in interstitial water was complex.展开更多
The experiments were carried out in continuous flow acidogenic reactors with molasses used as substrate to study the effects of pH and redox potential on fermentation types. The conditions for each fermentation type w...The experiments were carried out in continuous flow acidogenic reactors with molasses used as substrate to study the effects of pH and redox potential on fermentation types. The conditions for each fermentation type were investigated at different experimental stages of start up, pH regulating and redox potential regulating. The experiments confirmed that butyric acid type fermentation would occur at pH > 6, the propionic acid type fermentation at pH about 5.5 with E h> -278 mV, and the ethanol type fermentation at pH < 4.5. A higher redox potential will lead to propionic acid type fermentation because propionogens are facultative anaerobic bacteria.展开更多
The relation between EH [Se(VI)/Se(IV)] and pH of soil aqueous extract in Kaschin-Beck disease region and the effects of natural redox agents, namely humic substances, MnO2 and Fe2+, on the redox property of the syste...The relation between EH [Se(VI)/Se(IV)] and pH of soil aqueous extract in Kaschin-Beck disease region and the effects of natural redox agents, namely humic substances, MnO2 and Fe2+, on the redox property of the system were studied. The results indicated that both humic acid and Fe2+ could enhance the reducibility of Se(VI) and MnO2, a limited oxidizability for Se(IV). Fe2+ showed a weak reducibility only at low pH value. The reducibilities of three sulfur-containing compounds for Se(VI) were in following order:thioglycollic acid > L-cysteine > sulfide展开更多
By using 1-methyl-2-formyl-5-substituted pyrroles (1-Y), 1-methyl-2-formyl-5-substituted pyrrole phenylhydrazones (2-Y) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl)-hydrazones (3-Y) as model structures ...By using 1-methyl-2-formyl-5-substituted pyrroles (1-Y), 1-methyl-2-formyl-5-substituted pyrrole phenylhydrazones (2-Y) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl)-hydrazones (3-Y) as model structures for nitrogen-containing heterocyclic aromatic compounds, correlation analysis of their redox potential data show that the transition states (TS) of the polarographic process are mainly affected by the polar effects, but spin-delocalizatin effects also exist.展开更多
In this greenhouse experiment, we investigated the effects of two constant groundwater levels: 10 cm groundwater level (GW-10) and 40 cm groundwater level (GW-40) and one change groundwater level, which was 40-10-40 c...In this greenhouse experiment, we investigated the effects of two constant groundwater levels: 10 cm groundwater level (GW-10) and 40 cm groundwater level (GW-40) and one change groundwater level, which was 40-10-40 cm (GW-40-10-40) on Cadmium (Cd) uptake and seed yield of Soybean plant in Cd contaminated soils (1.57 mg·kg-1). The experimental soil layer was made with gravel layer (14 cm), non-polluted soil (15 cm) and polluted soil (25 cm). The redox potential of every soil layer was measured from sowing to harvesting. The soil layer (10 – 40 cm) of GW-10 was always in reduction condition and that of GW-40 was always in oxidation condition. First 50 days of GW 40-10-40 were in oxidation and next 50 days in reduction and final 20 days again returned in oxidation condition. Soybean seed Cd concentration was significantly highest in GW-40-10-40 (1.16 ± 0.13 mg·kg-1) and lowest in GW-40 (0.81 ± 0.12 mg·kg-1). Cd concentration of stem was found significantly higher in GW-40 (1.7 ± 0.2 mg·kg-1) than GW-10 (0.91 ± 0.08 mg·kg-1) and GW-40-10-40 (1.28 ± 0.13 mg·kg-1). There was no significant difference in root Cd concentration among these 3 treatments. Main stem height of soybean plant and 100 seed weight of GW-40 were significantly higher than those of GW-10. The result revealed that, soil redox condition is an important factor for Cd uptake in soybean plant and seed yield of soybean. This study will help to manage the farming process more appropriately with the aim of minimizing uptake of Cd and other toxic metals in grain crops.展开更多
The ruminal redox potential (Eh) can reflect the microbiological activity and dynamics of fermentation in the rumen. It might be an important indicator of rumen fermentation in combination with pH. However, the rumina...The ruminal redox potential (Eh) can reflect the microbiological activity and dynamics of fermentation in the rumen. It might be an important indicator of rumen fermentation in combination with pH. However, the ruminal Eh has been rarely studied in dairy cows due to the difficulty of its measurement, and the relationship between ruminal Eh and pH is not clear. The objective of this study was to investigate the relationship between ruminal Eh and pH of dairy cows by meta-analysis of systematic measurements from different experiments. A database was constructed from 22 experiments on cannulated dairy cattle including 57 dietary treatments. The ruminal pH and Eh were measured without air contact between 0 and 8 h post-feeding. The results demonstrated a quadratic correlation between ruminal Eh and pH with a reliable within-animal variation (Eh = -1697 + 540.7 pH -47.7 pH2, nobservation = 70, nanimal = 26, P Eh, but not always to the same extent. Some of them still influenced the relationship between ruminal Eh and pH. While the mechanism of the interaction between ruminal Eh and pH remains to be elucidated, it would be interesting to associate Eh to microbial profile, ruminal VFA concentration and milk production performance in future studies.展开更多
Soil redox potential(Eh)plays an important role in the biogeochemical cycling of soil nutrients.Whereas its effect soil process and nutrients'availability under elevated atmospheric CO_(2) concentration and warmin...Soil redox potential(Eh)plays an important role in the biogeochemical cycling of soil nutrients.Whereas its effect soil process and nutrients'availability under elevated atmospheric CO_(2) concentration and warming has seldom been investigated.Thus,in this study,a field experiment was used to elucidate the effect of elevated CO_(2) concentration and warming on soil Eh,redox-sensitive elements and root radial oxygen loss(ROL).We hypothesized elevated CO_(2) and warming could alter soil Eh by promoting or inhibiting ROL.We found that soil Eh in the rhizosphere was significantly higher than that of non-rhizosphere.Elevated CO_(2) enhanced soil Eh by 11.5%,which corresponded to a significant decrease in soil Fe^(2+)and Mn^(2+)concentration.Under elevated CO_(2),the concentration of Fe^(2+)and Mn^(2+)decreased by 14.7%and 13.7%,respectively.We also found that elevated CO_(2) altered rice root aerenchyma structure and promoted rice root ROL.Under elevated CO_(2),rice root ROL increased by 79.5%and 112.2%for Yangdao 6 and Changyou 5,respectively.Warming had no effect on soil Eh and rice root ROL.While warming increased the concentration of Mn^(2+)and SO_(4)^(2-)by 4.9%and 19.3%,respectively.There was a significant interaction between elevated CO_(2) and warming on Fe^(2+)and Mn^(2+).Under elevated CO_(2),warming had no effect on the concentration of Fe^(2+)but decreased Mn^(2+)concentration significantly.Our study demonstrated that elevated atmospheric CO_(2) in the future could increase soil Eh by promoting rice root ROL,which will alter some soil nutrients'availability,such as Fe^(2+)and Mn^(2+).展开更多
Benefitting from the tunable heterogeneous interface and electronic interaction, metal-polymer-based hybrid composites have attracted wide attention. It is highly desired to develop advanced synthesis methodology and ...Benefitting from the tunable heterogeneous interface and electronic interaction, metal-polymer-based hybrid composites have attracted wide attention. It is highly desired to develop advanced synthesis methodology and understand the structure-performance relationship. Herein, with the aniline oligomer as the key enabler, we resolve the inferior dynamics issue in the Ag+-aniline reaction system, and successfully fabricate a sub-micron anisotropic eccentric Ag@polyaniline(PANI) particle(an average size up to 340 nm) at room temperature. We demonstrate the synergy mechanism of polyvinyl pyrrolidone and insitu generated PANI for modifying the dynamic reaction interface. We further clarify the H+concentration and the surfactant types serve as main descriptors to tune the reaction dynamics. Besides, by applying other aniline oligomers, a series of similar eccentric structures can also be obtained, indicative of the good applicability of our strategy. Such a sub-micron eccentric structure furnishes the Ag@PANI composites with sound performance for microwave absorption, as demonstrated by a minimum reflection loss(RL) value of-35 d B with an effective absorption bandwidth of 3.7 GHz. This study provides an inspiring scope/concept of eccentric microstructure engineering for better meeting the demands in the high-tech military, energy, environment fields, and beyond.展开更多
Aqueous organic redoxflow batteries(AORFBs)have pioneered new routes for large-scale energy storage.The tunable nature of redox-active organic molecules provides a robust foundation for creating innovative AORFBs with ...Aqueous organic redoxflow batteries(AORFBs)have pioneered new routes for large-scale energy storage.The tunable nature of redox-active organic molecules provides a robust foundation for creating innovative AORFBs with exceptional performance.Molecular engineering endows various organic molecules with considerable advantages in solubility,stability,and redox potential.Advanced characterizations have enabled a comprehensive understanding of the redox reaction and degradation mechanisms of these organic molecules.Computational chemistry and machine learning have guided the development of new organic molecules.The practical application of AORFBs will depend on the complementary efforts of multiple parties.This paper consolidates the current design principles of molecular engineering,degradation mechanisms,characterization techniques,and the utilization of computational chemistry.It also offers perspectives and forecasts the necessary attributes and strategic efforts for the next-generation AORFBs,aiming to provide the research community with a deeper understanding.展开更多
Bacterial small laccases(SLAC) are promising industrial biocatalysts due to their ability to oxidize a broad range of substrates with exceptional thermostability and tolerance for alkaline p H. Electron transfer betwe...Bacterial small laccases(SLAC) are promising industrial biocatalysts due to their ability to oxidize a broad range of substrates with exceptional thermostability and tolerance for alkaline p H. Electron transfer between substrate, copper centers, and O2is one of the key steps in the catalytic turnover of SLAC. However, limited research has been conducted on the electron transfer pathway of SLAC and SLAC-catalyzed reactions, hindering further engineering of SLAC to produce tunable biocatalysts for novel applications. Herein, the combinational use of electron paramagnetic resonance(EPR) and ultraviolet-visible(UV-vis) spectroscopic methods coupled with redox titration were employed to monitor the electron transfer processes and obtain further insights into the electron transfer pathway in SLAC. The reduction potentials for type 1 copper(T1Cu), type 2 copper(T2Cu) and type 3copper(T3Cu) were determined to be 367 ± 2 mV, 378 ± 5 m V and 403 ± 2 mV,respectively. Moreover, the reduction potential of a selected substrate of SLAC, hydroquinone(HQ), was determined to be 288 mV using cyclic voltammetry(CV). In this way, an electron transfer pathway was identified based on the reduction potentials. Specifically,electrons are transferred from HQ to T1Cu, then to T2Cu and T3Cu, and finally to O2.Furthermore, superhyperfine splitting observed via EPR during redox titration indicated a modification in the covalency of T2Cu upon electron uptake, suggesting a conformational alteration in the protein environment surrounding the copper sites, which could potentially influence the reduction potential of the copper sites during catalytic processes. The results presented here not only provide a comprehensive method for analyzing the electron transfer pathway in metalloenzymes through reduction potential measurements, but also offer valuable insights for further engineering and directed evolution studies of SLAC in the aim for biotechnological and industrial applications.展开更多
Based on the bioleaching mechanism and electrochemical studies of metal sulfides, the dissolution rates of chalcocite and pyrite are controlled by redox potentials. Experiment on the bioleaching of chalcocite and pyri...Based on the bioleaching mechanism and electrochemical studies of metal sulfides, the dissolution rates of chalcocite and pyrite are controlled by redox potentials. Experiment on the bioleaching of chalcocite and pyrite under constant redox potential by sparging with nitrogen gas was demonstrated. By leaching at low and constant redox potential(〈760 mV, vs SHE), copper recoveries of 90 %–98 % are achieved, which are 10 times more than iron recoveries. The iron-oxidizing bacterial populations are observed to continue to reduce under oxygen limitation conditions, but the Acidithiobacillus that have only sulfur-oxidizing capabilities are an attractive alternative for redox-controlled bioleaching of chalcocite.Thus, the described redox control technique might be one of the effective approaches to balance acid and iron in Zijinshan copper bio-heap leaching practice.展开更多
Comparisons on the bioleaching and sterile oxidation of pyrite were performed at controlled redox potential of 900 mV(vs.SHE) and different temperatures of 30 and 60℃.For sterile experiments,the redox potential of ir...Comparisons on the bioleaching and sterile oxidation of pyrite were performed at controlled redox potential of 900 mV(vs.SHE) and different temperatures of 30 and 60℃.For sterile experiments,the redox potential of irrigation solution was controlled by adding hydrogen peroxide solution(15 wt%),while the redox potential of irrigation solution for bioleaching was elevated by flowing through the packed bed in which bacteria were activated and colonized.The rate of pyrite bioleaching is faster than that of sterile oxidation at temperature of 30℃.The reason is that the potential gradient of leaching solution in bioleaching column is much smaller than that in sterile column.The redox potentials of irrigation solution and leaching solution are similar for bioleaching;however,the redox potential difference of irrigation solution and leaching solution for sterile oxidation is about 150 mV.When temperature increases to 60℃ for sterile oxidation,the rate of pyrite leaching is faster than that of bioleaching at temperature of 30℃,even though the redox potential gradient of leaching solution is great.The mineralogy analyses of pyrite residue were performed by scanning electron microscopy-energy-dispersive spectroscopy(SEM-EDS),X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) analyses.The results confirm that pyrite oxidation might only occur at specific sites with high surface energy on surface and obeys the "indirect mechanism" whether there are bacteria or not.The pyrite oxidation rate is not inhibited by inert sulfur on residue surface at elevated redox potential.According to the conclusions,the way to accelerate pyrite oxidation is proposed.展开更多
Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is ...Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is thought to be involved in many recently tested catalytic trifluoromethylation reactions. To provide helpful physical chemical data for mechanistic studies on trifluoromethylation reactions, the redox potentials of a variety of trifluoromethyl-containing compounds and trifluoro- methylated radicals were studied by quantum-chemical methods. First, eoB97X-D was found to be a reliable method in predicting the ionization potentials, electron affinities, bond dissociation enthalpies and redox potentials of trifluoromethylcontaining compounds. One-electron absolute redox potentials of 79 trifluoromethyl substrates and 107 trifluoromethylated radicals in acetonitrile were then calculated with this method. The theoretical results were found to be helpful for interpreting experimental observations such as the relative reaction efficiency of different trifluoromethylation reagents. Finally, the bond dissociation free energies (BDFE) of various compounds were found to have a good linear relationship with the related bond dissociation enthalpies (BDE). Based on this observation, a convenient method was proposed to predict one-electron redox potentials of neutral molecules.展开更多
Understanding the role of microbes in the solubility of cadmium(Cd) is of fundamental importance for remediation of Cd toxicity. The present study aimed to identify the microbes that involved in regulating Cd solubili...Understanding the role of microbes in the solubility of cadmium(Cd) is of fundamental importance for remediation of Cd toxicity. The present study aimed to identify the microbes that involved in regulating Cd solubility and to reveal possible mechanisms. Therefore,microbial communities were investigated through high-throughput sequencing approach, the molecular ecological network was constructed and metagenomes were predicted. Our results indicated that redox conditions affected both the solubility of soil Cd and the microbial communities. Anaerobic microbes, such as Anaerolineaceae, did not only play important roles in shaping the microbial community in soils, but might also be involved in regulating the Cd solubility. Two possible mechanisms that how Anaerolineaceae involved in Cd solubility are(1) Anaerolineaceae are important organic matter degraders under anoxic conditions and(2) Anaerolineaceae can co-exist with methane metabolism microbes, while methane metabolism promotes the precipitation of soluble Cd. Thus, application of Anaerolineaceae in bioremediation of soil Cadmium contamination is a potential approach. The study provided a novel insight into the role of microbial community in the regulation of Cd solubility under different redox conditions, and suggested a potential approach for the remediation of soil Cd contamination.展开更多
In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a q...In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a quantum yield of 0.67,much higher than that of systems with other metal complexes of rnesoporphyrin dimethyl ester.Neither EDTA nor MV^(2+) quenches the stationary fluorescence of SnP,implying that the reaction does not take place at the singlet state.With flash photolysis we obtain the T-T absorption spectrum of SnP(λ_(max)-440 nm).By following the decay of this absorption,the triplet life time of SnP is estimated to be 41 μs.The life time is related to the concentration of either MV^(2+) or EDTA.Good linear relationships are obtained by plotting τ_0/τ vs.the concentration of MV^(2+) or EDTA(Stern-Volmer plot),from which we determine the quenching constants:k_q(MV^(2+))=5.5×10~7 mol^(-7) s^(-1);kq(EDTA)=2.7×10~7 mol^(-1),s^(-1).The data suggests that upon photolysis of the above ternary system,both oxidative quenching and reductive quenching of the triplet state of the sensitizer are occurring.From the measured phosphorescence spectrum(λ_(max) 704nm)and the ground state redox potentials (E_(1/2)^(red)~-0.84V,E_(1/2)^(ox)~ Ag/AgCl,KCl(sat.)),we obtain the redox potential of triplet SnP to be E (P^+/P)~-0.33 V, E(P/P-)~+0.92 V.Matching this data with the redox potential of MV^(2+) and EDTA,we establish the fact that during the photolysis of the SnP/MV^(2+)/EDTA ternary system,both oxidative and reductive quenching are thermodynamically favorable processes.This is also the reason why the SnP sensitized reaction is much more efficient relative to other mesoporphyrin derivatives.展开更多
Background: The redox status of intra-uterine growth retardation(IUGR) piglets post-weaning has been poorly studied.Methods: Newborns from twenty-four sows were weighted, weaned at 21 d and fed a starter diet unti...Background: The redox status of intra-uterine growth retardation(IUGR) piglets post-weaning has been poorly studied.Methods: Newborns from twenty-four sows were weighted, weaned at 21 d and fed a starter diet until sampling.Sampling was done at 14 d post-weaning. A piglet was defined as IUGR when its birth weight was 2 SD below the mean birth weight of the total population. At weaning, eighteen piglets with nearly equal body weight from each category(i.e. IUGR or normal birth weight(NBW) piglets) were selected and then allocated to two treatments,consisted of six replicates with each pen having three piglets.Results: Compared with NBW group, IUGR significantly decreased average daily gain(P 〈 0.001), average daily feed intake(P = 0.003), and feed efficiency(P 〈 0.001) of piglets during the first two weeks post-weaning. IUGR decreased the activities of total antioxidant capacity(P = 0.019), total superoxide dismutase(T-SOD, P = 0.023),and ceruloplasmin(P = 0.044) but increased the levels of malondialdehyde(P = 0.040) and protein carbonyl(P = 0.010) in plasma. Similarly, the decreased activities of T-SOD(P = 0.005), copper- and zinc-containing superoxide dismutase(Cu/Zn-SOD, P = 0.002), and catalase(P = 0.049) was observed in the liver of IUGR piglets than these of NBW piglets. IUGR decreased hepatic Cu/Zn-SOD activity(P = 0.023) per unit of Cu/Zn-SOD protein in piglets when compared with NBW piglets. In addition, IUGR piglets exhibited the decreases in accumulation of copper in both plasma(P = 0.001) and liver(P = 0.014), as well as the concentrations of iron(P = 0.002) and zinc(P = 0.048) in liver. Compared with NBW, IUGR down-regulated m RNA expression of Cu/Zn-SOD(P = 0.021) in the liver of piglets.Conclusions: The results indicated that IUGR impaired antioxidant capacity and resulted in oxidative damage in fully weaned piglets, which might be associated with the decreased levels of redox-active trace minerals. This study highlights the importance of redox status in IUGR offspring and provides a rationale for alleviating oxidative damage by dietary interventions aiming to supplement trace minerals and to restore redox balance in the future.展开更多
In this study,photovoltage technique is applied in the development of a monolithically integrated sensor for redox(reduction–oxidation)potential and pH measurement.The sensor employs the electrolyte–insulator–semic...In this study,photovoltage technique is applied in the development of a monolithically integrated sensor for redox(reduction–oxidation)potential and pH measurement.The sensor employs the electrolyte–insulator–semiconductor structure,with deposition of a layer of gold metal on partial surface of insulator silicon dioxide.Silicon dioxide and gold layer on a single chip form two distinct sensing sites,by sharing the same measuring system,the detection of redox potential and pH variation can be realized.In this work,the sensor characteristics is tested,and the sensitivity for redox potential and pH measurement is53.8 mV/log([Fe(II)]/[Fe(III)])and 44.3 mV/pH respectively.To demonstrate the validity of the sensor in extracellular detection,neonatal rat kidney cells are cultured on the sensor surface and then packaged in a flow chamber,thus the acidification rate of metabolites and the redox potential variation in extracellular microenvironment can be continuously monitored.Experimental results indicate increasing acidification and reducing potentials under physiological conditions.The synthesis parameters have potentials in detail revelation of cell metabolism.展开更多
基金supported by the National Natural Science Foundation of China(Nos:51503038 and 51873037).
文摘The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.
基金the National Natural Science Foundation of China (22209091)the Natural Science Foundation of Shandong Province (ZR2020QB057)+1 种基金the Key Program of National Natural Science Foundation of China (22133006)the Yankuang Group 2019 Science and Technology Program (YKKJ2019AJ05JG-R60)。
文摘It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced into the lattice of hexagonal ZnIn_(2)S_(4) nanosheets(Ni/ZnIn_(2)S_(4))via directionalsubstituting Zn atom with the facile hydrothermal method.The electronic structure calculations indicate that the introduction of Ni atom effectively extracts more electrons and acts as active site for subsequent reduction reaction.Besides the optimized light absorption range,the elevation of Efand ECBendows Ni/ZnIn_(2)S_(4) photocatalyst with the increased electron concentration and the enhanced reduction ability for surface reaction.Moreover,ultrafast transient absorption spectroscopy,as well as a series of electrochemical tests,demonstrates that Ni/ZnIn_(2)S_(4) possesses 2.15 times longer lifetime of the excited charge carriers and an order of magnitude increase for carrier mobility and separation efficiency compared with pristine ZnIn_(2)S_(4).These efficient kinetics performances of charge carriers and enhanced redox capacity synergistically boost photocatalytic activity,in which a 3-times higher conversion efficiency of nitrobenzene reduction was achieved upon Ni/ZnIn_(2)S_(4).Our study not only provides in-depth insights into the effect of atomic directional-substitution on the kinetic behavior of photogenerated charges,but also opens an avenue to the synchronous optimization of redox capacity and carrier-kinetics performance for efficient solar energy conversion.
基金Project(2010CB630904) supported by the National Basic Research Program of ChinaProject(50621063) supported by the Chinese Science Foundation for Distinguished Group
文摘The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2+ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe(III) to Fe(II) in the solutions containing synthetic extracellular polymeric substances (EPS).When the solution potential is lower than 650 mV (vs SHE),the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe(III) ions is up to 20 g/L but increases with increasing the concentration of Fe(III) ions;jarosites formed by bio-oxidized Fe3+ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2+ ions inside and outside EPS space into Fe^3+ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.
基金Project supported by the National Natural Science Foundation of China(No.40401029).
文摘The sediment redox potential was raised in the laboratory to estimate reduction of internal available phosphorus loads,such as soluble reactive phosphorus(SRP)and total phosphorus(TP),as well as the main elements of sediment extracts in Dianchi Lake.Several strongly reducing substances in sediments,which mainly originated from anaerobic decomposition of primary producer residues,were responsible for the lower redox potential.In a range of -400 to 200 mV raising the redox potential of sediments decreased TP and SRP in interstitial water.Redox potentials exceeding 320 mV caused increases in TP,whereas SRP maintained a relatively constant minimum level.The concentrations of Al,Fe, Ca^(2+),Mg^(2+),K^+,Na^+ and S in interstitial water were also related to the redox potential of sediments,suggesting that the mechanism for redox potential to regulate the concentration of phosphorus in interstitial water was complex.
文摘The experiments were carried out in continuous flow acidogenic reactors with molasses used as substrate to study the effects of pH and redox potential on fermentation types. The conditions for each fermentation type were investigated at different experimental stages of start up, pH regulating and redox potential regulating. The experiments confirmed that butyric acid type fermentation would occur at pH > 6, the propionic acid type fermentation at pH about 5.5 with E h> -278 mV, and the ethanol type fermentation at pH < 4.5. A higher redox potential will lead to propionic acid type fermentation because propionogens are facultative anaerobic bacteria.
文摘The relation between EH [Se(VI)/Se(IV)] and pH of soil aqueous extract in Kaschin-Beck disease region and the effects of natural redox agents, namely humic substances, MnO2 and Fe2+, on the redox property of the system were studied. The results indicated that both humic acid and Fe2+ could enhance the reducibility of Se(VI) and MnO2, a limited oxidizability for Se(IV). Fe2+ showed a weak reducibility only at low pH value. The reducibilities of three sulfur-containing compounds for Se(VI) were in following order:thioglycollic acid > L-cysteine > sulfide
基金the National Natural Science Foundation of China and the China Postdoctoral Science Foundation for financial support.
文摘By using 1-methyl-2-formyl-5-substituted pyrroles (1-Y), 1-methyl-2-formyl-5-substituted pyrrole phenylhydrazones (2-Y) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl)-hydrazones (3-Y) as model structures for nitrogen-containing heterocyclic aromatic compounds, correlation analysis of their redox potential data show that the transition states (TS) of the polarographic process are mainly affected by the polar effects, but spin-delocalizatin effects also exist.
文摘In this greenhouse experiment, we investigated the effects of two constant groundwater levels: 10 cm groundwater level (GW-10) and 40 cm groundwater level (GW-40) and one change groundwater level, which was 40-10-40 cm (GW-40-10-40) on Cadmium (Cd) uptake and seed yield of Soybean plant in Cd contaminated soils (1.57 mg·kg-1). The experimental soil layer was made with gravel layer (14 cm), non-polluted soil (15 cm) and polluted soil (25 cm). The redox potential of every soil layer was measured from sowing to harvesting. The soil layer (10 – 40 cm) of GW-10 was always in reduction condition and that of GW-40 was always in oxidation condition. First 50 days of GW 40-10-40 were in oxidation and next 50 days in reduction and final 20 days again returned in oxidation condition. Soybean seed Cd concentration was significantly highest in GW-40-10-40 (1.16 ± 0.13 mg·kg-1) and lowest in GW-40 (0.81 ± 0.12 mg·kg-1). Cd concentration of stem was found significantly higher in GW-40 (1.7 ± 0.2 mg·kg-1) than GW-10 (0.91 ± 0.08 mg·kg-1) and GW-40-10-40 (1.28 ± 0.13 mg·kg-1). There was no significant difference in root Cd concentration among these 3 treatments. Main stem height of soybean plant and 100 seed weight of GW-40 were significantly higher than those of GW-10. The result revealed that, soil redox condition is an important factor for Cd uptake in soybean plant and seed yield of soybean. This study will help to manage the farming process more appropriately with the aim of minimizing uptake of Cd and other toxic metals in grain crops.
文摘The ruminal redox potential (Eh) can reflect the microbiological activity and dynamics of fermentation in the rumen. It might be an important indicator of rumen fermentation in combination with pH. However, the ruminal Eh has been rarely studied in dairy cows due to the difficulty of its measurement, and the relationship between ruminal Eh and pH is not clear. The objective of this study was to investigate the relationship between ruminal Eh and pH of dairy cows by meta-analysis of systematic measurements from different experiments. A database was constructed from 22 experiments on cannulated dairy cattle including 57 dietary treatments. The ruminal pH and Eh were measured without air contact between 0 and 8 h post-feeding. The results demonstrated a quadratic correlation between ruminal Eh and pH with a reliable within-animal variation (Eh = -1697 + 540.7 pH -47.7 pH2, nobservation = 70, nanimal = 26, P Eh, but not always to the same extent. Some of them still influenced the relationship between ruminal Eh and pH. While the mechanism of the interaction between ruminal Eh and pH remains to be elucidated, it would be interesting to associate Eh to microbial profile, ruminal VFA concentration and milk production performance in future studies.
基金supported by the National Natural Science Foundation of China (No.42277328)the Sino-German Mobility Program (No.M-0105)。
文摘Soil redox potential(Eh)plays an important role in the biogeochemical cycling of soil nutrients.Whereas its effect soil process and nutrients'availability under elevated atmospheric CO_(2) concentration and warming has seldom been investigated.Thus,in this study,a field experiment was used to elucidate the effect of elevated CO_(2) concentration and warming on soil Eh,redox-sensitive elements and root radial oxygen loss(ROL).We hypothesized elevated CO_(2) and warming could alter soil Eh by promoting or inhibiting ROL.We found that soil Eh in the rhizosphere was significantly higher than that of non-rhizosphere.Elevated CO_(2) enhanced soil Eh by 11.5%,which corresponded to a significant decrease in soil Fe^(2+)and Mn^(2+)concentration.Under elevated CO_(2),the concentration of Fe^(2+)and Mn^(2+)decreased by 14.7%and 13.7%,respectively.We also found that elevated CO_(2) altered rice root aerenchyma structure and promoted rice root ROL.Under elevated CO_(2),rice root ROL increased by 79.5%and 112.2%for Yangdao 6 and Changyou 5,respectively.Warming had no effect on soil Eh and rice root ROL.While warming increased the concentration of Mn^(2+)and SO_(4)^(2-)by 4.9%and 19.3%,respectively.There was a significant interaction between elevated CO_(2) and warming on Fe^(2+)and Mn^(2+).Under elevated CO_(2),warming had no effect on the concentration of Fe^(2+)but decreased Mn^(2+)concentration significantly.Our study demonstrated that elevated atmospheric CO_(2) in the future could increase soil Eh by promoting rice root ROL,which will alter some soil nutrients'availability,such as Fe^(2+)and Mn^(2+).
基金the support and funding from the National Natural Science Foundation of China(Nos.51673156,52202301)the Natural Science Basic Research Plan in Shaanxi Province of China(No.2022JQ-143)+1 种基金China Postdoctoral Science Foundation(No.2022TQ0256)the Fundamental Research Funds for the Central Universities(No.D5000210607)。
文摘Benefitting from the tunable heterogeneous interface and electronic interaction, metal-polymer-based hybrid composites have attracted wide attention. It is highly desired to develop advanced synthesis methodology and understand the structure-performance relationship. Herein, with the aniline oligomer as the key enabler, we resolve the inferior dynamics issue in the Ag+-aniline reaction system, and successfully fabricate a sub-micron anisotropic eccentric Ag@polyaniline(PANI) particle(an average size up to 340 nm) at room temperature. We demonstrate the synergy mechanism of polyvinyl pyrrolidone and insitu generated PANI for modifying the dynamic reaction interface. We further clarify the H+concentration and the surfactant types serve as main descriptors to tune the reaction dynamics. Besides, by applying other aniline oligomers, a series of similar eccentric structures can also be obtained, indicative of the good applicability of our strategy. Such a sub-micron eccentric structure furnishes the Ag@PANI composites with sound performance for microwave absorption, as demonstrated by a minimum reflection loss(RL) value of-35 d B with an effective absorption bandwidth of 3.7 GHz. This study provides an inspiring scope/concept of eccentric microstructure engineering for better meeting the demands in the high-tech military, energy, environment fields, and beyond.
基金supported by the National Natural Science Foundation of China(Grant Nos.U2004214and 22350710185).
文摘Aqueous organic redoxflow batteries(AORFBs)have pioneered new routes for large-scale energy storage.The tunable nature of redox-active organic molecules provides a robust foundation for creating innovative AORFBs with exceptional performance.Molecular engineering endows various organic molecules with considerable advantages in solubility,stability,and redox potential.Advanced characterizations have enabled a comprehensive understanding of the redox reaction and degradation mechanisms of these organic molecules.Computational chemistry and machine learning have guided the development of new organic molecules.The practical application of AORFBs will depend on the complementary efforts of multiple parties.This paper consolidates the current design principles of molecular engineering,degradation mechanisms,characterization techniques,and the utilization of computational chemistry.It also offers perspectives and forecasts the necessary attributes and strategic efforts for the next-generation AORFBs,aiming to provide the research community with a deeper understanding.
基金supported by the National Natural Science Foundation of China (21825703, 21927814)the National Key R&D Program of China (2019YFA0405600, 2019YFA0706900, 2021YFA1200104, 2022YFC3400500)+3 种基金the Strategic Priority Research Program of Chinese Academy of Sciences (XDB0540200, XDB37040201)Plans for Major Provincial Science&Technology Projects (202303a07020004)Basic Research Program Based on Major Scientific Infrastructures,CAS (JZHKYPT-2021-05)the Youth Innovation Promotion Association,CAS (2022455)
文摘Bacterial small laccases(SLAC) are promising industrial biocatalysts due to their ability to oxidize a broad range of substrates with exceptional thermostability and tolerance for alkaline p H. Electron transfer between substrate, copper centers, and O2is one of the key steps in the catalytic turnover of SLAC. However, limited research has been conducted on the electron transfer pathway of SLAC and SLAC-catalyzed reactions, hindering further engineering of SLAC to produce tunable biocatalysts for novel applications. Herein, the combinational use of electron paramagnetic resonance(EPR) and ultraviolet-visible(UV-vis) spectroscopic methods coupled with redox titration were employed to monitor the electron transfer processes and obtain further insights into the electron transfer pathway in SLAC. The reduction potentials for type 1 copper(T1Cu), type 2 copper(T2Cu) and type 3copper(T3Cu) were determined to be 367 ± 2 mV, 378 ± 5 m V and 403 ± 2 mV,respectively. Moreover, the reduction potential of a selected substrate of SLAC, hydroquinone(HQ), was determined to be 288 mV using cyclic voltammetry(CV). In this way, an electron transfer pathway was identified based on the reduction potentials. Specifically,electrons are transferred from HQ to T1Cu, then to T2Cu and T3Cu, and finally to O2.Furthermore, superhyperfine splitting observed via EPR during redox titration indicated a modification in the covalency of T2Cu upon electron uptake, suggesting a conformational alteration in the protein environment surrounding the copper sites, which could potentially influence the reduction potential of the copper sites during catalytic processes. The results presented here not only provide a comprehensive method for analyzing the electron transfer pathway in metalloenzymes through reduction potential measurements, but also offer valuable insights for further engineering and directed evolution studies of SLAC in the aim for biotechnological and industrial applications.
基金financially supported by the National Natural Science Foundation of China (No.50934002)the National Basic Research Program of China (No.2010CB630905)the National High Technology Research and Development Program of China (No.2012AA060502)
文摘Based on the bioleaching mechanism and electrochemical studies of metal sulfides, the dissolution rates of chalcocite and pyrite are controlled by redox potentials. Experiment on the bioleaching of chalcocite and pyrite under constant redox potential by sparging with nitrogen gas was demonstrated. By leaching at low and constant redox potential(〈760 mV, vs SHE), copper recoveries of 90 %–98 % are achieved, which are 10 times more than iron recoveries. The iron-oxidizing bacterial populations are observed to continue to reduce under oxygen limitation conditions, but the Acidithiobacillus that have only sulfur-oxidizing capabilities are an attractive alternative for redox-controlled bioleaching of chalcocite.Thus, the described redox control technique might be one of the effective approaches to balance acid and iron in Zijinshan copper bio-heap leaching practice.
基金financially supported by the Research Fund for Program of Efficient Gold Extraction from Refractory Gold Ore of Sichuan Province,China (No.12120113088100)the National Natural Science Foundation of China (Nos.41401541 and 51474075)the Bureau of International Co-operation,Chinese Academy of Sciences (No.122111KYSB20150013)
文摘Comparisons on the bioleaching and sterile oxidation of pyrite were performed at controlled redox potential of 900 mV(vs.SHE) and different temperatures of 30 and 60℃.For sterile experiments,the redox potential of irrigation solution was controlled by adding hydrogen peroxide solution(15 wt%),while the redox potential of irrigation solution for bioleaching was elevated by flowing through the packed bed in which bacteria were activated and colonized.The rate of pyrite bioleaching is faster than that of sterile oxidation at temperature of 30℃.The reason is that the potential gradient of leaching solution in bioleaching column is much smaller than that in sterile column.The redox potentials of irrigation solution and leaching solution are similar for bioleaching;however,the redox potential difference of irrigation solution and leaching solution for sterile oxidation is about 150 mV.When temperature increases to 60℃ for sterile oxidation,the rate of pyrite leaching is faster than that of bioleaching at temperature of 30℃,even though the redox potential gradient of leaching solution is great.The mineralogy analyses of pyrite residue were performed by scanning electron microscopy-energy-dispersive spectroscopy(SEM-EDS),X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) analyses.The results confirm that pyrite oxidation might only occur at specific sites with high surface energy on surface and obeys the "indirect mechanism" whether there are bacteria or not.The pyrite oxidation rate is not inhibited by inert sulfur on residue surface at elevated redox potential.According to the conclusions,the way to accelerate pyrite oxidation is proposed.
基金supported by the National Natural Science Foundation of China(21325208,21172209,21361140372,21202006)Specialized Research Fund for the Doctoral Program(20123402110051)+5 种基金Fundamental Research Funds for the Central Universities(WK2060190025)Chinese Academy of Sciences(KJCX2-EW-J02)Fok Ying Tung Education FoundationAnhui Provincial Natural Science Foundation(1308085QB38)China Grid project funded by Ministry of Education of Chinathe supercomputer center of Shanghai and University of Science and Technology of China
文摘Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is thought to be involved in many recently tested catalytic trifluoromethylation reactions. To provide helpful physical chemical data for mechanistic studies on trifluoromethylation reactions, the redox potentials of a variety of trifluoromethyl-containing compounds and trifluoro- methylated radicals were studied by quantum-chemical methods. First, eoB97X-D was found to be a reliable method in predicting the ionization potentials, electron affinities, bond dissociation enthalpies and redox potentials of trifluoromethylcontaining compounds. One-electron absolute redox potentials of 79 trifluoromethyl substrates and 107 trifluoromethylated radicals in acetonitrile were then calculated with this method. The theoretical results were found to be helpful for interpreting experimental observations such as the relative reaction efficiency of different trifluoromethylation reagents. Finally, the bond dissociation free energies (BDFE) of various compounds were found to have a good linear relationship with the related bond dissociation enthalpies (BDE). Based on this observation, a convenient method was proposed to predict one-electron redox potentials of neutral molecules.
基金supported by the National Natural Science Foundation of China (Nos.31570113 and 41573072)the Scientific Research Fund of Hunan Provincial Education Department in China (No.17 K035)+1 种基金Chinese Postdoctoral Funding Planthe Central South University Postdoctoral Research Funding for D.M.(No.201699)
文摘Understanding the role of microbes in the solubility of cadmium(Cd) is of fundamental importance for remediation of Cd toxicity. The present study aimed to identify the microbes that involved in regulating Cd solubility and to reveal possible mechanisms. Therefore,microbial communities were investigated through high-throughput sequencing approach, the molecular ecological network was constructed and metagenomes were predicted. Our results indicated that redox conditions affected both the solubility of soil Cd and the microbial communities. Anaerobic microbes, such as Anaerolineaceae, did not only play important roles in shaping the microbial community in soils, but might also be involved in regulating the Cd solubility. Two possible mechanisms that how Anaerolineaceae involved in Cd solubility are(1) Anaerolineaceae are important organic matter degraders under anoxic conditions and(2) Anaerolineaceae can co-exist with methane metabolism microbes, while methane metabolism promotes the precipitation of soluble Cd. Thus, application of Anaerolineaceae in bioremediation of soil Cadmium contamination is a potential approach. The study provided a novel insight into the role of microbial community in the regulation of Cd solubility under different redox conditions, and suggested a potential approach for the remediation of soil Cd contamination.
文摘In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a quantum yield of 0.67,much higher than that of systems with other metal complexes of rnesoporphyrin dimethyl ester.Neither EDTA nor MV^(2+) quenches the stationary fluorescence of SnP,implying that the reaction does not take place at the singlet state.With flash photolysis we obtain the T-T absorption spectrum of SnP(λ_(max)-440 nm).By following the decay of this absorption,the triplet life time of SnP is estimated to be 41 μs.The life time is related to the concentration of either MV^(2+) or EDTA.Good linear relationships are obtained by plotting τ_0/τ vs.the concentration of MV^(2+) or EDTA(Stern-Volmer plot),from which we determine the quenching constants:k_q(MV^(2+))=5.5×10~7 mol^(-7) s^(-1);kq(EDTA)=2.7×10~7 mol^(-1),s^(-1).The data suggests that upon photolysis of the above ternary system,both oxidative quenching and reductive quenching of the triplet state of the sensitizer are occurring.From the measured phosphorescence spectrum(λ_(max) 704nm)and the ground state redox potentials (E_(1/2)^(red)~-0.84V,E_(1/2)^(ox)~ Ag/AgCl,KCl(sat.)),we obtain the redox potential of triplet SnP to be E (P^+/P)~-0.33 V, E(P/P-)~+0.92 V.Matching this data with the redox potential of MV^(2+) and EDTA,we establish the fact that during the photolysis of the SnP/MV^(2+)/EDTA ternary system,both oxidative and reductive quenching are thermodynamically favorable processes.This is also the reason why the SnP sensitized reaction is much more efficient relative to other mesoporphyrin derivatives.
基金supported by the National Natural Science Foundation of China (31272454)
文摘Background: The redox status of intra-uterine growth retardation(IUGR) piglets post-weaning has been poorly studied.Methods: Newborns from twenty-four sows were weighted, weaned at 21 d and fed a starter diet until sampling.Sampling was done at 14 d post-weaning. A piglet was defined as IUGR when its birth weight was 2 SD below the mean birth weight of the total population. At weaning, eighteen piglets with nearly equal body weight from each category(i.e. IUGR or normal birth weight(NBW) piglets) were selected and then allocated to two treatments,consisted of six replicates with each pen having three piglets.Results: Compared with NBW group, IUGR significantly decreased average daily gain(P 〈 0.001), average daily feed intake(P = 0.003), and feed efficiency(P 〈 0.001) of piglets during the first two weeks post-weaning. IUGR decreased the activities of total antioxidant capacity(P = 0.019), total superoxide dismutase(T-SOD, P = 0.023),and ceruloplasmin(P = 0.044) but increased the levels of malondialdehyde(P = 0.040) and protein carbonyl(P = 0.010) in plasma. Similarly, the decreased activities of T-SOD(P = 0.005), copper- and zinc-containing superoxide dismutase(Cu/Zn-SOD, P = 0.002), and catalase(P = 0.049) was observed in the liver of IUGR piglets than these of NBW piglets. IUGR decreased hepatic Cu/Zn-SOD activity(P = 0.023) per unit of Cu/Zn-SOD protein in piglets when compared with NBW piglets. In addition, IUGR piglets exhibited the decreases in accumulation of copper in both plasma(P = 0.001) and liver(P = 0.014), as well as the concentrations of iron(P = 0.002) and zinc(P = 0.048) in liver. Compared with NBW, IUGR down-regulated m RNA expression of Cu/Zn-SOD(P = 0.021) in the liver of piglets.Conclusions: The results indicated that IUGR impaired antioxidant capacity and resulted in oxidative damage in fully weaned piglets, which might be associated with the decreased levels of redox-active trace minerals. This study highlights the importance of redox status in IUGR offspring and provides a rationale for alleviating oxidative damage by dietary interventions aiming to supplement trace minerals and to restore redox balance in the future.
基金supported by the National Nat-ural Science Foundation of China(81027003)the National Basic Research Program of China(2009CB320303)the National Public Welfare Project of China(201305010)
文摘In this study,photovoltage technique is applied in the development of a monolithically integrated sensor for redox(reduction–oxidation)potential and pH measurement.The sensor employs the electrolyte–insulator–semiconductor structure,with deposition of a layer of gold metal on partial surface of insulator silicon dioxide.Silicon dioxide and gold layer on a single chip form two distinct sensing sites,by sharing the same measuring system,the detection of redox potential and pH variation can be realized.In this work,the sensor characteristics is tested,and the sensitivity for redox potential and pH measurement is53.8 mV/log([Fe(II)]/[Fe(III)])and 44.3 mV/pH respectively.To demonstrate the validity of the sensor in extracellular detection,neonatal rat kidney cells are cultured on the sensor surface and then packaged in a flow chamber,thus the acidification rate of metabolites and the redox potential variation in extracellular microenvironment can be continuously monitored.Experimental results indicate increasing acidification and reducing potentials under physiological conditions.The synthesis parameters have potentials in detail revelation of cell metabolism.