Lead (Pb) inhibited the activities of Na+ -K+ ATPase (IC50= 2.0×10^(-6) M), K + -Para-Nitrophenyl phosphatase (PNPPase) (IC50= 3.5×10^(-6) M) and [3H]-ouabain binding (IC50 = 4.0×10^(-5) M) in rat brain...Lead (Pb) inhibited the activities of Na+ -K+ ATPase (IC50= 2.0×10^(-6) M), K + -Para-Nitrophenyl phosphatase (PNPPase) (IC50= 3.5×10^(-6) M) and [3H]-ouabain binding (IC50 = 4.0×10^(-5) M) in rat brain P2 fraction. A variable temperature or pH significantly elevated the inhibition of Na+-K+ ATPase by Pb in buffered acidic, neutral and alkaline pH ranges. Noncompetitive inhibition with respect to activation of Na+ -K+ ATPase by ATP was indicated by a variation in Vmax values with no significant changes in Km values at any temperature studied. In the presence of Pb, for Na+ -K+ ATPase at pH 6.5 and 8.5, Vmax was decreased with an increase in Km values suggesting a mixed type of inhibition. Sulfhydryl agents such as dithiothreitol (DTT) and cvsteine (Cyst), but not glutathione (GSH) offered varied levels of protection against Pb-inhibition of Na + -K+ ATPase at pH 7.5 and 8.5. The present data suggest that inhibition of Na+ -K+ ATPase by Pb is both temperature and pH-dependent. These results also indicate that Pb inhibited Na + -K + ATPase by interfering with phosphorylation of enzyme molecule and dephosphorylation of the enzyme-phosphoryl complex and exerted an effect similar to that of SH-blocking agents.展开更多
Bensulfuron-Methyl(BSM)is a highly active sul-fonylurea herbicide that effectively controls most an-nual and perennial broadleaf or sedge weeds in paddyfield.However,the activity of BSM is affected byseveral evironmen...Bensulfuron-Methyl(BSM)is a highly active sul-fonylurea herbicide that effectively controls most an-nual and perennial broadleaf or sedge weeds in paddyfield.However,the activity of BSM is affected byseveral evironmental factors.Using corn seedlings asmaterial,we found that under different temperatures展开更多
As a versatile and environmentally benign oxidant,hydrogen peroxide(H_(2)O_(2))is highly desired in sanitation,disinfection,environmental remediation,and the chemical industry.Compared with the conventional anthraquin...As a versatile and environmentally benign oxidant,hydrogen peroxide(H_(2)O_(2))is highly desired in sanitation,disinfection,environmental remediation,and the chemical industry.Compared with the conventional anthraquinone process,the electrosynthesis of H_(2)O_(2)through the two-electron oxygen reduction reaction(2e^(−)ORR)is an efficient,competitive,and promising avenue.Electrocatalysts and devices are two core factors in 2e^(−)ORR,but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear.To this end,this review adopts a multiscale perspective to summarize recent advancements in the design principles,catalytic mechanisms,and application prospects of 2e^(−)ORR catalysts,with a particular focus on the influence of pH conditions,aiming at providing guidance for the selective design of advanced 2e^(−)ORR catalysts for highly-efficient H_(2)O_(2)production.Moreover,in response to diverse on-site application demands,we elaborate on the evolution of H_(2)O_(2)electrosynthesis devices,from rotating ring-disk electrodes and H-type cells to diverse flow-type cells.We elaborate on their characteristics and shortcomings,which can be beneficial for their further upgrades and customized applications.These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.展开更多
The adsorption/desorption of OH*on electrode surfaces is pivotal in numerous electrocatalytic reactions.To understand the effect of electrolyte pH on that process,in this work,an advanced approach combining ab initio ...The adsorption/desorption of OH*on electrode surfaces is pivotal in numerous electrocatalytic reactions.To understand the effect of electrolyte pH on that process,in this work,an advanced approach combining ab initio molecular dynamics(AIMD)with free energy perturbation is employed to calculate the dehydrogenation free energy of water chemisorbed at differently electrified Pt(111)/electrolyte interfaces.Our findings reveal that the onset potential for OH*formation shifts negatively as the pH increases at low pH condition(pH<4.3),aligning with the cyclic voltammetry curves observed in experimental studies.It indicates the dissociation of chemisorbed water is the primary route for OH*adsorption at low pH condition.Furthermore,it is also found that the variation in dehydrogenation energy across different pH is primarily due to the local hydrogen bonding network surrounding the chemisorbed water.In addition,it is proposed that at high pH conditions OH-oxidation emerges as the primary route for OH*adsorption on Pt(111)constrained by the water chemisorption process.This work provides crucial insights into the pH-dependent adsorption behavior of OH*on the Pt(111)surface and aims to guide the optimization of electrolytes to boost the efficiency of related reactions.展开更多
Phosphoric acid/phosphate solu-tions are commonly used as buffer solutions in the fundamental stud-ies in electrochemistry.Informa-tion on the nature of adsorbed(bi)phosphate as well as the do-main structures is of gr...Phosphoric acid/phosphate solu-tions are commonly used as buffer solutions in the fundamental stud-ies in electrochemistry.Informa-tion on the nature of adsorbed(bi)phosphate as well as the do-main structures is of great impor-tance in unveiling the impact on electrochemical processes occur-ring at electrode electrolyte interface.In this work,the pH effect on the adsorption of phosphate related species on Pd(111)electrode has been investigated by cyclic voltammetry over a broad pH range from 1 to 14.Af-ter carefully analyzing the related onset desorption potential of(bi)phosphate adsorbate to the thermodynamic equilibrium potential of the corresponding electrode reactions,three dif-ferent phosphate related adsorbates have been identified,which are highly pH-dependent.Our analysis reveals that the dominant phosphate anions in bulk solution undergo deprotona-tion upon adsorption.At pH<1.5,the main adsorbate on Pd(111)is;H_(2)PO_(4)^(λ_(1)^(-))in solutions with 1.5<pH<7,the main adsorbate changes into.HPO_(4)^(λ_2^(-))At higher pHs,PO_(4)^(λ_(3)^(-))on electrode surface dominates.The exact charging value ofλ_(i),which represents the true va-lence of the(bi)phosphate adsorbate,could be determined using theoretical calculations.In addition,our results can not rule out the possibility of co-adsorbed H_(3)PO_(4)molecules on Pd(111)at pH<1.5,which needs to be proved by infrared spectroscopy in the future.展开更多
The Co-based catalysts were prepared with different cobalt acetate solutions.Effects of pH value were studied deeply on Fischer–Tropsch synthesis(FTS)through a semi-batch reactor.Among all impregnation solutions(wate...The Co-based catalysts were prepared with different cobalt acetate solutions.Effects of pH value were studied deeply on Fischer–Tropsch synthesis(FTS)through a semi-batch reactor.Among all impregnation solutions(water,butanol,amyl alcohol,acetic acid,nitric acid and ammonium nitrate),the catalyst prepared by NH4NO3solution showed the highest catalytic activity due to its small particle size and high reduction degree.However,the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS.According to FT-IR spectra results,the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity.Whereas,the high activity of catalysts prepared from NH4NO3solution could be explained by the high intensity of absorbed CO on the catalysts.The cobalt species on the catalysts prepared under lower pH conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher pH value.展开更多
The photo-catalytic degradation pathway and degradation products of methylene blue, rhodamine B, methyl orange, and malachite green in aqueous TiO2 suspension irradiated by high pressure mercury lamp by means of UV-vi...The photo-catalytic degradation pathway and degradation products of methylene blue, rhodamine B, methyl orange, and malachite green in aqueous TiO2 suspension irradiated by high pressure mercury lamp by means of UV-visible absorption spectra and ion chromatography were investigated. The photo-catalysis degradation of dye solutions with charges was greatly effected by pH value owing to the electrostatic model. The photo-degradation rate of dyes anion increased with the decrease of pH value, in contrast, the photo-degradation rate of dyes cation increased with the increase of pH value. And the absorption peaks diminished with a blue shift. After illuminated for 30 minutes, a part of dye chemicals were completely mineralized and transferred into inorganic species including chloride ion, ammonium ion, nitrate ion, sulfate ion. And the addition of 100 mmol/L H2O2 promoted the formation of inorganic species. In this study, the quantity of ammonium ion was much more than that of nitrate ion. That indicated the formation of nitrate is from ammonium. The purification rate of COD in four kinds of dye solution was 71.7%-88.7%. The decrease of COD of dyes solution implies the feasibility of the environmental application of photo-catalyzed process.展开更多
This study investigated the effects of pH on the transport of Pb 2＋ , Mn 2＋ , Zn 2＋ and Ni 2＋ through lateritic soil columns. Model results by fitting the symmetric breakthrough curves （BTCs） of bromide （Br ） ...This study investigated the effects of pH on the transport of Pb 2＋ , Mn 2＋ , Zn 2＋ and Ni 2＋ through lateritic soil columns. Model results by fitting the symmetric breakthrough curves （BTCs） of bromide （Br ） with CXTFIT model suggested that physical non-equilibrium processes were absent in the columns. The heavy metal BTCs were, however, asymmetrical and exhibited a tailing phenomenon, indicating the presence of chemical non-equilibrium processes in the columns. The retardation factors of Pb 2＋ were the largest of the four metal ions at both pH 4.0 （33.3） and pH 5.0 （35.4）. The use of Langmuir isotherm parameters from batch studies with HYDRUS-1D did not predict the BTCs well. Rather the two-site model （TSM） described the heavy metal BTCs better than the equilibrium linear/nonlinear Langmuir model. The fraction of instantaneous sorption sites （ f ） of all four metal ions on the lateritic soil was consistently about 30%–44% of the total sorption sites.展开更多
The hydrogen peroxide oxidation reaction (HPOOR) on Au(111) electrode in alkaline solutions with pH values ranging from 10 to 13 was examined systematically. HPOOR activity increased and the slope of the i-E curve dec...The hydrogen peroxide oxidation reaction (HPOOR) on Au(111) electrode in alkaline solutions with pH values ranging from 10 to 13 was examined systematically. HPOOR activity increased and the slope of the i-E curve decreased with increasing pH. HO2- is suggested to be the main reactive intermediate for HPOOR in alkaline media. The fast kinetics for HPOOR in alkaline solution is facilitated by the electrostatic interaction between the positively charged electrode and the reactive anions (i.e., HO2- and HO-), which increases the concentration of these reactants and the thermodynamic driving force for HO2- oxidation at the reaction plane.展开更多
In this work,we report a novel octa-nuclear uranyl(U8)motif[(UO2)8O4(μ3-OH)2(μ2-OH)2]4+embedded in a uranyl-oxalate coordination polymer(compound 1)based on a U-shaped linker with extra-long xylylene chains for stab...In this work,we report a novel octa-nuclear uranyl(U8)motif[(UO2)8O4(μ3-OH)2(μ2-OH)2]4+embedded in a uranyl-oxalate coordination polymer(compound 1)based on a U-shaped linker with extra-long xylylene chains for stabilizing the resulting high-nuclear motif through additional cross-linking connectivity.A comparison with dimeric and monomeric uranyl compounds obtained at different pH value from the same hydrothermal system reveals that,solution pH plays a vital role in formation of this octa-nuclear uranyl motif by promoting hydrolysis of uranyl source.Since high similarity of eight uranium centers in this nearly planar U8 motif here,overlapping and broadening of signals in fluorescence,infra-red(IR)and Raman spectra can be found.展开更多
Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what th...Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what the key factors are of CO2 RR kinetics and selectivity will be of great help in optimizing electrolysers for CO2 reduction.In this work,we report our results of hydrogen evolution and CO2 reduction on Pt(111)and Pt film electrodes in CO2 saturated acid solution by cyclic voltammetry and infrared spectroscopy.In solution with pH>2,the major process is HER and the interfacial pH increases abruptly during HER;COad is the only adsorbed intermediate detected in CO2 reduction by infrared spectroscopy;the rate for COad formation increases with the coverage of UPD-H and reaches maximum at the onset potential for HER;the decrease of COad formation under HER is attributed to the available limited sites and the limited residence time for the reduction intermediate(Had),which is necessary for CO2 adsorption and reduction.展开更多
In the present study the adsorptive properties of p-aminobenzoic acid with hypercrosslinked and multi-functional polymeric adsorbents at different solution pHs were systematically investigated in accordance with the p...In the present study the adsorptive properties of p-aminobenzoic acid with hypercrosslinked and multi-functional polymeric adsorbents at different solution pHs were systematically investigated in accordance with the particular physicochemical characteristics of the aromatic amphoteric compound involving both Lewis acid and Lewis base functional groups. It was found that the equilibrium adsorption data of the three polymeric adsorbents fitted well in the Langmuir and Freundlich isotherm equations. Studies at various pH levels indicate that the capacity of the adsorbents for adsorption of the ionic forms of adsorbate is less than that for the corresponding neutral species. At pH 3.78, the adsorption capacities of the three adsorbents are the highest. Whereas the adsorption property of multi-functional polymeric adsorbent NJ-99 is the largest, which may be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of p-aminobenzoic acid. The trend of the adsorption capacities of the three adsorbents towards p-aminobenzoic acid with the solution pH is in accord with the dissociation curve of the neutral molecular p-aminobenzoic acid. The adsorption forces include π-π interaction, hydrogen-bonding interaction and electrostatic attraction or repulsion when there exist the molecular and ionic adsorbing species at different pHs in aqueous solution.展开更多
The renal excretion of gentamicin, an aminoglycoside antibiotic, was studied in the isolated perfused rat kidney (IPRK) model. Dose-linearity experiments were carried out at four doses (400, 800, 1600, 3200 μg), targ...The renal excretion of gentamicin, an aminoglycoside antibiotic, was studied in the isolated perfused rat kidney (IPRK) model. Dose-linearity experiments were carried out at four doses (400, 800, 1600, 3200 μg), targeting initial perfusate levels of 5, 10, 20 and 40 μg/ml. Additionally, gentamicin was co-perfused with sodium bicarbonate (0.25 mM) and/or cimetidine (2 mM) to evaluate the effect of urinary alkalization and secretory inhibition on gentamicin excretion and kidney accumulation. Gentamicin displayed net reabsorption in the IPRK, consistent with extensive luminal uptake. Kinetic analysis indicated that luminal transport of gentamicin (kidney ? urine) is the rate-determining step for gentamicin urinary excretion. Clearance and cumulative excretion decreased with increased gentamicin dose. Gentamicin kidney accumulation, estimated by mass balance, ranged from ~20% - 30%. Urinary alkalization significantly increased gentamicin excretion, with no effect on kidney accumulation. Conversely, cimetidine co-administration did not affect gentamicin clearance in the IPRK, but kidney accumulation was significantly reduced. When both sodium bicarbonate and cimetidine were administered together, gentamicin kidney accumulation decreased ~80% with corresponding increases in clearance and excretion ratio (XR) compared to gentamicin alone. A main strategy to reduce the incidence of nephrotoxicity with gentamicin therapy (up to ~25%) involves reducing kidney accumulation of the compound. The results of this research suggest that the combination of urinary alkalization and inhibition of basolateral secretion (blood → kidney) may be a viable approach to mitigate aminoglycoside toxicity, and warrants further investigation.展开更多
In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbo...In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.展开更多
Combining the characteristics of the black pulping liquor that contains a lot of lignin and other biomass resources, the technology of comprehensive waste utilization is employed. The reconstructive preparation of mod...Combining the characteristics of the black pulping liquor that contains a lot of lignin and other biomass resources, the technology of comprehensive waste utilization is employed. The reconstructive preparation of modified urea-formaldehyde glue by adding black pulping liquor and the application in extruding the medium density fibre board using this modified urea-formaldehyde glue is researched. Results show that when applying the preparation technology that alkaline reaction and then weak acid reaction, the appropriate preparation process is as follows： the adding urea process is divided into three stages （proportion 2 ： 1 ： 1） ; the pH value is 8.0, and the reaction time is 40 min in the addition reaction stage; the pH value will be naturally reduced to 3.5 -5.0, and the reaction time is 45 min in the aggregation reaction stage; the pH value is 8.0 in the urea complement stage. And the optimal condition of the reconstructive preparation the modified ureaformaldehyde glue is adding the condensed black pulping liquor after hydroxymethylation in the beginning of polycondensation reaction by 5% proportion. The application in extruding medium density fibre board with this modified urea-fosmaldehyde glue is proved feasible.展开更多
The effect of brine salinity,cation type,pH,and produced sand on zeta potential(ZP)measurements with and without the presence of silica nanoparticles is investigated through pH measurement,static tests for sand and ZP...The effect of brine salinity,cation type,pH,and produced sand on zeta potential(ZP)measurements with and without the presence of silica nanoparticles is investigated through pH measurement,static tests for sand and ZP measurements as well as Field Emission Scanning Electron Microscope(FESEM)analyses.Three important factors were investigated:composition of the injected brine,surface charge and pH.Their influence on stability of nanoparticles in the injected brine and amount of sand segregation was determined and the analysis of the new outcomes based on rock/brine ZP measurements was reported.The results show that the use of silica nanoparticles with high pH helps in preventing sand production and that pH has a main effect on the surface charge of the sand particle released,affecting the ZP of the solution.Nanoparticles can be active as a coating on sand grains and prevent sand segregation during water flooding.Divalent cations have been found to acquire a more substantial impact on neutralizing the negative charge of the sand particles than monovalent cations at the same concentration and pH conditions at 25℃.The value of ZP becomes of higher negative value with the decrease of brine salinity.The effectiveness of SiO_(2)nanoparticles is quite different for soft water and smart water.For soft water,the nanoparticles work more effective at pH higher than 8;and for smart water,the nanoparticles perform better at pH lower than 8.To reduce sand production with the use of silica nanoparticles,it is highly suggested to increase pH,as pH and sand production mechanisms were observed to be inversely related.展开更多
The pH gradient caused by H^(+)/OH^(−)transport on an electrode surface is the key factor determining reaction performance,but its detailed impact on the electrode reaction kinetics has yet to be clarified.Here,the pH...The pH gradient caused by H^(+)/OH^(−)transport on an electrode surface is the key factor determining reaction performance,but its detailed impact on the electrode reaction kinetics has yet to be clarified.Here,the pH gradient effect was determined by developing electrode reaction equations,considering the overpotential assigned to the pH gradient called pH overpotential.The pH gradient effect was revealed to involve two aspects:(1)the Nernst pH overpotential,accounting for the common Nernst relationship with pH,and(2)the pH-dependent function of the electron-transfer coefficient(α_(pH)).Both parts were verified experimentally using oxygen reduction reaction and hydrogen evolution reaction,obviously,with differentα_(pH) functions.Detailedα_(pH) function effect was clarified based on numerical calculations of the electrode reaction equations.We found that the effect could be assessed suitably by an apparent constant(α_(app))and a nonlinear fitting method proposed forα_(app) value estimation.The results of this study provide the kinetic fundamentals of electrode reactions involving H^(+)/OH^(−)and contribute to the understanding and assessment of their performance with the H^(+)/OH^(−)transport effect.展开更多
The electrocatalytic hydrogen evolution reaction is a crucial technique for green hydrogen production.However,finding affordable,stable,and efficient catalyst materials to replace noble metal catalysts remains a signi...The electrocatalytic hydrogen evolution reaction is a crucial technique for green hydrogen production.However,finding affordable,stable,and efficient catalyst materials to replace noble metal catalysts remains a significant challenge.Recent experimental breakthroughs in the synthesis of two-dimensional bilayer borophene provide a theoretical framework for exploring their physical and chemical properties.In this study,we systematically considered nine types of bilayer borophenes as potential electrocatalysts for the hydrogen evolution reaction.Our first-principles calculations revealed that bilayer borophenes exhibit high stability and excellent conductivity,possessing a relatively large specific surface area with abundant active sites.Both surface boron atoms and the bridge sites between two boron atoms can serve as active sites,displaying high activity for the hydrogen evolution reaction.Notably,the Gibbs free energy change associated with adsorption for these bilayer borophenes can reach as low as−0.002 eV,and the Tafel reaction energy barriers are lower(0.70 eV)than those on Pt.Moreover,the hydrogen evolution reaction activity of these two-dimensional bilayer borophenes can be described by engineering their work function.Additionally,we considered the effect of pH on hydrogen evolution reaction activity,with significant activity observed in an acidic environment.These theoretical results reveal the excellent catalytic performance of two-dimensional bilayer borophenes and provide crucial guidance for the experimental exploration of multilayer boron for various energy applications.展开更多
The oxygen reduction kinetics on polycobaltprotoporphyrin(PCoPP)film has been examined with the rotating disc electrode technique in O_2-saturated solution of various pH.PCoPP film promotes the oxygen reduction proces...The oxygen reduction kinetics on polycobaltprotoporphyrin(PCoPP)film has been examined with the rotating disc electrode technique in O_2-saturated solution of various pH.PCoPP film promotes the oxygen reduction process via two electrons to produce peroxide over wide pH range. When pH value of solution decreases,catalytic activity of PCoPP film increases.Possible catalytic mechanisms have been proposed for oxygen reduction.展开更多
The permanganate(Mn(VII))oxidation has emerged as a promising technology for the remediation and treatment of the groundwater and surface water contaminated with the organic compounds.Nonetheless,only a few studies ha...The permanganate(Mn(VII))oxidation has emerged as a promising technology for the remediation and treatment of the groundwater and surface water contaminated with the organic compounds.Nonetheless,only a few studies have been conducted to explore the role of the heavy metals(especially the redox-active ones)during the Mn(VII)oxidation process.In this study,taking Pb(II)as an example,its influence on the Mn(VII)decontamination performance has been extensively investigated.It was found that,with the presence of Pb(II),Mn(VII)could degrade diclofenac(DCF),2,4-dichlorophenol,and aniline more effectively than without.For instance,over a wide pH range of 4.5–8.0,the dosing of 10μmol/L Pb(II)accelerated the DCF removal rate from 0.006–0.25 min–1 to 0.05–0.46 min–1 with a promotion factor of 1.9–9.4.Although the UV-vis spectroscopic and high resolution transmission electron microscopy analyses suggested that Mn(VII)could react with Pb(II)to produce Mn(IV)and Pb(IV)at pH 6.0–8.0,further experiments revealed that Pb(II)did not exert its enhancing effect through promoting the generation of MnO_(2),as the reactivity of MnO_(2)was poor under the employed pH range.At pH below 5.0,it was interesting to find that,a negligible amount of MnO_(2)was formed in the Mn(VII)/Pb(II)system in the absence of contaminants,while once MnO_(2)was generated in the presence of contaminants,it could catalyze the Pb(II)oxidation to Pb(IV)by Mn(VII).Collectively,by highlighting the conversion process of Pb(II)to Pb(IV)by either Mn(VII)or MnO_(2),the reactive Pb(III)intermediates were proposed to account for the Pb(II)enhancement effect.展开更多
文摘Lead (Pb) inhibited the activities of Na+ -K+ ATPase (IC50= 2.0×10^(-6) M), K + -Para-Nitrophenyl phosphatase (PNPPase) (IC50= 3.5×10^(-6) M) and [3H]-ouabain binding (IC50 = 4.0×10^(-5) M) in rat brain P2 fraction. A variable temperature or pH significantly elevated the inhibition of Na+-K+ ATPase by Pb in buffered acidic, neutral and alkaline pH ranges. Noncompetitive inhibition with respect to activation of Na+ -K+ ATPase by ATP was indicated by a variation in Vmax values with no significant changes in Km values at any temperature studied. In the presence of Pb, for Na+ -K+ ATPase at pH 6.5 and 8.5, Vmax was decreased with an increase in Km values suggesting a mixed type of inhibition. Sulfhydryl agents such as dithiothreitol (DTT) and cvsteine (Cyst), but not glutathione (GSH) offered varied levels of protection against Pb-inhibition of Na + -K+ ATPase at pH 7.5 and 8.5. The present data suggest that inhibition of Na+ -K+ ATPase by Pb is both temperature and pH-dependent. These results also indicate that Pb inhibited Na + -K + ATPase by interfering with phosphorylation of enzyme molecule and dephosphorylation of the enzyme-phosphoryl complex and exerted an effect similar to that of SH-blocking agents.
文摘Bensulfuron-Methyl(BSM)is a highly active sul-fonylurea herbicide that effectively controls most an-nual and perennial broadleaf or sedge weeds in paddyfield.However,the activity of BSM is affected byseveral evironmental factors.Using corn seedlings asmaterial,we found that under different temperatures
基金supported by the National Natural Science Foundation of China(Nos.22102073,22075147).
文摘As a versatile and environmentally benign oxidant,hydrogen peroxide(H_(2)O_(2))is highly desired in sanitation,disinfection,environmental remediation,and the chemical industry.Compared with the conventional anthraquinone process,the electrosynthesis of H_(2)O_(2)through the two-electron oxygen reduction reaction(2e^(−)ORR)is an efficient,competitive,and promising avenue.Electrocatalysts and devices are two core factors in 2e^(−)ORR,but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear.To this end,this review adopts a multiscale perspective to summarize recent advancements in the design principles,catalytic mechanisms,and application prospects of 2e^(−)ORR catalysts,with a particular focus on the influence of pH conditions,aiming at providing guidance for the selective design of advanced 2e^(−)ORR catalysts for highly-efficient H_(2)O_(2)production.Moreover,in response to diverse on-site application demands,we elaborate on the evolution of H_(2)O_(2)electrosynthesis devices,from rotating ring-disk electrodes and H-type cells to diverse flow-type cells.We elaborate on their characteristics and shortcomings,which can be beneficial for their further upgrades and customized applications.These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
基金support from the National Natural Science Foundation of China(Nos.22272193,22225302,21991151,and 21991150)the Ningbo Natural Science Foundation(No.2022J294)+1 种基金the Yongjiang Talent Introduction Program(No.2021A-115-G)Key Laboratory of Advanced Marine Materials,Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,Ningbo.(No.2021A-115-G).
文摘The adsorption/desorption of OH*on electrode surfaces is pivotal in numerous electrocatalytic reactions.To understand the effect of electrolyte pH on that process,in this work,an advanced approach combining ab initio molecular dynamics(AIMD)with free energy perturbation is employed to calculate the dehydrogenation free energy of water chemisorbed at differently electrified Pt(111)/electrolyte interfaces.Our findings reveal that the onset potential for OH*formation shifts negatively as the pH increases at low pH condition(pH<4.3),aligning with the cyclic voltammetry curves observed in experimental studies.It indicates the dissociation of chemisorbed water is the primary route for OH*adsorption at low pH condition.Furthermore,it is also found that the variation in dehydrogenation energy across different pH is primarily due to the local hydrogen bonding network surrounding the chemisorbed water.In addition,it is proposed that at high pH conditions OH-oxidation emerges as the primary route for OH*adsorption on Pt(111)constrained by the water chemisorption process.This work provides crucial insights into the pH-dependent adsorption behavior of OH*on the Pt(111)surface and aims to guide the optimization of electrolytes to boost the efficiency of related reactions.
基金supported by the National Natural Science Foundation of China(No.22172151)。
文摘Phosphoric acid/phosphate solu-tions are commonly used as buffer solutions in the fundamental stud-ies in electrochemistry.Informa-tion on the nature of adsorbed(bi)phosphate as well as the do-main structures is of great impor-tance in unveiling the impact on electrochemical processes occur-ring at electrode electrolyte interface.In this work,the pH effect on the adsorption of phosphate related species on Pd(111)electrode has been investigated by cyclic voltammetry over a broad pH range from 1 to 14.Af-ter carefully analyzing the related onset desorption potential of(bi)phosphate adsorbate to the thermodynamic equilibrium potential of the corresponding electrode reactions,three dif-ferent phosphate related adsorbates have been identified,which are highly pH-dependent.Our analysis reveals that the dominant phosphate anions in bulk solution undergo deprotona-tion upon adsorption.At pH<1.5,the main adsorbate on Pd(111)is;H_(2)PO_(4)^(λ_(1)^(-))in solutions with 1.5<pH<7,the main adsorbate changes into.HPO_(4)^(λ_2^(-))At higher pHs,PO_(4)^(λ_(3)^(-))on electrode surface dominates.The exact charging value ofλ_(i),which represents the true va-lence of the(bi)phosphate adsorbate,could be determined using theoretical calculations.In addition,our results can not rule out the possibility of co-adsorbed H_(3)PO_(4)molecules on Pd(111)at pH<1.5,which needs to be proved by infrared spectroscopy in the future.
基金financial support from the National Natural Science Foundation of China(21528302)Zhejiang Province Natural Science Foundation(LQ15B060004)
文摘The Co-based catalysts were prepared with different cobalt acetate solutions.Effects of pH value were studied deeply on Fischer–Tropsch synthesis(FTS)through a semi-batch reactor.Among all impregnation solutions(water,butanol,amyl alcohol,acetic acid,nitric acid and ammonium nitrate),the catalyst prepared by NH4NO3solution showed the highest catalytic activity due to its small particle size and high reduction degree.However,the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS.According to FT-IR spectra results,the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity.Whereas,the high activity of catalysts prepared from NH4NO3solution could be explained by the high intensity of absorbed CO on the catalysts.The cobalt species on the catalysts prepared under lower pH conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher pH value.
文摘The photo-catalytic degradation pathway and degradation products of methylene blue, rhodamine B, methyl orange, and malachite green in aqueous TiO2 suspension irradiated by high pressure mercury lamp by means of UV-visible absorption spectra and ion chromatography were investigated. The photo-catalysis degradation of dye solutions with charges was greatly effected by pH value owing to the electrostatic model. The photo-degradation rate of dyes anion increased with the decrease of pH value, in contrast, the photo-degradation rate of dyes cation increased with the increase of pH value. And the absorption peaks diminished with a blue shift. After illuminated for 30 minutes, a part of dye chemicals were completely mineralized and transferred into inorganic species including chloride ion, ammonium ion, nitrate ion, sulfate ion. And the addition of 100 mmol/L H2O2 promoted the formation of inorganic species. In this study, the quantity of ammonium ion was much more than that of nitrate ion. That indicated the formation of nitrate is from ammonium. The purification rate of COD in four kinds of dye solution was 71.7%-88.7%. The decrease of COD of dyes solution implies the feasibility of the environmental application of photo-catalyzed process.
基金the National Center of Excellence for Environmental and Hazardous Waste Management(NCE-EHWM)the Geology Department of Chulalongkorn University
文摘This study investigated the effects of pH on the transport of Pb 2＋ , Mn 2＋ , Zn 2＋ and Ni 2＋ through lateritic soil columns. Model results by fitting the symmetric breakthrough curves （BTCs） of bromide （Br ） with CXTFIT model suggested that physical non-equilibrium processes were absent in the columns. The heavy metal BTCs were, however, asymmetrical and exhibited a tailing phenomenon, indicating the presence of chemical non-equilibrium processes in the columns. The retardation factors of Pb 2＋ were the largest of the four metal ions at both pH 4.0 （33.3） and pH 5.0 （35.4）. The use of Langmuir isotherm parameters from batch studies with HYDRUS-1D did not predict the BTCs well. Rather the two-site model （TSM） described the heavy metal BTCs better than the equilibrium linear/nonlinear Langmuir model. The fraction of instantaneous sorption sites （ f ） of all four metal ions on the lateritic soil was consistently about 30%–44% of the total sorption sites.
基金supported by the National Natural Science Foundation of China(No.21473175 and No.21273215)the National Key Basic Research Program of China from the Ministry of Science andTechnology of China(No.2015CB932301)
文摘The hydrogen peroxide oxidation reaction (HPOOR) on Au(111) electrode in alkaline solutions with pH values ranging from 10 to 13 was examined systematically. HPOOR activity increased and the slope of the i-E curve decreased with increasing pH. HO2- is suggested to be the main reactive intermediate for HPOOR in alkaline media. The fast kinetics for HPOOR in alkaline solution is facilitated by the electrostatic interaction between the positively charged electrode and the reactive anions (i.e., HO2- and HO-), which increases the concentration of these reactants and the thermodynamic driving force for HO2- oxidation at the reaction plane.
基金National Natural Science Foundation of China(21671191,21577144,11405186)。
文摘In this work,we report a novel octa-nuclear uranyl(U8)motif[(UO2)8O4(μ3-OH)2(μ2-OH)2]4+embedded in a uranyl-oxalate coordination polymer(compound 1)based on a U-shaped linker with extra-long xylylene chains for stabilizing the resulting high-nuclear motif through additional cross-linking connectivity.A comparison with dimeric and monomeric uranyl compounds obtained at different pH value from the same hydrothermal system reveals that,solution pH plays a vital role in formation of this octa-nuclear uranyl motif by promoting hydrolysis of uranyl source.Since high similarity of eight uranium centers in this nearly planar U8 motif here,overlapping and broadening of signals in fluorescence,infra-red(IR)and Raman spectra can be found.
基金supported by the National Natural Science Foundation of China (No.21473175 and No.21273215)the Ministry of Science and Technology of China (No.2015CB932301)
文摘Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what the key factors are of CO2 RR kinetics and selectivity will be of great help in optimizing electrolysers for CO2 reduction.In this work,we report our results of hydrogen evolution and CO2 reduction on Pt(111)and Pt film electrodes in CO2 saturated acid solution by cyclic voltammetry and infrared spectroscopy.In solution with pH>2,the major process is HER and the interfacial pH increases abruptly during HER;COad is the only adsorbed intermediate detected in CO2 reduction by infrared spectroscopy;the rate for COad formation increases with the coverage of UPD-H and reaches maximum at the onset potential for HER;the decrease of COad formation under HER is attributed to the available limited sites and the limited residence time for the reduction intermediate(Had),which is necessary for CO2 adsorption and reduction.
基金This work was supported by the Opening Foundation of Jiangsu Provincial Key Laboratory of Coastal Wetland Bioresources and Environmental Protection of China (No. JLCBE05006).
文摘In the present study the adsorptive properties of p-aminobenzoic acid with hypercrosslinked and multi-functional polymeric adsorbents at different solution pHs were systematically investigated in accordance with the particular physicochemical characteristics of the aromatic amphoteric compound involving both Lewis acid and Lewis base functional groups. It was found that the equilibrium adsorption data of the three polymeric adsorbents fitted well in the Langmuir and Freundlich isotherm equations. Studies at various pH levels indicate that the capacity of the adsorbents for adsorption of the ionic forms of adsorbate is less than that for the corresponding neutral species. At pH 3.78, the adsorption capacities of the three adsorbents are the highest. Whereas the adsorption property of multi-functional polymeric adsorbent NJ-99 is the largest, which may be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of p-aminobenzoic acid. The trend of the adsorption capacities of the three adsorbents towards p-aminobenzoic acid with the solution pH is in accord with the dissociation curve of the neutral molecular p-aminobenzoic acid. The adsorption forces include π-π interaction, hydrogen-bonding interaction and electrostatic attraction or repulsion when there exist the molecular and ionic adsorbing species at different pHs in aqueous solution.
文摘The renal excretion of gentamicin, an aminoglycoside antibiotic, was studied in the isolated perfused rat kidney (IPRK) model. Dose-linearity experiments were carried out at four doses (400, 800, 1600, 3200 μg), targeting initial perfusate levels of 5, 10, 20 and 40 μg/ml. Additionally, gentamicin was co-perfused with sodium bicarbonate (0.25 mM) and/or cimetidine (2 mM) to evaluate the effect of urinary alkalization and secretory inhibition on gentamicin excretion and kidney accumulation. Gentamicin displayed net reabsorption in the IPRK, consistent with extensive luminal uptake. Kinetic analysis indicated that luminal transport of gentamicin (kidney ? urine) is the rate-determining step for gentamicin urinary excretion. Clearance and cumulative excretion decreased with increased gentamicin dose. Gentamicin kidney accumulation, estimated by mass balance, ranged from ~20% - 30%. Urinary alkalization significantly increased gentamicin excretion, with no effect on kidney accumulation. Conversely, cimetidine co-administration did not affect gentamicin clearance in the IPRK, but kidney accumulation was significantly reduced. When both sodium bicarbonate and cimetidine were administered together, gentamicin kidney accumulation decreased ~80% with corresponding increases in clearance and excretion ratio (XR) compared to gentamicin alone. A main strategy to reduce the incidence of nephrotoxicity with gentamicin therapy (up to ~25%) involves reducing kidney accumulation of the compound. The results of this research suggest that the combination of urinary alkalization and inhibition of basolateral secretion (blood → kidney) may be a viable approach to mitigate aminoglycoside toxicity, and warrants further investigation.
基金supported by the National Natural Science Foundation of China(21972131)。
文摘In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.
基金Sponsored by the Ministerial Level Advanced Research Foundation(20060013)
文摘Combining the characteristics of the black pulping liquor that contains a lot of lignin and other biomass resources, the technology of comprehensive waste utilization is employed. The reconstructive preparation of modified urea-formaldehyde glue by adding black pulping liquor and the application in extruding the medium density fibre board using this modified urea-formaldehyde glue is researched. Results show that when applying the preparation technology that alkaline reaction and then weak acid reaction, the appropriate preparation process is as follows： the adding urea process is divided into three stages （proportion 2 ： 1 ： 1） ; the pH value is 8.0, and the reaction time is 40 min in the addition reaction stage; the pH value will be naturally reduced to 3.5 -5.0, and the reaction time is 45 min in the aggregation reaction stage; the pH value is 8.0 in the urea complement stage. And the optimal condition of the reconstructive preparation the modified ureaformaldehyde glue is adding the condensed black pulping liquor after hydroxymethylation in the beginning of polycondensation reaction by 5% proportion. The application in extruding medium density fibre board with this modified urea-fosmaldehyde glue is proved feasible.
文摘The effect of brine salinity,cation type,pH,and produced sand on zeta potential(ZP)measurements with and without the presence of silica nanoparticles is investigated through pH measurement,static tests for sand and ZP measurements as well as Field Emission Scanning Electron Microscope(FESEM)analyses.Three important factors were investigated:composition of the injected brine,surface charge and pH.Their influence on stability of nanoparticles in the injected brine and amount of sand segregation was determined and the analysis of the new outcomes based on rock/brine ZP measurements was reported.The results show that the use of silica nanoparticles with high pH helps in preventing sand production and that pH has a main effect on the surface charge of the sand particle released,affecting the ZP of the solution.Nanoparticles can be active as a coating on sand grains and prevent sand segregation during water flooding.Divalent cations have been found to acquire a more substantial impact on neutralizing the negative charge of the sand particles than monovalent cations at the same concentration and pH conditions at 25℃.The value of ZP becomes of higher negative value with the decrease of brine salinity.The effectiveness of SiO_(2)nanoparticles is quite different for soft water and smart water.For soft water,the nanoparticles work more effective at pH higher than 8;and for smart water,the nanoparticles perform better at pH lower than 8.To reduce sand production with the use of silica nanoparticles,it is highly suggested to increase pH,as pH and sand production mechanisms were observed to be inversely related.
基金supported by the National Natural Science Foundation of China(grant nos.51525805,51727812,and 51808526).
文摘The pH gradient caused by H^(+)/OH^(−)transport on an electrode surface is the key factor determining reaction performance,but its detailed impact on the electrode reaction kinetics has yet to be clarified.Here,the pH gradient effect was determined by developing electrode reaction equations,considering the overpotential assigned to the pH gradient called pH overpotential.The pH gradient effect was revealed to involve two aspects:(1)the Nernst pH overpotential,accounting for the common Nernst relationship with pH,and(2)the pH-dependent function of the electron-transfer coefficient(α_(pH)).Both parts were verified experimentally using oxygen reduction reaction and hydrogen evolution reaction,obviously,with differentα_(pH) functions.Detailedα_(pH) function effect was clarified based on numerical calculations of the electrode reaction equations.We found that the effect could be assessed suitably by an apparent constant(α_(app))and a nonlinear fitting method proposed forα_(app) value estimation.The results of this study provide the kinetic fundamentals of electrode reactions involving H^(+)/OH^(−)and contribute to the understanding and assessment of their performance with the H^(+)/OH^(−)transport effect.
基金supported by the National Natural Science Foundation of China(Grant Nos.12264043 and 11864033)the Supercomputing Center of Dalian University of Technology.
文摘The electrocatalytic hydrogen evolution reaction is a crucial technique for green hydrogen production.However,finding affordable,stable,and efficient catalyst materials to replace noble metal catalysts remains a significant challenge.Recent experimental breakthroughs in the synthesis of two-dimensional bilayer borophene provide a theoretical framework for exploring their physical and chemical properties.In this study,we systematically considered nine types of bilayer borophenes as potential electrocatalysts for the hydrogen evolution reaction.Our first-principles calculations revealed that bilayer borophenes exhibit high stability and excellent conductivity,possessing a relatively large specific surface area with abundant active sites.Both surface boron atoms and the bridge sites between two boron atoms can serve as active sites,displaying high activity for the hydrogen evolution reaction.Notably,the Gibbs free energy change associated with adsorption for these bilayer borophenes can reach as low as−0.002 eV,and the Tafel reaction energy barriers are lower(0.70 eV)than those on Pt.Moreover,the hydrogen evolution reaction activity of these two-dimensional bilayer borophenes can be described by engineering their work function.Additionally,we considered the effect of pH on hydrogen evolution reaction activity,with significant activity observed in an acidic environment.These theoretical results reveal the excellent catalytic performance of two-dimensional bilayer borophenes and provide crucial guidance for the experimental exploration of multilayer boron for various energy applications.
文摘The oxygen reduction kinetics on polycobaltprotoporphyrin(PCoPP)film has been examined with the rotating disc electrode technique in O_2-saturated solution of various pH.PCoPP film promotes the oxygen reduction process via two electrons to produce peroxide over wide pH range. When pH value of solution decreases,catalytic activity of PCoPP film increases.Possible catalytic mechanisms have been proposed for oxygen reduction.
基金This work was supported by the National Key Research and Development Program of China(No.2019YFC1805202)the National Natural Science Foundation of China(Grant Nos.22076143 and 22025601)+1 种基金the State Key Laboratory of Pollution Control and Resource Reuse Foundation(No.PCRRF18021)the Shanghai Science and Technology Development Funds(No.20QB1404800).
文摘The permanganate(Mn(VII))oxidation has emerged as a promising technology for the remediation and treatment of the groundwater and surface water contaminated with the organic compounds.Nonetheless,only a few studies have been conducted to explore the role of the heavy metals(especially the redox-active ones)during the Mn(VII)oxidation process.In this study,taking Pb(II)as an example,its influence on the Mn(VII)decontamination performance has been extensively investigated.It was found that,with the presence of Pb(II),Mn(VII)could degrade diclofenac(DCF),2,4-dichlorophenol,and aniline more effectively than without.For instance,over a wide pH range of 4.5–8.0,the dosing of 10μmol/L Pb(II)accelerated the DCF removal rate from 0.006–0.25 min–1 to 0.05–0.46 min–1 with a promotion factor of 1.9–9.4.Although the UV-vis spectroscopic and high resolution transmission electron microscopy analyses suggested that Mn(VII)could react with Pb(II)to produce Mn(IV)and Pb(IV)at pH 6.0–8.0,further experiments revealed that Pb(II)did not exert its enhancing effect through promoting the generation of MnO_(2),as the reactivity of MnO_(2)was poor under the employed pH range.At pH below 5.0,it was interesting to find that,a negligible amount of MnO_(2)was formed in the Mn(VII)/Pb(II)system in the absence of contaminants,while once MnO_(2)was generated in the presence of contaminants,it could catalyze the Pb(II)oxidation to Pb(IV)by Mn(VII).Collectively,by highlighting the conversion process of Pb(II)to Pb(IV)by either Mn(VII)or MnO_(2),the reactive Pb(III)intermediates were proposed to account for the Pb(II)enhancement effect.
