Both π and σ transition states on the potential energy surface of the nitration of benzene with nitronium ion have been successfully optimized using unrestricted hybrid DFT procedure B3LYP with the triple-zeta 6-311...Both π and σ transition states on the potential energy surface of the nitration of benzene with nitronium ion have been successfully optimized using unrestricted hybrid DFT procedure B3LYP with the triple-zeta 6-311G ** basis set without any assumption. Subsequently, a σreactant-complex and a σ intermediate (Wheland intermediate) were located by the intrinsic reaction coordinate (IRC) calculation. The reaction pathway and the experimental observation lacking the kinetic isotopic effect in the title nitration were confirmed on geometries, atomic charges, energies, IR spectra and thermodynamic properties of all stationary points. The activation energy of 8.370 kJ/mol in the gas phase and the order of 1010 mol η L-1 η s-1 of rate constant were obtained for the reaction. The results both in thermodynamics and kinetics show that the electrophilic substitute mechanism is more preferable than the electron transfer mechanism of radical pairs. The solvent effect on the geometries of stationary points and the reaction mechanism were systematically studied for the nitration of benzene with nitronium by self-consistent reaction field (SCRF) technique with different dielectric constants of 5.0, 25.0, 50.0 and 78.5. It was then found that the solvent effect would depress the activation energy and finally make the formation of σ-TS without energy barrier in aqueous solution. Furthermore, the linear correlations given by charge migrations of NO2 group, dipole moments of solute, gaps of HOMO and LUMO and solvent stabilization energies in different solvents were demonstrated for both theoretically and experimentally concerned Wheland intermediate.展开更多
Based upon the thiophene-2,5-dicarboxylic acid(H_(2)Tdc),a novel[Sc_(3)(μ_(2)-OH)_(3)(CO_(2))_(4)O_(6)]n inorganic chain-based Sc-MOF with decorated nitrate ions,{[Sc_(3)(OH)_(2)(Tdc)_(3)(NO_(3))]⋅H_(2)O}_(∞)(AEU-1;...Based upon the thiophene-2,5-dicarboxylic acid(H_(2)Tdc),a novel[Sc_(3)(μ_(2)-OH)_(3)(CO_(2))_(4)O_(6)]n inorganic chain-based Sc-MOF with decorated nitrate ions,{[Sc_(3)(OH)_(2)(Tdc)_(3)(NO_(3))]⋅H_(2)O}_(∞)(AEU-1;AEU for Army Engineering University of PLA),was synthesized,which shows good water and chemical stabilities.Significantly,due to channel constriction accompanied by the polar window caused by introducing nitrate ions,AEU-1 exhibits high C_(2)H_(6)/C_(2)H_(4)adsorption selectivity comparable to many famous C_(2)H_(6)-selective MOFs,making it a promising candidate for the purification of methanol-to-olefin(MTO)products.Furthermore,theoretical investigations reveal that the introduced nitrate ions in AEU-1 as the main adsorption sites could provide strong interactions between the framework and C2H6/C3H6 in the full-contacting mode,leading to an increase in the adsorption enthalpies(Qst)of C_(2)H_(6)and C_(3)H_(6),and thus further improving the C_(2)H_(6)/C_(2)H_(4)and C_(3)H_(6)/C_(2)H_(4)adsorption selectivity.Our work could open up a new avenue for constructing MOFs with inorganic polar moieties as adsorption sites for one-step C_(2)H_(4)purification and C3H6 recovery from MTO mixtures with high selectivity.展开更多
Ammonium toxicity in plants remains poorly understood despite extensive research.While nitrate is known to benefit plant growth,the synergistic effects of nitrate in mitigating ammonium toxicity,even at low concentrat...Ammonium toxicity in plants remains poorly understood despite extensive research.While nitrate is known to benefit plant growth,the synergistic effects of nitrate in mitigating ammonium toxicity,even at low concentrations,are not fully elucidated.This review delves into the physiological and molecular nature of this phenomenon.To date,nitrate-dependent alleviation of ammonium toxicity is the result of cumulative consequences of the role of nitrate as a nutrient and signal in plant performance.The ability to counteract the ammonium-induced acidification through nitrate uptake and metabolism,the enhancement of potassium uptake as an essential nitrate counterion,and the nitratedependent signaling of key factors involved in ammonium assimilation,ROS scavenging,and growth hormone biosynthesis,are the most relevant hallmarks.In addition,evidence suggests that the availability of nitrate and ammonium has driven ecological selection in plants,determining current N preferences,and may have led to the selection of nitrate-dependent and ammonium-sensitive domesticated crops and the inefficient use of N fertilizers in agriculture.As ammonium toxicity limits N fertilization options and reduces agricultural yields,when it could be a more sustainable and cheaper alternative to nitrate,this review provides a better understanding of how plants use nitrate to counteract the problematic aspects of ammonium nutrition.展开更多
La1-x Cax MnO3 （x=0-0.3） perovskite-type oxides were synthesized by citrate sol-gel method. The physical and chemical properties were characterized by X-ray diffraction （XRD）, Brumauer-Emmett-Teller method （BET）...La1-x Cax MnO3 （x=0-0.3） perovskite-type oxides were synthesized by citrate sol-gel method. The physical and chemical properties were characterized by X-ray diffraction （XRD）, Brumauer-Emmett-Teller method （BET）, X-ray photoelectron spectroscopy （XPS）, NO＋O2 -TPD （temperature-programmed desorption）, activated oxygen evaluation and H2 -TPR （temperature-programmed reduction） technologies. The results showed that NO catalytic oxidation activity was significantly improved by Ca substitution, especially for lower temperature activity. The La0.9 Ca0.1 MnO 3 sample showed the maximum conversion of 82% at 300 oC. The monodentate nitrates played a crucial role for the formation of NO2 . The reducibility of Mn 4＋ ions and reactivity of activated oxygen were favorable for the catalytic performances of NO oxidation.展开更多
An extensive series of experiments was carried out in order to identify suitable catalysts to boost the reaction rate of wet air oxidation of real textile wastewaters at relatively mild temperature and pressure. Exper...An extensive series of experiments was carried out in order to identify suitable catalysts to boost the reaction rate of wet air oxidation of real textile wastewaters at relatively mild temperature and pressure. Experimental results indicated that all catalysts tested in this investigation had shown an impressive increase in the initial COD and TOC removal rate as well as the COD and TOC removal levels in two hours reaction. Among all the catalysts tested, copper salts were more effective than the rest. Anions of the salt solutions also played a role in the catalytic process with nitrate ions having better effect than sulfate ions. Hence copper nitrates were more effective than copper sulfates. It was also found that a mixture of salts with different metals performed better than either of the component single salt alone.展开更多
Nutrition is an important factor for the growth and development of plants. Among the main nutritional elements, there are nitrogen （N） and calcium （Ca）. The N comes from two forms of inorganic ions, ammonium （NH...Nutrition is an important factor for the growth and development of plants. Among the main nutritional elements, there are nitrogen （N） and calcium （Ca）. The N comes from two forms of inorganic ions, ammonium （NH4＋） and nitrate （NO3） whose functions in the plant are the increase in leaf area and improving the succulence of many crops, among other essential physiological processes. Both the deficit and excess NO3- have a negative impact on plants increasing susceptibility to insect pests and pathogens, while Ca as divalent ion absorbed Ca2＋ plays an important role in control of physiological disorders and the resistance of plants to diseases to increase the mechanical strength. The N and Ca have a close relationship in the nutritional role of the plant, because the Ca absorption acting nitrates, so that a proper balance affects plants better growth and higher strength.展开更多
An ion chromatographic method with a valve switching facility was developed to determine trace nitrate concentrations in seawater using two pumps, two different suppressors, and two columns. A carbohydrate membrane de...An ion chromatographic method with a valve switching facility was developed to determine trace nitrate concentrations in seawater using two pumps, two different suppressors, and two columns. A carbohydrate membrane desalter was used to reduce the high concentrations of sodium salts in samples. In this method, trace nitrate was eluted from the concentrator column to the analytical columns, while the matrix fl owed to waste. Neither chemical pre-treatment nor sample dilution was required. In the optimized separation conditions, the method showed good linearity( R >0.99) in the 0.05 and 50 mg/L concentration range, and satisfactory repeatability(RSD<5%, n =6). The limit of detection for nitrate was 0.02 mg/L. Results showed that the valve switching system was suitable and practical for the determination of trace nitrate in seawater.展开更多
Air pollution in China is complex,and the formation mechanism of chemical components in particulate matter is still unclear.This study selected three consecutive heavy haze pollution episodes(HPEs)during winter in Bei...Air pollution in China is complex,and the formation mechanism of chemical components in particulate matter is still unclear.This study selected three consecutive heavy haze pollution episodes(HPEs)during winter in Beijing for continuous field observation,including an episode with heavy air pollution under red alert.Clean days during the observation period were selected for comparison.The HPE characteristics of Beijing in winter were:under the influence of adverse meteorological conditions such as high relative humidity,temperature inversion and low wind speed;and strengthening of secondary transformation reactions,which further intensified the accumulation of secondary aerosols and other pollutants,promoting the explosive growth of PM_(2.5).PM_(2.5)/CO values,as indicators of the contribution of secondary transformation in PM_(2.5),were approximately 2 times higher in the HPEs than the average PM_(2.5)/CO during the clean period.The secondary inorganic aerosols(sulfate nitrate and ammonium salt)were significantly enhanced during the HPEs,and the conversion coefficients were remarkably improved.In addition,it is interesting to observe that the production of sulfate tended to exceed that of nitrate in the late stage of all three HPEs.The existence of aqueous phase reactions led to the explosive growth sulfur oxidation ratio(SOR)and rapid generation of sulfate under high relative humidity(RH>70%).展开更多
Egusi seed shells (ESS) were used as precursor for the preparation of two activated carbons (ACs) following H3PO4 and ZnCl2 activation. The effect of factors controlling the preparation of ACs such as chemical activat...Egusi seed shells (ESS) were used as precursor for the preparation of two activated carbons (ACs) following H3PO4 and ZnCl2 activation. The effect of factors controlling the preparation of ACs such as chemical activating agent concentration (2 - 10 M), activation temperature (400°C - 700°C) and residence time (30 - 120 min) were optimized using the Box-Behnken Design (BBD). The optimized activated carbons based H3PO4 (ACP) and ZnCl2 (ACZ) were characterized by N2 adsorption, elemental analysis, atomic force microscopy (AFM), Boehm titration and Fourier transformed infrared (FTIR) techniques. The specific surface area was found to be 1053.91 and 1009.89 m2·g-1 for ACP and ACZ respectively. The adsorbents had similar surface functionalities and were both microporous. The effect of various parameters such as initial pH, concentration, and contact time on the adsorption of nitrate ions on ACP and ACZ in aqueous solution was studied. ACZ demonstrated better adsorption capacity (8.26 mg·g-1) compared to ACP (5.65 mg·g-1) at the same equilibrium time of 20 min. The adsorption process was governed by a “physical interactions” phenomenon for both adsorbents.展开更多
Sorption recovery of palladium (II) from nitrate weak acidic model solutions and solutions of spent catalysts on some ion exchangers with different physical and chemical structure has been investigated. The palladium ...Sorption recovery of palladium (II) from nitrate weak acidic model solutions and solutions of spent catalysts on some ion exchangers with different physical and chemical structure has been investigated. The palladium concentration in contacting solutions was 5.0 ? 10-5 – 1.0 ? 10-3 mol/L at nitric acid and potassium nitrate con-centrations 0.01 and 1.0 mol/L, respectively. It was shown that anion exchangers AV-17-8 as well as Purolite S 985 and A 500 possess the best sorption and kinetic properties. These sorbents can be recommended for selective recovery of palladium from solutions of spent catalysts.展开更多
Mesoporous titanium dioxide films were fabricated on titanium plates by micro-arc oxidation method.To increase the photocatalytic activity of the films,NH4NO3 was added to the H2SO4 solution,and anodizing was carried ...Mesoporous titanium dioxide films were fabricated on titanium plates by micro-arc oxidation method.To increase the photocatalytic activity of the films,NH4NO3 was added to the H2SO4 solution,and anodizing was carried out at high voltages using a DC power supply.The crystal structure,chemical composition,surface morphology and the optical property of the films were investigated by XPS,XRD,UV-VIS spectroscopy and SEM.The photocatalytic activity of the films was evaluated by the decomposition of aniline blue,and the activity of the films for the degradation turned out to be improved by the additives to the electrolyte solution.The enhanced photocatalytic activity might result from the increased porosity and nitrate ion incorporation into the anodic films by micro arcing,and thereby the TiO2 layer might exhibit an improved absorption property for the visible light.展开更多
Cheeses are characterized by several chemical-physical properties that make it difficult for the microorganisms growth, consequently. The actual European legislation allows the addition of few food additives in this t...Cheeses are characterized by several chemical-physical properties that make it difficult for the microorganisms growth, consequently. The actual European legislation allows the addition of few food additives in this type of food products. In this work, the entire procedure of extraction, purification, chromatographic separations and quali/quantitative determination of seven food additives (sorbic acid, benzoic acid, lactic acid, acetic acid, nitrites, nitrates and phosphates) was developed and applied for the analysis of different types of cheese (mozzarella, cheese spread, semi-hard and hard cheeses). Through validation procedure it was possible to evaluate the most important validation parameters. Extended calibration curves (r > 0.990) were obtained for all the analyzed compounds. Recovery values ranged from 72.8% to 98.4% and a good repeatability was obtained, with precision levels in the range of 0.03% - 0.11% (n = 6). The potential and feasibility of the method were tested by analysing real samples, such as mozzarella, cheese spread, semi-hard and hard cheeses, confirming that the method is well suited to satisfy the demands for accurate confirmation analyses of seven food additives in cheeses, which is especially valuable in official check analyses and in monitoring schemes.展开更多
Plants need to be efficient in nutrient management, especially when they face the temporal nutrient defficiencies. Understanding how crops respond to nitrogen （N） starvation would help in the selection of crop culti...Plants need to be efficient in nutrient management, especially when they face the temporal nutrient defficiencies. Understanding how crops respond to nitrogen （N） starvation would help in the selection of crop cultivars more tolerant to N deficiency. In the present work, the physiological responses of two wheat cultivars, Yannong 19 （YN） and Qinmai 11 （QM）, to N starvation conditions were investigated. The two cultivars differed in biomass and N rearrangement between shoots and roots during N starvation. QM allocated more N to roots and exhibited higher root/shoot biomass ratio than YN. However, tissue measurement indicated that both cultivars had similar nitrate content in leaves and roots and similar remobilization rate in roots. Microelectrode measurement showed that vacuolar nitrate activity （concentration） in roots of QM was lower than that in roots of YN, especially in epidermal cells. Nitrate remobilization rates from root vacuoles of two cultivars were also identical. Moreover, vacuolar nitrate remobilization rate was proportional to vacuolar nitrate activity. During N starvation, nitrate reductase activity （NRA） was decreased but there were no significant differences between the two cultivars. Nitrate efflux from roots reduced after external N removal and QM seemed to have higher nitrate efflux rate.展开更多
Bioactive calcium silicates prepared by sol–gel routes mainly use calcium nitrate as the calcium precursor. However, the toxic nitrate ions are usually removed by calcination（i.e. 550 8C or over）, which poses great...Bioactive calcium silicates prepared by sol–gel routes mainly use calcium nitrate as the calcium precursor. However, the toxic nitrate ions are usually removed by calcination（i.e. 550 8C or over）, which poses great challenge for the in situ preparation of inorganic/polymer composites, as polymer moieties could not survive such temperatures. In this study, we prepared 70Si30Ca（70 mol% Si O_2 and 30 mol%Ca O） bioactive glass at low temperatures where polymer could survive（i.e. 200 8C and 350 8C）, and proposed to remove the residual nitrate ions through soaking. Deionized water and simulated body fluid（SBF） were employed as the soaking medium. The results showed that the residual nitrate ions could be removed as quickly as 0.5 h while maintain the bioactivity of the samples. This technique may open the possibility of preparing sol–gel derived bioactive glass/polymer hybrids in situ with reduced potential toxicity.展开更多
The molecular dynamics method is used to investigate the interaction between one-six nitrate anions and water clusters absorbing six ozone molecules. The infrared（IR） absorption and reflection spectra are reshaped s...The molecular dynamics method is used to investigate the interaction between one-six nitrate anions and water clusters absorbing six ozone molecules. The infrared（IR） absorption and reflection spectra are reshaped significantly, and new peaks appear at Raman spectra due to the addition of ozone and nitrate anions to the disperse water system. After ozone and nitrate anions are captured, the average（in frequency） IR reflection coefficient of the water disperse system increased drastically and the absorption coefficient fell.展开更多
Chemical reduction of nitrate using metal nanoparticles has received increasing interest due to over-dependence on groundwater and consequence health hazard of the nitrate ion. One major drawback of this technique is ...Chemical reduction of nitrate using metal nanoparticles has received increasing interest due to over-dependence on groundwater and consequence health hazard of the nitrate ion. One major drawback of this technique is the agglomeration of nanoparticles leading to the formation of large floes. A low cost biopolymeric material, poly [β-（1-4）-2-amino-2-deoxy-D-glucopyranose] （β-PADG） obtained from deacetylated chitin was used as stabilizer to synthesize zero valent nickel （ZVNi） nanoparticles. The β-PADG-ZVNi nanocomposite was characterized using infra red （IR）, UV-Vis spectrophotometric techniques and Scanning Electron Microscope （SEM）. The morphology of the composite showed that β-PADG stabilized-ZVNi nanoparticles were present as discrete particles. The mean particle size was estimated to be （7.76 ± 2.98） nm and surface area of 87.10 m2/g. The stabilized-ZVNi nanoparticles exhibited markedly greater reactivity for reduction of nitrate in water with 100% conversion within 2 hr contact owing to less agglomeration. Varying the β-PADG-to-ZVNi ratio and the ZVNi-to-nitrate molar ratio generally led to a faster nitrate reduction. About 3.4-fold difference in the specific reaction rate constant suggests that the application of the β-PADG-stabilizer not only increased the specific surface area of the resultant nanoparticles, but also greatly enhanced the surface reactivity of the nanoparticles per unit area.展开更多
A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted...A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted porphyrin. The influence of nitrate salts and complex metal ion to the reaction were investigated. The extent of 2\|nitration increased with the electronegativity of the central metal. When Cu(NO 3 ) 2 · 3H 2O was used as nitrating reagent, almost quantitative yields of 2\|nitro porphyrin were obtained in the case of Cu(Ⅱ) or Ni(Ⅱ) chelates, while Zn(Ⅱ) or Mn(Ⅲ) chelates gave 50% and 30% yields respectively. If Zn(NO 3 ) 2 ·10H 2 O was used as nitrating agent, no product was found for Cu(Ⅱ) or Ni(Ⅱ) chelates, 12% was found for Zn(Ⅱ) chelates. The other metal ion and nitrate salts were also found in quite different influence.展开更多
Flow-electrode capacitive deionization(FCDI)represents a promising approach for ion separation from aqueous solutions.However,the optimization of spacer,particularly for nitrate-contaminated groundwa-ter systems,has o...Flow-electrode capacitive deionization(FCDI)represents a promising approach for ion separation from aqueous solutions.However,the optimization of spacer,particularly for nitrate-contaminated groundwa-ter systems,has often been overlooked.This research comprehensively investigates the influence of using a conductive(carbon cloth,CC)spacer on nitrate removal performance within FCDI system,comparing it to a non-conductive(nylon net,NN)spacer.In both CC and NN FCDI systems,it is unsurprisingly that nitrate removal efficiency improved notably with the increasing current density and hydraulic retention time(HRT).Interestingly,the specific energy consumption(SEC)for nitrate removal did not show obvious fluctuations when the current density and HRT varied in both systems.Under the auspiciously optimized process parameters,CC-FCDI attained a 20%superior nitrate removal efficiency relative to NN-FCDI,ac-companied by a notably diminished SEC for CC-FCDI,registering at a mere 28%of NN-FCDI.This great improvement can be primarily attributed to the decrement in FCDI internal resistance after using con-ductive spacer,which further confirmed by electrochemical tests such as linear sweep voltammetry(LSV)and electrochemical impedance spectroscopy(EIS).Upon prolonged continuous nitrate removal at the optimized conditions,the CC-FCDI system achieved a consistent 90%nitrate removal efficiency with a low SEC of 2.7-7.8 kWh/kg NO_(3)-N,underscoring its steady performance.Overall,this study highlights the pivotal importance of careful spacer design and optimization in realizing energy-efficient groundwater treatment via FCDI.展开更多
Atmospheric fine particulate matters (PM2.5) were collected with an Envirotech Instrument (Model APM 550) at the roof of Khundkur Mukarram Hussain Science Building, University of Dhaka, Bangladesh between January and ...Atmospheric fine particulate matters (PM2.5) were collected with an Envirotech Instrument (Model APM 550) at the roof of Khundkur Mukarram Hussain Science Building, University of Dhaka, Bangladesh between January and February, 2013. PM2.5 samples were collected on Quartz fiber filters during day and night time. Water soluble ions (sulfate, nitrate, phosphate, chloride, bromide, sodium, potassium and calcium) were analyzed with Ion Chromatography (Model 881, Metrohm Ltd., Switzerland) and Flame photometer (Model PFP7, Jenway, UK). Average PM2.5 mass was 136.1 μg·mDž during day time and 246.8 μg·mDž during night time with a total average of 191.4 μg·mDž. Nighttime PM2.5 concentration was about double compared than that of daytime presumable due to the low ambient temperatures with high emissions from heavy duty vehicles. The 24-hour average PM2.5 mass (average of day and night) was about eight times higher than WHO (25.0 μg·mDž) and about three times higher than DoE, Bangladesh (65.0 μg·mDž) limit values. The total average concentrations of sulfate, nitrate, phosphate, bromide, chloride, sodium, potassium and calcium were 5.30, 7.75, 0.62, 0.16, 1.19, 1.30, 8.11, and 3.09 μg·mDž, respectively. The concentrations of the water soluble ions were much higher during nighttime than daytime except nitrate, bromide and potassium. Excellent correlations were observed between sulfate and nitrate, sodium and chloride, bromide and phosphate indicating joint sources of origin. Potassium, sulfate, nitrate and calcium are the most dominant species in PM2.5. Water soluble ionic components in Dhaka contributed about 15% mass of the PM2.5. Ratio analysis showed that sodium and chloride were from mainly sea salt. Potassium has varieties of sources other than biomass burning. Sulfate and nitrate are mainly from fossil fuel origin. This is the first study of the day and night variation of the water soluble ionic species at the fine particulate matters (PM2.5) in Bangladesh.展开更多
基金This work was supported by the National Natural Science Foundation of China(Grant No.20173028).
文摘Both π and σ transition states on the potential energy surface of the nitration of benzene with nitronium ion have been successfully optimized using unrestricted hybrid DFT procedure B3LYP with the triple-zeta 6-311G ** basis set without any assumption. Subsequently, a σreactant-complex and a σ intermediate (Wheland intermediate) were located by the intrinsic reaction coordinate (IRC) calculation. The reaction pathway and the experimental observation lacking the kinetic isotopic effect in the title nitration were confirmed on geometries, atomic charges, energies, IR spectra and thermodynamic properties of all stationary points. The activation energy of 8.370 kJ/mol in the gas phase and the order of 1010 mol η L-1 η s-1 of rate constant were obtained for the reaction. The results both in thermodynamics and kinetics show that the electrophilic substitute mechanism is more preferable than the electron transfer mechanism of radical pairs. The solvent effect on the geometries of stationary points and the reaction mechanism were systematically studied for the nitration of benzene with nitronium by self-consistent reaction field (SCRF) technique with different dielectric constants of 5.0, 25.0, 50.0 and 78.5. It was then found that the solvent effect would depress the activation energy and finally make the formation of σ-TS without energy barrier in aqueous solution. Furthermore, the linear correlations given by charge migrations of NO2 group, dipole moments of solute, gaps of HOMO and LUMO and solvent stabilization energies in different solvents were demonstrated for both theoretically and experimentally concerned Wheland intermediate.
基金supported by the Youth Autonomous Innovation Funding from Army Engineering University of PLA(KYJBJKQTZQ23005)the Basic Discipline Incubation Funding from Army Engineering University of PLA(KYJBJKQTZK23011).
文摘Based upon the thiophene-2,5-dicarboxylic acid(H_(2)Tdc),a novel[Sc_(3)(μ_(2)-OH)_(3)(CO_(2))_(4)O_(6)]n inorganic chain-based Sc-MOF with decorated nitrate ions,{[Sc_(3)(OH)_(2)(Tdc)_(3)(NO_(3))]⋅H_(2)O}_(∞)(AEU-1;AEU for Army Engineering University of PLA),was synthesized,which shows good water and chemical stabilities.Significantly,due to channel constriction accompanied by the polar window caused by introducing nitrate ions,AEU-1 exhibits high C_(2)H_(6)/C_(2)H_(4)adsorption selectivity comparable to many famous C_(2)H_(6)-selective MOFs,making it a promising candidate for the purification of methanol-to-olefin(MTO)products.Furthermore,theoretical investigations reveal that the introduced nitrate ions in AEU-1 as the main adsorption sites could provide strong interactions between the framework and C2H6/C3H6 in the full-contacting mode,leading to an increase in the adsorption enthalpies(Qst)of C_(2)H_(6)and C_(3)H_(6),and thus further improving the C_(2)H_(6)/C_(2)H_(4)and C_(3)H_(6)/C_(2)H_(4)adsorption selectivity.Our work could open up a new avenue for constructing MOFs with inorganic polar moieties as adsorption sites for one-step C_(2)H_(4)purification and C3H6 recovery from MTO mixtures with high selectivity.
基金supported by an MCIN RyC Programme MCIN/AEI/10.13039/501100011033the‘European Union Next Generation EU/PRTR’under grant no.RYC2021-032345-I+1 种基金supported by the AEI(grant no.PID2019-107463RJ-I00/AEI/10.13039/501100011033)the Regional Research and Development Programme of the Government of Navarre(call 2019,project NitroHealthy,PC068).
文摘Ammonium toxicity in plants remains poorly understood despite extensive research.While nitrate is known to benefit plant growth,the synergistic effects of nitrate in mitigating ammonium toxicity,even at low concentrations,are not fully elucidated.This review delves into the physiological and molecular nature of this phenomenon.To date,nitrate-dependent alleviation of ammonium toxicity is the result of cumulative consequences of the role of nitrate as a nutrient and signal in plant performance.The ability to counteract the ammonium-induced acidification through nitrate uptake and metabolism,the enhancement of potassium uptake as an essential nitrate counterion,and the nitratedependent signaling of key factors involved in ammonium assimilation,ROS scavenging,and growth hormone biosynthesis,are the most relevant hallmarks.In addition,evidence suggests that the availability of nitrate and ammonium has driven ecological selection in plants,determining current N preferences,and may have led to the selection of nitrate-dependent and ammonium-sensitive domesticated crops and the inefficient use of N fertilizers in agriculture.As ammonium toxicity limits N fertilization options and reduces agricultural yields,when it could be a more sustainable and cheaper alternative to nitrate,this review provides a better understanding of how plants use nitrate to counteract the problematic aspects of ammonium nutrition.
基金Project supported by National High Technology Research and Development Program of China(863Program,2011AA03A405)
文摘La1-x Cax MnO3 （x=0-0.3） perovskite-type oxides were synthesized by citrate sol-gel method. The physical and chemical properties were characterized by X-ray diffraction （XRD）, Brumauer-Emmett-Teller method （BET）, X-ray photoelectron spectroscopy （XPS）, NO＋O2 -TPD （temperature-programmed desorption）, activated oxygen evaluation and H2 -TPR （temperature-programmed reduction） technologies. The results showed that NO catalytic oxidation activity was significantly improved by Ca substitution, especially for lower temperature activity. The La0.9 Ca0.1 MnO 3 sample showed the maximum conversion of 82% at 300 oC. The monodentate nitrates played a crucial role for the formation of NO2 . The reducibility of Mn 4＋ ions and reactivity of activated oxygen were favorable for the catalytic performances of NO oxidation.
文摘An extensive series of experiments was carried out in order to identify suitable catalysts to boost the reaction rate of wet air oxidation of real textile wastewaters at relatively mild temperature and pressure. Experimental results indicated that all catalysts tested in this investigation had shown an impressive increase in the initial COD and TOC removal rate as well as the COD and TOC removal levels in two hours reaction. Among all the catalysts tested, copper salts were more effective than the rest. Anions of the salt solutions also played a role in the catalytic process with nitrate ions having better effect than sulfate ions. Hence copper nitrates were more effective than copper sulfates. It was also found that a mixture of salts with different metals performed better than either of the component single salt alone.
文摘Nutrition is an important factor for the growth and development of plants. Among the main nutritional elements, there are nitrogen （N） and calcium （Ca）. The N comes from two forms of inorganic ions, ammonium （NH4＋） and nitrate （NO3） whose functions in the plant are the increase in leaf area and improving the succulence of many crops, among other essential physiological processes. Both the deficit and excess NO3- have a negative impact on plants increasing susceptibility to insect pests and pathogens, while Ca as divalent ion absorbed Ca2＋ plays an important role in control of physiological disorders and the resistance of plants to diseases to increase the mechanical strength. The N and Ca have a close relationship in the nutritional role of the plant, because the Ca absorption acting nitrates, so that a proper balance affects plants better growth and higher strength.
基金Supported by the National Special Fund for Major Research Instrumentation Development(No.2012YQ090229)the Instrument Functional Exploitation and Technical Innovation Fund,Chinese Academy of Sciences(No.yg2010072)the Shandong Provincial Technology Development Plan Fund(Nos.2011SJGZ06,2012SJGZ12,2012424012)
文摘An ion chromatographic method with a valve switching facility was developed to determine trace nitrate concentrations in seawater using two pumps, two different suppressors, and two columns. A carbohydrate membrane desalter was used to reduce the high concentrations of sodium salts in samples. In this method, trace nitrate was eluted from the concentrator column to the analytical columns, while the matrix fl owed to waste. Neither chemical pre-treatment nor sample dilution was required. In the optimized separation conditions, the method showed good linearity( R >0.99) in the 0.05 and 50 mg/L concentration range, and satisfactory repeatability(RSD<5%, n =6). The limit of detection for nitrate was 0.02 mg/L. Results showed that the valve switching system was suitable and practical for the determination of trace nitrate in seawater.
基金supported by the Natural Science Foundation of Beijing Municipal(No.8202052)the National Natural Science Foundation of China(Nos.21777191,42075082 and 41875147)+2 种基金S&T Development Fund of Chinese Academy of Meteorological Sciences(No.2020KJ001)Basic Research Fund of Chinese Academy of Meteorological Sciences(No.2020Z002)supported by the Innovation Team for Haze-fog Observation and Forecasts of Ministry of Science and Technology of the People’s Republic of China and China Meteorological Administration
文摘Air pollution in China is complex,and the formation mechanism of chemical components in particulate matter is still unclear.This study selected three consecutive heavy haze pollution episodes(HPEs)during winter in Beijing for continuous field observation,including an episode with heavy air pollution under red alert.Clean days during the observation period were selected for comparison.The HPE characteristics of Beijing in winter were:under the influence of adverse meteorological conditions such as high relative humidity,temperature inversion and low wind speed;and strengthening of secondary transformation reactions,which further intensified the accumulation of secondary aerosols and other pollutants,promoting the explosive growth of PM_(2.5).PM_(2.5)/CO values,as indicators of the contribution of secondary transformation in PM_(2.5),were approximately 2 times higher in the HPEs than the average PM_(2.5)/CO during the clean period.The secondary inorganic aerosols(sulfate nitrate and ammonium salt)were significantly enhanced during the HPEs,and the conversion coefficients were remarkably improved.In addition,it is interesting to observe that the production of sulfate tended to exceed that of nitrate in the late stage of all three HPEs.The existence of aqueous phase reactions led to the explosive growth sulfur oxidation ratio(SOR)and rapid generation of sulfate under high relative humidity(RH>70%).
文摘Egusi seed shells (ESS) were used as precursor for the preparation of two activated carbons (ACs) following H3PO4 and ZnCl2 activation. The effect of factors controlling the preparation of ACs such as chemical activating agent concentration (2 - 10 M), activation temperature (400°C - 700°C) and residence time (30 - 120 min) were optimized using the Box-Behnken Design (BBD). The optimized activated carbons based H3PO4 (ACP) and ZnCl2 (ACZ) were characterized by N2 adsorption, elemental analysis, atomic force microscopy (AFM), Boehm titration and Fourier transformed infrared (FTIR) techniques. The specific surface area was found to be 1053.91 and 1009.89 m2·g-1 for ACP and ACZ respectively. The adsorbents had similar surface functionalities and were both microporous. The effect of various parameters such as initial pH, concentration, and contact time on the adsorption of nitrate ions on ACP and ACZ in aqueous solution was studied. ACZ demonstrated better adsorption capacity (8.26 mg·g-1) compared to ACP (5.65 mg·g-1) at the same equilibrium time of 20 min. The adsorption process was governed by a “physical interactions” phenomenon for both adsorbents.
文摘Sorption recovery of palladium (II) from nitrate weak acidic model solutions and solutions of spent catalysts on some ion exchangers with different physical and chemical structure has been investigated. The palladium concentration in contacting solutions was 5.0 ? 10-5 – 1.0 ? 10-3 mol/L at nitric acid and potassium nitrate con-centrations 0.01 and 1.0 mol/L, respectively. It was shown that anion exchangers AV-17-8 as well as Purolite S 985 and A 500 possess the best sorption and kinetic properties. These sorbents can be recommended for selective recovery of palladium from solutions of spent catalysts.
基金supported by the research program of the Kookmin University in Korea
文摘Mesoporous titanium dioxide films were fabricated on titanium plates by micro-arc oxidation method.To increase the photocatalytic activity of the films,NH4NO3 was added to the H2SO4 solution,and anodizing was carried out at high voltages using a DC power supply.The crystal structure,chemical composition,surface morphology and the optical property of the films were investigated by XPS,XRD,UV-VIS spectroscopy and SEM.The photocatalytic activity of the films was evaluated by the decomposition of aniline blue,and the activity of the films for the degradation turned out to be improved by the additives to the electrolyte solution.The enhanced photocatalytic activity might result from the increased porosity and nitrate ion incorporation into the anodic films by micro arcing,and thereby the TiO2 layer might exhibit an improved absorption property for the visible light.
文摘Cheeses are characterized by several chemical-physical properties that make it difficult for the microorganisms growth, consequently. The actual European legislation allows the addition of few food additives in this type of food products. In this work, the entire procedure of extraction, purification, chromatographic separations and quali/quantitative determination of seven food additives (sorbic acid, benzoic acid, lactic acid, acetic acid, nitrites, nitrates and phosphates) was developed and applied for the analysis of different types of cheese (mozzarella, cheese spread, semi-hard and hard cheeses). Through validation procedure it was possible to evaluate the most important validation parameters. Extended calibration curves (r > 0.990) were obtained for all the analyzed compounds. Recovery values ranged from 72.8% to 98.4% and a good repeatability was obtained, with precision levels in the range of 0.03% - 0.11% (n = 6). The potential and feasibility of the method were tested by analysing real samples, such as mozzarella, cheese spread, semi-hard and hard cheeses, confirming that the method is well suited to satisfy the demands for accurate confirmation analyses of seven food additives in cheeses, which is especially valuable in official check analyses and in monitoring schemes.
基金supported by grants from the National Basic Research Program of China (973 Program, 2007CB109303)the National Natural Science Foundation of China (30871588 and 31000934)the Yangzhou University 'Crop Science' Project funded by the Priority Program of Jiangsu on Higher Education Institutions, China
文摘Plants need to be efficient in nutrient management, especially when they face the temporal nutrient defficiencies. Understanding how crops respond to nitrogen （N） starvation would help in the selection of crop cultivars more tolerant to N deficiency. In the present work, the physiological responses of two wheat cultivars, Yannong 19 （YN） and Qinmai 11 （QM）, to N starvation conditions were investigated. The two cultivars differed in biomass and N rearrangement between shoots and roots during N starvation. QM allocated more N to roots and exhibited higher root/shoot biomass ratio than YN. However, tissue measurement indicated that both cultivars had similar nitrate content in leaves and roots and similar remobilization rate in roots. Microelectrode measurement showed that vacuolar nitrate activity （concentration） in roots of QM was lower than that in roots of YN, especially in epidermal cells. Nitrate remobilization rates from root vacuoles of two cultivars were also identical. Moreover, vacuolar nitrate remobilization rate was proportional to vacuolar nitrate activity. During N starvation, nitrate reductase activity （NRA） was decreased but there were no significant differences between the two cultivars. Nitrate efflux from roots reduced after external N removal and QM seemed to have higher nitrate efflux rate.
基金supported by NSFC (Nos. 81470101, 51173193)Royal Society/Natural Science Foundation of China international exchange (No. 51411130151)
文摘Bioactive calcium silicates prepared by sol–gel routes mainly use calcium nitrate as the calcium precursor. However, the toxic nitrate ions are usually removed by calcination（i.e. 550 8C or over）, which poses great challenge for the in situ preparation of inorganic/polymer composites, as polymer moieties could not survive such temperatures. In this study, we prepared 70Si30Ca（70 mol% Si O_2 and 30 mol%Ca O） bioactive glass at low temperatures where polymer could survive（i.e. 200 8C and 350 8C）, and proposed to remove the residual nitrate ions through soaking. Deionized water and simulated body fluid（SBF） were employed as the soaking medium. The results showed that the residual nitrate ions could be removed as quickly as 0.5 h while maintain the bioactivity of the samples. This technique may open the possibility of preparing sol–gel derived bioactive glass/polymer hybrids in situ with reduced potential toxicity.
文摘The molecular dynamics method is used to investigate the interaction between one-six nitrate anions and water clusters absorbing six ozone molecules. The infrared（IR） absorption and reflection spectra are reshaped significantly, and new peaks appear at Raman spectra due to the addition of ozone and nitrate anions to the disperse water system. After ozone and nitrate anions are captured, the average（in frequency） IR reflection coefficient of the water disperse system increased drastically and the absorption coefficient fell.
文摘Chemical reduction of nitrate using metal nanoparticles has received increasing interest due to over-dependence on groundwater and consequence health hazard of the nitrate ion. One major drawback of this technique is the agglomeration of nanoparticles leading to the formation of large floes. A low cost biopolymeric material, poly [β-（1-4）-2-amino-2-deoxy-D-glucopyranose] （β-PADG） obtained from deacetylated chitin was used as stabilizer to synthesize zero valent nickel （ZVNi） nanoparticles. The β-PADG-ZVNi nanocomposite was characterized using infra red （IR）, UV-Vis spectrophotometric techniques and Scanning Electron Microscope （SEM）. The morphology of the composite showed that β-PADG stabilized-ZVNi nanoparticles were present as discrete particles. The mean particle size was estimated to be （7.76 ± 2.98） nm and surface area of 87.10 m2/g. The stabilized-ZVNi nanoparticles exhibited markedly greater reactivity for reduction of nitrate in water with 100% conversion within 2 hr contact owing to less agglomeration. Varying the β-PADG-to-ZVNi ratio and the ZVNi-to-nitrate molar ratio generally led to a faster nitrate reduction. About 3.4-fold difference in the specific reaction rate constant suggests that the application of the β-PADG-stabilizer not only increased the specific surface area of the resultant nanoparticles, but also greatly enhanced the surface reactivity of the nanoparticles per unit area.
文摘A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted porphyrin. The influence of nitrate salts and complex metal ion to the reaction were investigated. The extent of 2\|nitration increased with the electronegativity of the central metal. When Cu(NO 3 ) 2 · 3H 2O was used as nitrating reagent, almost quantitative yields of 2\|nitro porphyrin were obtained in the case of Cu(Ⅱ) or Ni(Ⅱ) chelates, while Zn(Ⅱ) or Mn(Ⅲ) chelates gave 50% and 30% yields respectively. If Zn(NO 3 ) 2 ·10H 2 O was used as nitrating agent, no product was found for Cu(Ⅱ) or Ni(Ⅱ) chelates, 12% was found for Zn(Ⅱ) chelates. The other metal ion and nitrate salts were also found in quite different influence.
基金supported by Shanxi Province Basic Research Program(Free Exploration Category)(No.202203021221041)National Natural Science Foundation of China(No.52300016)+1 种基金China Postdoctoral Science Foundation(No.2023M733379)Students Innovation and Entrepreneurship Foundation of USTC(No.CY2022G12).
文摘Flow-electrode capacitive deionization(FCDI)represents a promising approach for ion separation from aqueous solutions.However,the optimization of spacer,particularly for nitrate-contaminated groundwa-ter systems,has often been overlooked.This research comprehensively investigates the influence of using a conductive(carbon cloth,CC)spacer on nitrate removal performance within FCDI system,comparing it to a non-conductive(nylon net,NN)spacer.In both CC and NN FCDI systems,it is unsurprisingly that nitrate removal efficiency improved notably with the increasing current density and hydraulic retention time(HRT).Interestingly,the specific energy consumption(SEC)for nitrate removal did not show obvious fluctuations when the current density and HRT varied in both systems.Under the auspiciously optimized process parameters,CC-FCDI attained a 20%superior nitrate removal efficiency relative to NN-FCDI,ac-companied by a notably diminished SEC for CC-FCDI,registering at a mere 28%of NN-FCDI.This great improvement can be primarily attributed to the decrement in FCDI internal resistance after using con-ductive spacer,which further confirmed by electrochemical tests such as linear sweep voltammetry(LSV)and electrochemical impedance spectroscopy(EIS).Upon prolonged continuous nitrate removal at the optimized conditions,the CC-FCDI system achieved a consistent 90%nitrate removal efficiency with a low SEC of 2.7-7.8 kWh/kg NO_(3)-N,underscoring its steady performance.Overall,this study highlights the pivotal importance of careful spacer design and optimization in realizing energy-efficient groundwater treatment via FCDI.
文摘Atmospheric fine particulate matters (PM2.5) were collected with an Envirotech Instrument (Model APM 550) at the roof of Khundkur Mukarram Hussain Science Building, University of Dhaka, Bangladesh between January and February, 2013. PM2.5 samples were collected on Quartz fiber filters during day and night time. Water soluble ions (sulfate, nitrate, phosphate, chloride, bromide, sodium, potassium and calcium) were analyzed with Ion Chromatography (Model 881, Metrohm Ltd., Switzerland) and Flame photometer (Model PFP7, Jenway, UK). Average PM2.5 mass was 136.1 μg·mDž during day time and 246.8 μg·mDž during night time with a total average of 191.4 μg·mDž. Nighttime PM2.5 concentration was about double compared than that of daytime presumable due to the low ambient temperatures with high emissions from heavy duty vehicles. The 24-hour average PM2.5 mass (average of day and night) was about eight times higher than WHO (25.0 μg·mDž) and about three times higher than DoE, Bangladesh (65.0 μg·mDž) limit values. The total average concentrations of sulfate, nitrate, phosphate, bromide, chloride, sodium, potassium and calcium were 5.30, 7.75, 0.62, 0.16, 1.19, 1.30, 8.11, and 3.09 μg·mDž, respectively. The concentrations of the water soluble ions were much higher during nighttime than daytime except nitrate, bromide and potassium. Excellent correlations were observed between sulfate and nitrate, sodium and chloride, bromide and phosphate indicating joint sources of origin. Potassium, sulfate, nitrate and calcium are the most dominant species in PM2.5. Water soluble ionic components in Dhaka contributed about 15% mass of the PM2.5. Ratio analysis showed that sodium and chloride were from mainly sea salt. Potassium has varieties of sources other than biomass burning. Sulfate and nitrate are mainly from fossil fuel origin. This is the first study of the day and night variation of the water soluble ionic species at the fine particulate matters (PM2.5) in Bangladesh.
