Competitive binding of CU2+ and Zn2+ to live cells of shewanella putrefaciens

Binding of Cu2+ and Zn2+ to live cells of Shewanella putrefaciens was measured at pH 4, 5.5, and 7 for dissolved metal concentrations ranging from 0.1 to 100 microM. Release of organic compounds by the cells resulted in concentrations of dissolved organic carbon (DOC) between 0.5 and 1.6 mM. A discrete site, nonelectrostatic model was used to describe Cu2+ and Zn2+ binding to the cells. Binding of Zn2+, which increased with increasing pH over the entire range of dissolved Zn2+ concentration, could be explained by invoking two types of cell wall binding sites: acidic and neutral functional groups. Binding of Cu2+ exhibited a more complex pH dependence: at dissolved metal concentrations below 1 microM, binding to the cells actually increased with decreasing pH. This behavior could be reproduced by (1) assuming the existence of a small fraction of high-affinity binding sites in the cell wall (approximately 5%) and (2) including metal complexation by dissolved organic ligands. The latter compete with the neutral cell wall groups and decrease Zn2+ and Cu2+ binding at pH 5.5 and 7. The observed isotherms implied that binding of the metals was only weakly affected by cell wall charging. Model parameters derived from the single-metal binding isotherms were able to account for the observed competition of Zn2+ and Cu2+ for cell wall sites when both metals were present.     

Cations reduce antimicrobial efficacy of lysozyme-chelator combinations

Reduction of the antimicrobial efficacy of lysozyme-chelator combinations against two Escherichia coli O157:H7 strains on addition of mineral salts was studied. The objective of the study was to determine the effect of type and concentration of mono-, di-, and trivalent mineral salts on the antimicrobial effectiveness of lysozyme and various chelators against E. coli O157:H7. Seven salts (Al3+, Ca2+, Fe2+, Fe3+, K+, Mg2+, and Na+) at 1 to 10 mM were added to aqueous solutions of lysozyme and disodium ethylenediamine tetraacetic acid (EDTA), disodium pyrophosphate (DSPP), or pentasodium tripolyphosphate (PSTPP) at pH 6, 7, or 8 and applied to cultures of E. coli O157:H7 strains 932 and H1730. Inhibitory activity of lysozyme chelator combinations against both strains was completely lost after addition of > or = 1 mM Ca2+ and Mg2+ at pH 7 and 8. At pH 6, antimicrobial activity of lysozyme-EDTA against both strains was retained in the presence of calcium or magnesium cations. DSPP-lysozyme inhibited strain H1730 at pH 6 despite the presence of Mg2+. Concentrations above 4 mM Fe2+ neutralized activity of all lysozyme-chelator combinations. Reversal of inhibition by lysozyme-chelator complexes by the monovalent Na+ and K+ ions depended on E. coli O157:H7 strain type. Neither monovalent cation reversed inhibition of strain 932. However, Na+ and K+ reversed lysozyme-chelator inhibition of strain H1730. The addition of > or = 1 mM Fe3+ or Al3+ was effective in reversing inhibition of both strains by lysozyme and EDTA at pH 6, 7, and 8. Isothermal titration calorimetry was used to determine the amount of ion-specific competitive binding of free cations by EDTA-lysozyme combinations. A mechanistic model for the antimicrobial functionality of chelator-lysozyme combinations is proposed.     

Combining spectroscopic and potentiometric approaches to characterize competitive binding to humic substances

In an area that contains high concentrations of natural organic matter, it is expected that it plays an important role on the behavior of rare earth elements (REE), like europium, and of trivalent actinides. Competitive interactions with H+, inorganic species, major cations, e.g. Ca(II) or Mg(II), could influence these metals transport and bioavailability. Competitive experiments between cations, which can bind differently to humic substances and Eu3+, will bring an improved understanding of the competitive mechanisms. The aim of this study is to acquire data for Eu(III)/Cu(II) and Eu(III)/Ca(II) competitive binding to a sedimentary originated humic acid (Gorleben, Germany). The NICA-Donnan parameters for Ca2+, Cu2+, and Eu3+ obtained from competitive binding experiments using Ca2+ or Cu2+ ion selective electrodes were used to model time-resolved laser fluorescence spectroscopy (TRLFS) measurements. Eu3+ and CU2+ are in direct competition for the same type of sites, whereas Ca2+ has an indirect influence through electrostatic binding.     

木薯块根中β-葡萄糖苷酶的分离纯化及酶学性质

研究了木薯块根中β-葡萄糖苷酶的分离纯化及酶学性质。以缓冲液从木薯块根中获得粗提酶液,粗酶酶活力为9.37 U/g木薯干重;再分别通过丙酮沉淀、离子交换层析和凝胶过滤层析进行纯化,β-葡萄糖苷酶酶活力为1.14 U/g木薯干重,经纯化β-葡萄糖苷酶纯度提高了14.62倍,总活力回收率为12.14%,电泳测得其分子量约70 kDa。该酶米氏常数K_m为3.60 mmol/L,V_max为12.36μmol/(min·mg protein);其最适pH为7.0,pH在6.0～8.0之间有较好的稳定性;在40℃以内有良好稳定性,在4℃存放30 d酶活力剩余81.78%。Mn²⁺和K⁺对酶有一定的促进作用,Al³⁺、Cu²⁺、Mg²⁺、Zn²⁺、Ca²⁺、Ba²⁺、Na⁺、尿素和SDS对酶没有显著影响(P>0.05),而Fe³⁺、F...     

羊初乳热稳定性研究初探

本文以不同泌乳期的羊初乳为原料,研究了不同泌乳期的初乳的热稳定性,以及酸度,添加物磷酸盐、柠檬酸盐、蔗糖、钙离子、卡拉胶等对初乳热稳定性的影响。结果表明:初乳的热稳定性随泌乳期和pH值的增大而增大;磷酸盐、柠檬酸盐、蔗糖均对初乳的热稳定性有改善作用;而钙离子、卡拉胶使初乳的热稳定性下降。在80℃下初乳热稳定性改善最适条件为:pH6.9,柠檬酸0.02mol/L,磷酸盐0.2mol/L,蔗糖30%。     

Geochemical modulation of pesticide sorption on smectite clay

Pesticide adsorption by soil clays can be dramatically influenced by the exchangeable cations present. Among the common exchangeable base cations in soils (Ca2+, Mg2+, K+, and Na+), K+-saturated clays frequently demonstrate the strongest affinity for pesticides. In the presence of multiple exchangeable cations in the system, we hypothesize that the magnitude of pesticide sorption to soil minerals is proportional to the fraction of clay interlayers saturated with K+ ions. To test this hypothesis, we measured sorption of three pesticides with different polarities (dichlobenil, monuron, and biphenyl) by homoionic K- and Ca-smectite (SWy-2) in KCl/CaCl2 aqueous solutions. The presence of different amounts of KCl and CaCl2 resulted in varying populations of K+ and Ca2+ on the clay exchange sites. The sorption of dichlobenil and, to a lesser extent monuron, increased with the fraction of K+ on clay mineral exchange sites. Ca- and K-SWy-2 displayed the same sorption capacities for nonpolar biphenyl. X-ray diffraction patterns indicated that at lower fractions of K+-saturation, exchangeable K+ ions were randomly distributed in clay interlayers and did not enhance pesticide sorption. At higher populations of K+ (vs Ca2+), demixing occurred causing some clay interlayers, regions, or tactoids to become fully saturated by K+, manifesting greatly enhanced pesticide sorption. The forward and reverse cation exchange reactions influenced not only K+ and Ca2+ populations on clays but also the nanostructures of clay quasicrystals in aqueous solution which plays an important, if not dominant, role in controlling the extent of pesticide sorption. Modulating the cation type and composition on clay mineral surfaces through cation exchange processes provides an environmental-safe protocol to manipulate the mobility and availability of polar pesticides, which could have applications for pesticide formulation and in environmental remediation.     

Characterization of sorption sites on Pilayella littoralis and metal binding assessment using 113Cd and 27Al nuclear magnetic resonance

Metal interactions with the cellular structures of the marine alga Pilayella littoralis have been investigated to better understand how biomaterials sorb dissolved metals. Algae metal binding capacity at pH 5.0 was 2000, 850, 430, and 560 micromol g(-1) of dried material for Al(III), Cu(II), Cd(II), and Co(II), respectively. Binding site characterization was assessed by 1H and 13C nuclear magnetic resonance spectroscopy. Also, Fourier Transform Infrared spectroscopy (FTIR) provided some information about the types of functional groups that appear to be present in the algal material. The results suggested the presence of carboxylate, ether, amino, and hydroxyl groups. Investigation of metal competition for the alga binding sites was performed using 27Al and 113Cd NMR spectroscopy, which proved to be a valuable technique for Al and Cd sorption assessment. Aluminum and Cu were efficiently sorbed by the alga sites, and the binding affinity order of these metals was Al(III) > Cu(II) > Cd(II) > Co(II).     

盐地碱蓬红色素的提取工艺及稳定性研究

本研究以盐地碱蓬为原料,对碱蓬红色素的提取工艺以及光、热、pH值、氧化还原剂、糖、金属离子等对色素稳定性的影响进行了研究。结果表明：碱蓬红色素易溶于水而不溶于纯有机溶剂,最大吸收峰为538nm,初步确定碱蓬红色素为甜菜红素;较佳提取条件为：以水为提取剂,浸提温度40℃,浸提时间10min,料液比1:25(g/ml); 碱蓬红色素的耐光、耐热、耐氧化性较差,对还原剂有一定耐受性,适用pH 值范围为4～7;糖以及金属离子Fe3+、Fe2+、Mg2+、Ca2+ 对色素稳定性基本无影响,而Zn2+、Na+、K+、Al3+ 对色素的稳定性具有一定的影响。     

A biotic ligand model predicting acute copper toxicity for Daphnia magna: the effects of calcium, magnesium, sodium, potassium, and pH

The extent to which Ca2+, Mg2+, Na+, K+ ions and pH independently mitigate acute copper toxicity for the cladoceran Daphnia magna was examined. Higher activities of Ca2+, Mg2+, and Na+ (but not K+) linearly increased the 48-h EC50 (as Cu2+ activity), supporting the concept of competitive binding of these ions and copper ions to toxic action or transport sites at the organism-water interface (e.g. fish gill, the biotic ligand). The increase of the EC50 (as Cu2+ activity) with increasing H+, however, seemed to suggest cotoxicity of CuOH+ rather than proton competition. Based on the biotic ligand model (BLM) concept, we developed a methodology to estimate stability constants for the binding of Cu2+, CuOH+, Ca2+, Mg2+, Na+, and H+ to the biotic ligand, solely based on toxicity data. Following values were obtained: log K(CuBL) = 8.02, log K(CuOHBL)= 7.45, log K(CaBL) = 3.47, log K(MgBL) = 3.58, log K(NaBL) = 3.19, and log K(HBL) approximately 5.4. Further, we calculated that on average 39% of the biotic ligand sites need to be occupied by copper to induce a 50% acute effect for D. magna after 48 h of exposure. Using the estimated constants, a BLM was developed that can predict acute copper toxicity for D. magna as a function of water characteristics. The presented methodology can easily be applied for BLM development for other organisms and metals. After validation with laboratory and natural waters (including DOC), the developed model will support efforts to improve the ecological relevance of presently applied risk assessment procedures.     

Characterization of metal-cyanobacteria sorption reactions: a combined macroscopic and infrared spectroscopic investigation

In this study, we conducted synchrotron radiation Fourier transform infrared (IR) spectroscopy, potentiometric titration, and metal sorption experiments to characterize metal-cyanobacteria sorption reactions. Infrared spectra were collected with samples in solution for intact cyanobacterial filaments and separated exopolymeric sheath material to examine the deprotonation reactions of cell surface functional groups. The infrared spectra of intact cells sequentially titrated from pH 3.2 to 6.5 display an increase in peak intensity and area at 1400 cm(-1) corresponding to vibrational COO- frequencies from the formation of deprotonated carboxyl surface sites. Similarly, bulk acid-base titration of cyanobacterial filaments and sheath material indicates that the concentration of proton-active surface sites is higher on the cell wall compared to the overlying sheath. A three-site model provides an excellent fit to the titration curves of both intact cells and sheath material with corresponding pKa values of 4.7 +/- 0.4, 6.6 +/- 0.2, 9.2 +/- 0.3 and 4.8 +/- 0.3, 6.5 +/- 0.1, 8.7 +/- 0.2, respectively. Finally, Cu2+, Cd2+, and Pb2+ sorption experiments were conducted as a function of pH, and a site-specific surface complexation model was used to describe the metal sorption data. The modeling indicates that metal ions are partitioned between the exopolymer sheath and cell wall and that the carboxyl groups on the cyanobacterial cell wall are the dominant sink for metals at near neutral pH. These results demonstrate that the cyanobacterial surfaces are complex structures which contain distinct surface layers, each with unique molecular functional groups and metal binding properties.     

Arsenate and arsenite adsorption and desorption behavior on coprecipitated aluminum:iron hydroxides

Although arsenic adsorption/desorption behavior on aluminum and iron (oxyhydr)oxides has been extensively studied, little is known about arsenic adsorption/desorption behavior by bimetal Al:Fe hydroxides. In this study, influence of the Al:Fe molar ratio, pH, and counterion (Ca2+ versus Na+) on arsenic adsorption/desorption by preformed coprecipitated Al:Fe hydroxides was investigated. Adsorbents were formed by initial hydrolysis of mixed Al3+/ Fe3+ salts to form coprecipitated Al:Fe hydroxide products. At Al:Fe molar ratios < or = 1:4, Al3+ was largely incorporated into the iron hydroxide structure to form a poorly crystalline bimetal hydroxide; however, at higher Al:Fe molar ratios, crystalline aluminum hydroxides (bayerite and gibbsite) were formed. Although approximately equal As(V) adsorption maxima were observed for 0:1 and 1:4 Al:Fe hydroxides, the As(III) adsorption maximum was greater with the 0:1 Al: Fe hydroxide. As(V) and As(III) adsorption decreased with further increases in Al:Fe molar ratio. As(V) exhibited strong affinity to 0:1 and 1:4 Al:Fe hydroxides at pH 3-6. Adsorption decreased at pH > 6.5; however, the presence of Ca2+ compared to Na+ as the counterion enhanced As( retention by both hydroxides. There was more As(V) and especially As(III) desorption by phosphate with an increase in Al:Fe molar ratio.     

树脂法提取野酸梅皮色素工艺研究

研究大孔树脂分离纯化野酸梅皮色素的条件与方法,并对树脂法所得色素的性质进行检测。结果表明：D101树脂对野酸梅皮色素的吸附效果最佳,以体积分数80%乙醇溶液作洗脱剂洗脱效果较好;野酸梅果皮色素在酸性条件下(pH≤4)较为稳定,耐光、热性较差;金属离子Al3+、Fe3+、Mg2+、Cu2+、Na+对野酸梅果皮色素有不同程度的降色作用。     

羊奶脂肪酶特性的研究

对影响羊乳脂肪酶活性的温度、pH以及金属离子进行了研究。结果表明,羊奶中脂肪酶在37℃时活性最高,在40⁵0℃时具有较高的热稳定性;羊奶脂肪酶最适pH为6.5,在pH5.0⁶.5时稳定性较高;Ca2+和Fe2+对脂肪酶具有激活作用,而K+、Zn2+、Cu2+、Mn2+和Mg2+对脂肪酶具有抑制作用,低浓度的Al3+和Fe3+对脂肪酶活性具有抑制作用,而高浓度的Al3+和Fe3+对脂肪酶具有激活作用。      

茶绿色素稳定性的研究

对茶绿色素的稳定性进行研究.结果表明:荼绿色素的光谱特性在663 nm为特征吸收峰;茶绿色素对热较稳定;金属离子K+、Na+、Zn2+、Cu2+、Mg2+,Ca2+对该色素的稳定性影响较小,Al3+、Fe2+和Fe3+对其稳定性有明显的影响或破坏作用;pH对该色素的影响明显,在弱酸性条件下(pH=5～6)稳定性较好;光对该色素的稳定性影响较大;苯甲酸钠对该色素的稳定性影响较小;该色素抗氧化性较弱,抗还原性较强.     

萝卜红天然食用色素的提取及理化性质的研究

从萝卜中提取了食用色素。色素的理化性质表明 :pH值不同 ,色素吸收光谱不同 ,pH =3～ 4时 ,色素最大吸收波长为 5 14nm ,有一定的耐光性和耐热性 ;柠檬酸、苯甲酸、淀粉和NaCl的加入使色素增色 ,糖类加入使色素稍微减色 ,Cu2 +、Al3+、Fe3+使色素变色 ,K+、Na+、Ca2 +、Zn2 +、Mg2 +对色素无不良影响。     

香椿叶中提取槲皮素的稳定性研究

研究了槲皮素溶液稳定性的影响因素。结果表明，槲皮素溶液在pH=6．59～7．90条件下比较稳定；在还原剂Na2SO3,NaS2O3中不稳定，而在氧化剂H2O2中较为稳定；碳水化合物对槲皮素溶液的稳定性没有明显的影响；金属离子K^＋、Ca^2＋、Na^＋、Al^3＋对槲皮素溶液具有稳定作用，Mg^2＋、Zn^2＋、Fe^3＋对槲皮素溶液的稳定性有不利的影响；高温、自然光照射对槲皮素具有降解作用。     

金属离子Cu2+、Ca2+和Mg2+对抗蚜威与DNA结合作用的影响

在人体生理酸度(pH7.4)下,运用紫外、荧光光谱法和DNA 熔点实验研究抗蚜威与小牛胸腺DNA 的作用方式以及Cu2+、Ca2+ 和Mg2+ 分别对两者结合的影响。溴化乙锭(EB)竞争实验和DNA 熔点测定结果表明,抗蚜威主要是通过嵌插方式与DNA 碱基发生作用。3 种金属离子均能与抗蚜威络合,络合物的生成使体系的紫外吸收峰强度和形状发生改变,并能不同程度地猝灭DNA-EB 复合物的荧光;Cu2+、Ca2+ 的存在使DNA- 抗蚜威复合物的结合常数呈现先减弱后增强的趋势,而Mg2+ 的参与能增强两者之间的结合。由此推断出,金属离子对抗蚜威与DNA 结合的影响主要取决于金属离子与DNA 的碱基和磷酸基团间结合的相对亲和比。     

Role of surface alteration in determining the mobility of U(VI) in the presence of citrate: implications for extraction of U(VI) from soils

In the present study, the adsorption of U(VI) by a natural iron-rich sand in the presence of citrate was studied over a range of citrate concentrations and pH values. Adsorption of U(VI) on the iron-rich sand decreased in the presence of increasing concentrations of citrate. Adsorption of citrate to the sand was weak under most conditions studied. Several explanations for the adsorption behavior of U(VI) and citrate were investigated, including aqueous complexation of U(VI) by citrate, competition of U(VI) and citrate for adsorption sites, and extraction of Fe and Al from the sorbent surface by citrate (surface alteration). Although aqueous complexation of U(VI) by citrate may still play a significant role, both competitive adsorption and aqueous complexation proved to be inadequate explanations of the adsorption behavior. Both physical surface alteration (i.e., loss of surface area) and chemical surface alteration (i.e., change in the chemical composition of the sand surface) were investigated, with chemical surface alteration controlling the bulk of U(VI) adsorption. Considering these results, remediation schemes that involve organic complexing agents should address the possibility of surface alteration affecting radionuclide adsorption and mobility.     

离子交换纤维对糖液中钙离子的脱除

研究了强酸离子交换纤维对糖液中钙离子的吸附动力学和吸附等温线。试验表明 ,纤维对糖液中钙离子的吸附速度明显快于 732型树脂。吸附平衡等温线符合Langmuir方程。糖液操作流速在 4mL/min以内时 ,纤维动态吸附速度也很快 ,且糖液浓度对吸附速度影响较小 ,动态饱和吸附量可达 47mg/g干纤维。该纤维可用于糖液的除钙。     

Zinc toxicity to nitrification in soil and soilless culture can be predicted with the same biotic ligand model

The inhibitory effect of Zn on the nitrification process in ZnCl2 spiked soils (12 soils, pH range 4.8-7.5) was compared to toxic effects of Zn on the nitrification by Nitrosospira sp. in soilless solutions with varying pH (pH 6-8) and ionic composition. The nitrification was reduced by 20% at Zn solution concentrations (EC20) ranging between 7 and 1200 microM Zn in the soil pore water and between 5 and 150 microM Zn in the soilless solutions. Protective effects of H+, Ca2+, and Mg2+ against Zn2+ toxicity were observed in both systems. Zinc speciation was determined, and 60-90% of the Zn in the soils and 35-80% of the Zn in the soilless solutions was present as Zn2+. A biotic ligand model and a Freundlich-type model, incorporating the competition of Zn2+ ions with H+, Ca2+, and Mg2+ for binding on the biotic ligands, were used to model the results. The Zn2+ activities resulting in 20% reduction of the nitrification were well predicted using the same parameters for both (soil and soilless) systems, indicating that microorganisms in soil are exposed to zinc through the free zinc ion in soil pore water.