Zeta potential of anoxygenic phototrophic bacteria and Ca adsorption at the cell surface: possible implications for cell protection from CaCO3 precipitation in alkaline solutions

Electrophoretic mobility measurements and surface adsorption of Ca on living, inactivated, and heat-killed haloalkaliphilic Rhodovulum steppense, A-20s, and halophilic Rhodovulum sp., S-17-65 anoxygenic phototrophic bacteria (APB) cell surfaces were performed to determine the degree to which these bacteria metabolically control their surface potential equilibria. Zeta potential of both species was measured as a function of pH and ionic strength, calcium and bicarbonate concentrations. For both live APB in 0.1M NaCl, the zeta potential is close to zero at pH from 2.5 to 3 and decreases to -30 to -40 mV at pH of 5-8. In alkaline solutions, there is an unusual increase of zeta potential with a maximum value of -10 to -20 mV at a pH of 9-10.5. This increase of zeta potential in alkaline solutions is reduced by the presence of NaHCO(3) (up to 10 mM) and only slightly affected by the addition of equivalent amount of Ca. At the same time, for inactivated (exposure to NaN(3), a metabolic inhibitor) and heat-killed bacteria cells, the zeta potential was found to be stable (-30 to -60 mV, depending upon the ionic strength) between pH 5 and 11 without any increase in alkaline solutions. Adsorption of Ca ions on A-20s cells surface was more significant than that on S-17-65 cells and started at more acidic pHs, consistent with zeta potential measurements in the presence of 0.001-0.01 mol/L CaCl(2). Overall, these results indicate that APB can metabolically control their surface potential to electrostatically attract nutrients at alkaline pH, while rejecting/avoiding Ca ions to prevent CaCO(3) precipitation in the vicinity of cell surface and thus, cell incrustation.     

Dispersion stability of a ceramic glaze achieved through ionic surfactant adsorption

The adsorption of cetylpyridinium chloride (CPC) and sodium dodecylbenzenesulfonate (SDBS) onto a ceramic glaze mixture composed of limestone, feldspar, quartz, and kaolin has been investigated. Both adsorption isotherms and the average particle zeta potential have been studied in order to understand the suspension stability as a function of pH, ionic strength, and surfactant concentration. The adsorption of small amounts of cationic CPC onto the primarily negatively charged surfaces of the particles at pH 7 and 9 results in strong attraction and flocculation due to hydrophobic interactions. At higher surfactant concentrations a zeta potential of more than +60 mV results from the bilayered adsorbed surfactant, providing stability at salt concentrations < or = 0.01 M. At 0.1 M salt poor stability results despite substantial zeta potential values. Three mechanisms for SDBS adsorption have been identified. When anionic SDBS monomers either adsorb by electrostatic interactions with the few positive surface sites at high pH or adsorb onto like charged negative surface sites due to dispersion or hydrophobic interactions, the magnitude of the negative zeta potential increases slightly. At pH 9 this increase is enough to promote stability with an average zeta potential of more than -55 mV, whereas at pH 7 the zeta potential is lower at about -45 mV. The stability of suspensions at pH 7 is additionally due to steric repulsion caused by the adsorption of thick layers of neutrally charged Ca(DBS)2 complexes created when the surfactant interacts with dissolved calcium ions from the calcium carbonate component.     

Electrokinetic properties of sepiolite suspensions in different electrolyte media

The present paper deals with the electrokinetic characterization of sepiolite. A series of systematic zeta potential measurements have been carried out to determine the isoelectric point (iep) and potential-determining ions (pdi), and the effect of mono-, di-, and trivalent electrolytes such as NaCl, KCl, LiCl, NaNO(3), NaCH(3)COO, MgCl(2), CaCl(2), BaCl(2), CoCl(2), CuCl(2), Pb(NO(3))(2), Na(2)CO(3), Na(2)SO(4), AlCl(3), FeCl(3), and Na(3)PO(4) on the zeta potential of sepiolite. Zeta potential has been calculated with the aid of Smoluchowski's equation. Sepiolite yields an isoelectric point at pH 6.6. The zeta potential for the sepiolite has ranged from +23.3 mV at pH approximately 2 to -22.4 mV at pH approximately 8 at 20 +/- 2 degrees C in water. The valency of the ions have proven to have a great influence on the electrokinetic behavior of the suspension. Monovalent cations were found to have a weak effect, while di- and trivalent cations made the zeta potential positive. Charge reversal was observed for divalent cations at 1 x 10(-2) M and for trivalent cations at 3 x 10(-4) M. As a result, it can be said that monovalent cations are indifferent ions when di- and trivalent cations are potential-determining ions.     

Effects of heavy metals and oxalate on the zeta potential of magnetite

Zeta potential is a function of surface coverage by charged species at a given pH, and it is theoretically determined by the activity of the species in solution. The zeta potentials of particles occurring in soils, such as clay and iron oxide minerals, directly affect the efficiency of the electrokinetic soil remediation. In this study, zeta potential of natural magnetite was studied by conducting electrophoretic mobility measurements in single and binary solution systems. It was shown that adsorption of charged species of Co(2+), Ni(2+), Cu(2+), Zn(2+), Pb(2+), and Cd(2+) and precipitation of their hydroxides at the mineral surface are dominant processes in the charging of the surface in high alkaline suspensions. Taking Pb(2+) as an example, three different mechanisms were proposed for its effect on the surface charge: if pH<5, competitive adsorption with H(3)O(+); if 56, precipitation of heavy metal hydroxides prevails. Oxalate anion changed the associated surface charge by neutralizing surface positive charges by complexing with iron at the surface, and ultimately reversed the surface to a negative zeta potential. Therefore the adsorption ability of heavy metal ions ultimately changed in the presence of oxalate ion. The changes in the zeta potentials of the magnetite suspensions with solution pH before and after adsorption were utilized to estimate the adsorption ability of heavy metal ions. The mechanisms for heavy metals and oxalate adsorption on magnetite were discussed in the view of the experimental results and published data.     

Evaluating the surface charge of C18 stationary phases

The surface charge of four C18 stationary phases was investigated by measuring the flow induced streaming potential, a well known electrokinetic property of charged surfaces. Three of the stationary phases (Symmetry, Gemini, and Xterra-MS) had significantly positive streaming potentials at both pH 3 and 4.5. The fourth (Zorbax-SB) appeared to be essentially neutral at pH 3 and became negative at pH 4.5. Apparent zeta potentials ranged from approximately +16 to -4 mV. The retention behavior was also investigated using chloride as model anion and glycinamide (in its protonated form) as model cation. When the retention factor (k) of glycinamide was subtracted from k of chloride anion, the resulting delta k values showed very similar trends as apparent zeta potential values, suggesting that the simple chromatographic method could be used to estimate zeta potential values, or that the zeta potential values could be useful for ranking columns according to ion exchange or exclusion behavior. The anion exchange capacity of the Symmetry and Gemini columns was also estimated, using a published chromatographic procedure, and the results suggest about 2 microEq. capacity per gram of packing.     

Characterizing zeta potential of functional nanofibers in a microfluidic device

The measurement of surface charge on nanofibers was achieved by characterizing zeta potential of the nanofibers via a newly developed device for streaming current measurement. Low flow rates were sufficient to generate detectable streaming currents in the absence of an externally applied voltage without damaging nanofiber samples. Zeta potential was calculated by using the Helmholtz-Smoluchowski equation and the measured streaming currents. Two acrylic plates were machined and assembled to form a microfluidic channel that is 150 μm high, 2.0mm wide, and 30 mm long. Two electrodes for the measurement of streaming currents were housed in the top plate. Two nanofibers of pure polyacrylonitrile (PAN) fibers and charged (TiO(2) incorporated) PAN fibers were prepared and characterized in the device. Monobasic sodium phosphate and dibasic sodium phosphate were used to prepare four different pH buffer solutions ranging from pH 5 to pH 8 in order to characterize the zeta potentials. The pure PAN nanofibers had negatively-charged surfaces regardless of pH. However, the zeta potentials of PAN/TiO(2) nanofibers changed from positive to negative at pH 6.5. The zeta potential measurements made on the nanofibers in this new microfluidic device matched with those of the powdered raw materials using a commercial Zetasizer.     

Temperature and pressure effects on zeta potential values of reservoir minerals

An experimental study of the effect of temperature and pressure on zeta potential of typical reservoir minerals, including quartz, kaolinite, and calcite, is presented. Experiments included the design and construction of an electrophoretic cell for zeta potential measurements at variable pressure and temperature. Electrolyte concentration was varied in the range from 0.0001 to 0.1 M in the pH range from 2 to 9. For all the minerals it is found that the zeta potential decreases with temperature at a rate characteristic of each mineral; values are around -2.3 mV/degrees C for quartz, -0.96 mV/degrees C for kaolinite, and -2.1 mV/degrees C for calcite for pressure values less than 45 psi. The effect of pressure is found to depend on the mineral nature and pH of the electrolytic solution. In the case of quartz, a systematic increase in the value of the zeta potential with pressure is observed, whereas a decreasing trend is measured for the kaolinite. In the case of calcite, a decreasing trend is observed for pressures up to 45 psi, whereas the experimental data suggest an increasing trend for higher pressure values.     

Determination of intrinsic bacterial surface acidity constants using a donnan shell model and a continuous pK(a) distribution method

Intrinsic acidity constants (pK(a)(int)) for Bacillus subtilis (Gram+) and Escherichia coli (Gram-) cells were calculated from potentiometric titration data at different salt concentrations. Master curves were generated by replotting charge excess data as a function of pH(S) (pH at the location of surface reactive sites) where pH(S) was determined as a function of Donnan potential, Psi(DON). This potential decreased in magnitude with increasing ionic strength, from -48.5+/-0.2 to -3.5+/-0.0 mV for B. subtilis and -47.9+/-0.3 to -3.5+/-0.0 mV for E. coli at 0.01 and 0.5 M K(+), respectively, indicating an efficient surface charge neutralization by counterions. A fully optimized continuous (FOCUS) pK(a) distribution method revealed four binding sites on B. subtilis and E. coli surfaces from the master curves with pK(a)(int) values of 3.59+/-0.38, 4.33+/-0.57, 5.94+/-0.66, and 8.64+/-0.57 for B. subtilis and 3.73+/-0.44, 4.85+/-0.71, 6.56+/-0.64, and 8.79+/-0.62 for E. coli. These were assigned to functional groups according to reported pK(a) ranges of 2.0-6.0 (carboxylic acid), 3.2-3.5 (phosphodiesters), 5.6-7.2 (phosphoric acid), and 9.0-11.0 (amine groups). Average points of zero salt effect (pH(pzse)) for B. subtilis experiments were 6.63+/-0.21 and 6.42+/-0.08 as a function of pH(bulk) and pH(S), respectively. Under the same criteria, E. coli calculations yielded 5.73+/-0.23 and 5.45+/-0.05. An understanding of metal and proton reactivity on bacterial cell surfaces can be addressed quantitatively through the use of electrostatic and chemical equilibrium modeling techniques proposed in this study. The results are consistent with those of electrical force microscopy studies used to document the intrinsic electrochemical heterogeneity of bacterial cell surfaces.     

Effect of temperature on n-tetradecane emulsion in the presence of phospholipid DPPC and enzyme lipase or phospholipase A2

Zeta potentials and effective diameters of n-tetradecane emulsions in 1 M ethanol were investigated in the presence of 1,2-dipalmitoyl- sn-glycero-3-phosphocholine (DPPC) (1 mg/100 mL), Candida cylindracea lipase (CCL), and phospholipase PLA2 (1 mg/100 mL) at 20, 37, and 45 degrees C. The enzyme was added at the beginning of mechanical emulsion homogenization or 1 min before the end of stirring for 10 min at 10,000 rpm. It was found that DPPC decreases the negative zeta potentials at all three temperatures. The decrease was largest at 20 degrees C and smallest at 45 degrees C. The influence of the enzymes on the zeta potentials depended on the enzyme kind, time of its injection, and temperature. More negative values of the zeta potentials relative to n-C14H30/DPPC droplets were obtained if the lipase was present. Generally, the effective diameters correlate with the zeta potentials, i.e., lower zeta potential corresponds with bigger effective diameter. Possible reasons for the observed changes of the measured parameters are discussed.     

Stability of oil/water (ethanol,lysozyme or lysine) emulsions

Emulsions of n-tetradecane in water (0.1%^v/_^V) homogenized by ultrasounds (1 5 min) were stabilized by 0.5 or 1.0 M ethanol and in the presence of lysozyme (4 mg 100 ml⁻¹) or 1 mM lysine monohydrochloride (14.6 mg 100 ml⁻¹). The zeta potentials and multimodal size distributions of the droplets after 5, 15, 30, 60, 120 min, and 1 and 2 days were determined by dynamic light scattering technique using ZetaPlus apparatus (Brookhaven Instr., USA). Both parameters were determined on the same sample subsequently without any mixing. The effect of pH [4, 6.8 (natural), and 11] was also investigated. The most stable emulsions in 1 M ethanol solutions alone were at pH 6.8 and 11 (the effective diameter D_eff and 350 nm, respectively), while in 0.5 M at pH 4 (D_eff nm). The most stable emulsions with lysozyme were obtained at pH 4 and 1 M ethanol (D_eff nm), and with lysine at pH 6.8 and 0.5 M ethanol (D_eff nm). Except for the emulsions with lysozyme at pH 4 and 6.8, in the rest systems the zeta potentials were negative and ranged between −5 and −85 mV as a function of time and pH. The changes of zeta potential indicate that H⁺ ions are not much potential determining, while OH⁻ ions increase the negative zeta potentials. However, H⁺ ions affect functional groups of lysozyme molecules adsorbed on the alkane droplet, what appears in essential changes of zeta potential and even reversed sign of it in some systems. The results point that stability of these emulsions may also be determined by hydrogen bonding.     

High ionic strength electrokinetics of melamine-formaldehyde latex

The electrokinetic potential of melamine-formaldehyde latex at high ionic strengths was measured by means of two different instruments. The present study confirms that the zeta potentials in 1 M 1-1 electrolyte solutions can be as high as +/-20 mV. The IEP of latex at low ionic strengths was at pH 11. The increase in the electrolyte concentration induced a shift in the IEP to low pH for all studied salts, and this indicates specific adsorption of the anions. The magnitude of the shift depends chiefly on the nature of the anion and increases in the series Cl < NO(3) = Br < I, and the nature of the cation (Li, Na, K, Cs) plays a rather insignificant role.     

Extracellular β-class carbonic anhydrase of the alkaliphilic cyanobacterium Microcoleus chthonoplastes

The gene for β-class carbonic anhydrase (CA), which was designated as cahB1, was cloned from the genomic library of the alkaliphilic cyanobacterium Microcoleus chthonoplastes. The product of the cahB1 gene was expressed in Escherichia coli. The protein revealed high specific activity of CA, which was inhibited with ethoxyzolamide. The maximum activity of the recombinant CA was detected at alkaline pH (～9.0) and its minimum - at neutral pH (～7.0). Western blotting analysis with the antibodies raised against the recombinant CahB1 protein revealed its localization in cell envelopes of M. chthonoplastes. Immunocytochemical localization of the CahB1 in cells confirmed its extracellular location. The newly characterized CahB1 of Microcoleus was similar in amino acid and nucleotide sequences to well known β-CAs of Synechococcus sp. PCC 7942 (IcfA) and Synechocystis sp. PCC 6803 (CcaA), although those CAs were attributed to the carboxysomal shells of cyanobacteria. Previously we have reported β-class CA which was associated with PS II of alkaliphilic cyanobacteria. Here we first report extracellular localization of β-class CA and provide a scheme for its possible involvement in the maintenance of a balance between external sources of inorganic carbon and photosynthesis in extreme environments of soda lakes.     

Mechanisms and kinetics of humic acid adsorption onto chitosan-coated granules

Chitosan, a naturally abundant biopolymer, has widely been studied for metal adsorption from various aqueous solutions, but the extension of chitosan as an adsorbent to remove humic substances from water has seldom been explored. In this study, chitosan was coated on the surface of polyethyleneterephthalate (PET) granules through a dip and phase inversion process and was examined for humic acid removal in a series of batch adsorption experiments. Scanning electron microscopic (SEM) images showed that the PET granules were uniformly covered with a layer of chitosan and the chitosan layer possessed numerous open pores on the surface. Zeta potential study indicated that the chitosan-coated granules had positive zeta potentials at pH < 6.6 and negative zeta potentials at pH > 6.6. Adsorption of humic acid onto the chitosan-coated granules was found to be strongly pH-dependent. Significant amounts of humic acid were adsorbed under acidic and neutral pH conditions, but the adsorption capacity was reduced remarkably with increasing solution pH values. The adsorption isothermal data under various initial humic acid concentrations (at the same solution pH value) can be adequately modeled by the Langmuir and Freundlich models. X-ray photoelectron spectroscopy (XPS) revealed that the amino groups of the chitosan layer were protonated due to humic acid adsorption, suggesting the formation of organic complex between the protonated amino groups and humic acid. Kinetic study indicated that the adsorption process was transport-limited at low solution pH values, but became both transport- and attachment-limited at high solution pH values.     

Photoinduced surface potential change of bacteriorhodopsin mutant D96N measured by scanning surface potential microscopy

We report the direct measurement of photoinduced surface potential differences of wild-type (WT) and mutant D96N bacteriorhodopsin (BR) membranes at pH 7 and 10.5. Atomic force microscopy (AFM) and scanning surface potential microscopy (SSPM) were used to measure the BR membrane with the extracellular side facing up. We present AFM and SSPM images of WT and mutant D96N in which the light-dark transition occurred in the mid-scan of a single BR membrane. Photosteady-state populations of the M state were generated to facilitate measurement in each sample. The photoinduced surface potential of D96N is 63 mV (peak to valley) at pH 10.5 and is 48 mV at pH 7. The photoinduced surface potential of WT is 37 mV at pH 10.5 and approximately 0 at pH 7. Signal magnitudes are proportional to the amount of M produced at each pH. The results indicated that the surface potentials were generated by photoformation of surface charges on the extracellular side of the membrane. Higher surface potential correlated with a longer lifetime of the charges. A mechanistic basis for these signals is proposed, and it is concluded that they represent a steady-state measurement of the B2 photovoltage.     

Studies on the application of Fe-Zr mixed hydrous oxide membranes in ion-selective potentiometry

A solid membrane electrode selective to chloride ions has been prepared from Fe-Zr mixed hydrous oxide (with iron as a major constituent) with polystyrene as binder. Although the response of the electrode is non-Nernstian it can be utilized to estimate chloride in the concentration range 10(-4)-10(-1)M. The potentials generated across the membrane are reproducible within +/-0.2 mV and the response time is a few seconds. The standard deviation of the potential measurements is 0.4 mV at the 0.1M level. The useful pH range is 4-7 and the electrode can also be used in partially non-aqueous systems. The electrode exhibits fairly good selectivity for chloride.     

Surface behavior of nickel powders in aqueous suspensions

The colloidal behavior of nickel aqueous suspensions is studied and compared to that of NiO suspensions. Under acidic conditions, nickel readily dissolves, but no dissolution takes place at basic pH. Zeta potential is studied as a function of pH, showing that the isoelectric point (IEP) occurs at pH 3.5-4. Above the IEP there is a zeta potential plateau, which is associated to the predominance of NiO(OH) species. At pH 9 a new decrease in zeta potential is associated to NiO predominance. XPS studies support that suspensions prepared at pH >9 lead to NiO-enriched species, while suspensions prepared at lower pH form NiO(OH) species.     

Determination of trace amounts of estriol and estradiol by adsorptive cathodic stripping voltammetry.

Estriol and estradiol are electroinactive in the potential range from -200 to -1000 mV versus a silver-silver chloride electrode at a mercury electrode. The conversion of these estrogens into electroactive nitro derivatives of estrogens, which are used for voltammetric determination, was studied. Such nitro derivatives give a well defined cathodic stripping wave at -600 mV in pH 10.5 borate buffer. Estriol and estradiol are determined in the ranges 1 x 10(-9)-1.5 x 10(-6) and 5 x 10(-9)-2 x 10(-6) mol dm-3, respectively, by differential-pulse adsorptive stripping voltammetry at a hanging mercury drop electrode. Some steroids, such as estrone, interfere because the three estrogens have almost the same molecular structure and have similar nitro derivatives, but progesterone does not interfere and is reduced at significantly more negative potentials than the nitrated estrogens. It can be determined simultaneously with estriol or estradiol. A method was developed for the assay of estriol in pharmaceutical preparations.     

Role of acid–base interactions on the adhesion of oral streptococci and actinomyces to hexadecane and chloroform—influence of divalent cations and comparison between free energies of partitioning and free energies obtained by extended DLVO analysis

Calcium is an abundantly present, divalent cation in the oral cavity and plays a crucial role in the adhesion of oral microorganisms to tooth surfaces as well as in coaggregation and coadhesion among the oral microflora. The aim of this study was to determine the effects of divalent cation (Ca²⁺, Mg²⁺, Ba²⁺) adsorption on the adhesion of two actinomyces and two streptococcal strains to hexadecane (MATH) and chloroform (MATS) in order to detect changes in acid–base character of the cell surfaces. Initial removal rates of the organisms by hexadecane, lacking an acid–base interaction with the organisms, were always smaller than those by chloroform. Furthermore, adsorption of divalent cations generally increased the initial removal rates of the microorganisms, but no statistically significant differences among different cations were observed. Gibbs energies of partitioning calculated from the stationary end-point adhesion of the organisms ranged from −2 to −4 kT for adhesion to hexadecane and were about twofold more negative for adhesion to chloroform. Contact angles on lawns of microorganisms with and without adsorbed divalent cations were similar. Zeta potentials of all microorganisms were slightly negative under the conditions of MATH and MATS and became only 4 mV more positive upon divalent cation adsorption. Hexadecane had a zeta potentials of −21 mV in the potassium phosphate solution used, which became 13 mV less negative upon Ca²⁺ adsorption. An extended DLVO approach of microbial adhesion to hexadecane, based on microbial contact angles and zeta potentials, taking into account Lifshitz–van der Waals, acid–base and electrostatic interactions did not show any potential energy barrier and demonstrated a deep primary interaction minimum at close approach due to acid–base attraction. As the Gibbs energy of partioning was only −2 to −4 kT, it is concluded that for the collection of organisms studied here, the final contactable surface area is small and structural features on the cell surfaces like fibrils and fimbriae, maintain a distance of ca. 10–15 nm between the hexadecane and the overall cell surface and therewith prevent acid–base interactions to become operative to a significant extend. Furthermore, from the lack of influence of divalent cations on macroscopic cell surface contact angles and zeta potentials, it is suggested that cation adsorption is minor and localized to the fibrils and fimbriae.     

中东常压渣油热反应样品Zeta电位的研究

长期以来,有诸多研究者认识到了渣油的胶体性质,并且利用各种实验手段对其进行了研究。渣油的胶体稳定性对其热反应性能有重要影响作用。前人的研究认为,渣油胶体体系中的分散相主要是由沥青质构成,分散介质由芳香分和饱和分共同构成,吸附层由胶质构成。胶体的一个重要性质是电性质,渣油分子中含有大量的杂原子,使渣油极性分子的存在和渣油胶粒具有一定的电性。     

双敏性微凝胶的絮凝及聚沉行为

用沉降聚合法制备了聚(N-异丙基丙烯酰胺-co-甲基丙烯酸)微凝胶, 并用NMR, DLS分析测定了微凝胶结构及凝胶颗粒在不同离子强度下粒径和表面电势的变化. 25 ℃时在pH＝7的溶液中Zeta电位为－18 mV, 随离子强度增加, 逐渐减小. 当NaCl浓度达0.2 mol/L时基本不变, 表明微凝胶表面电荷受到屏蔽, 浓度继续增加主要使凝胶颗粒收缩. 加热引起微凝胶收缩, 颗粒表面电荷密度增大, Zeta电位增大. 在0.2 mol/L NaCl溶液中, 41 ℃时微凝胶的Zeta电位可达－12.4 mV, 使微凝胶稳定. 较高离子强度时, Zeta电位随温度升高发生突变, 微凝胶表面几乎为中性, 其突变温度与临界絮凝温度(CFT)相当. CFT随离子强度增加向低温迁移, 微凝胶聚集速率在高温时比低温时快.