Multiscale dynamics of the cell envelope of Shewanella putrefaciens as a response to pH change

The bacterial surface properties of gram-negative Shewanella putrefaciens were characterized by microbial adhesion to hydrocarbons (MATH), adhesion to polystyrene dishes, and electrophoresis at different values of pH and ionic strength. The bacterial adhesion to these two apolar substrates shows significant variations according to pH and ionic strength. Such behavior could be partly explained by electrostatic repulsions between bacteria and the solid or liquid interface. However, a similar trend was also observed at rather high ionic strength where electrostatic interactions are supposed to be screened. The nanomechanical properties at pH 4 and 10 and at high ionic strength were investigated by using atomic force microscopy (AFM). The indentation curves revealed the presence of a polymeric external layer that swells and softens up with increasing pH. This suggests a concomitant increase of the water permeability and so did of the hydrophilicity of the bacterial surface. Such evolution of the bacterial envelope in response to changes in pH brings new insight to the pH dependence in the bacterial adhesion tests. It especially demonstrates the necessity to consider the hydrophobic/hydrophilic surface properties of bacteria as not univocal for the various experimental conditions investigated.     

Bacterial attachment to iron-impregnated granular activated carbon

Bacterial attachment to iron-impregnated granular activated carbon (Fe-GAC) was investigated in this study using Enterococcus faecalis ATCC 10100 and charcoal-based GAC. Two sets of column experiments were performed under different ionic strengths and pH conditions. Breakthrough curves of bacteria were obtained by monitoring effluent. Mass recoveries and attachment rate coefficients were quantified from these curves. In addition, characteristics of Fe-GAC were analyzed using field emission scanning electron microscopy (FESEM) and X-ray spectrometry (EDS). Results show that Fe-GAC was characterized by mosaic-like deposition layers of iron oxides with about 2 μm in thickness. Color mapping with FESEM visualized the spatial distribution of carbon (yellow-green) and iron (red) on Fe-GAC. EDS indicates that iron was distinctly found from Fe-GAC at three peak positions. Results also reveal that bacterial attachment to Fe-GAC was affected by ionic strength and pH.Bacterial mass recoveries decreased from 62.9 to 41.7% with increasing ionic strength from 1 to 50 mM. This indicates that bacterial attachment to the surfaces of Fe-GAC was enhanced with increasing ionic strength. With increasing pH from 6.46 to 9.19, mass recoveries increased from 50.5 to 84.2%, indicating that bacterial attachment to Fe-GAC was reduced with increasing pH. This study demonstrates that iron oxides offer favorable attachment sites for bacteria on the surfaces of Fe-GAC and further improves the knowledge of bacterial removal in Fe-GAC.     

Multiscale dynamics of the cell envelope of Shewanella putrefaciens as a response to pH change

The bacterial surface properties of gram-negative Shewanella putrefaciens were characterized by microbial adhesion to hydrocarbons (MATH), adhesion to polystyrene dishes, and electrophoresis at different values of pH and ionic strength. The bacterial adhesion to these two apolar substrates shows significant variations according to pH and ionic strength. Such behavior could be partly explained by electrostatic repulsions between bacteria and the solid or liquid interface. However, a similar trend was also observed at rather high ionic strength where electrostatic interactions are supposed to be screened. The nanomechanical properties at pH 4 and 10 and at high ionic strength were investigated by using atomic force microscopy (AFM). The indentation curves revealed the presence of a polymeric external layer that swells and softens up with increasing pH. This suggests a concomitant increase of the water permeability and so did of the hydrophilicity of the bacterial surface. Such evolution of the bacterial envelope in response to changes in pH brings new insight to the pH dependence in the bacterial adhesion tests. It especially demonstrates the necessity to consider the hydrophobic/hydrophilic surface properties of bacteria as not univocal for the various experimental conditions investigated.     

Factors influencing reverse osmosis rejection of inorganic solutes from aqueous solution

Reverse osmosis (RO) rejection is strongly influenced by the distribution of solute between the membrane and solvent phases. For this reason, we examined the partition coefficients of inorganic compounds between water and cellulose acetate (CA) membranes. Cation and anion partition coefficients were determined by independent analyses. Effects of fixed (negative) membrane charges on CA are clearly apparent at low solute concentrations. The mean cation/anion partition coefficients decrease with the product of the cation and anion valence, and increase with increasing ionic size. Un-ionized inorganic compounds, HgC1₂ and HAuC1₄, are strongly sorbed by CA membranes. All of these observations are consistent with electrostatic theory.Experimental membrane/water partition coefficients are influenced by temperature, pH, and ion-pairing. CA membranes exhibit swelling and shrinkage when exposed to certain aqueous solutions. Swelling and shrinkage influence solute partition and diffusion coefficients, the water content of the membranes, and their RO rejection.The present results provide a comprehensive experimental basis for understanding the mechanism of RO rejection by CA membranes. Moreover, these results can be used to predict RO behavior under a wide variety of experimental conditions. The potential use of reverse osmosis in a variety of wastewater applications is considered in some detail.     

Fouling of reverse osmosis and nanofiltration membranes by humic acid—Effects of solution composition and hydrodynamic conditions

Fouling of reverse osmosis (RO) and nanofiltration (NF) membranes by humic acid, a recalcitrant natural organic matter (NOM), was systematically investigated. The membrane flux performance depended on both hydrodynamic conditions (flux and cross-flow velocity) and solution composition (humic acid concentration, pH, ionic strength, and calcium concentration), and was largely independent of virgin membrane properties. While increasing humic acid concentration and ionic strength, and lowering cross-flow velocity affected flux performance moderately, severe flux reduction occurred at high initial flux, low pH, and high calcium concentration. At a calcium concentration of 1 mM, all the membranes exhibited an identical stable flux, independent of their respective intrinsic membrane permeabilities. The effect of solution composition was more significant at higher fluxes. Improved salt rejection was observed as a result of humic acid fouling, which was likely due to Donnan exclusion by humic material close to membrane surfaces. Greater rejection improvement was observed for membranes with rougher surfaces.     

Influence of ionic strength and pH on the first 60 min of Pseudomonas aeruginosa attachment to ZnSe and to TiO2 monitored by ATR-IR spectroscopy

Establishing the factors which influence the attachment of bacteria to surfaces is important in both preventing and enhancing biofilm formation. The initial hour of attachment of Pseudomonas aeruginosa to ZnSe and to TiO₂ from solutions of different ionic strength and pH was studied using in situ attenuated total reflection infrared (ATR-IR) spectroscopy. The TiO₂ surface was prepared by dip-coating a ZnSe internal reflection element, which produced a 50 nm thick, continuous flat film. At pH 6.3 attachment was found to increase with ionic strength up to 0.03 mol l⁻¹ but to decrease at 0.15 mol l⁻¹. At an ionic strength of 0.003 mol l⁻¹ attachment increased with pH from 4 to 6.3 to 10, but at ionic strength of 0.03 mol l⁻¹ attachment was greater at pH 6.3 than at pH 10. The influence of ionic strength appears to be due to charge factors and/or related changes in the degree of extension of bacterial surface polymers. The complex trends in the influence of pH on attachment can not be explained solely in terms of bacterial and substrate charge, bacterial surface polymer extension or bacterial metabolic activity.     

External Stimuli Responsive Characteristics of Epoxy‐Polyamide/Starch Blend Films

Abstract

Polymeric films of varying crosslink densities and of different molar‐concentrations were prepared from the epoxidized oil/diglycedyl ether of bis‐phenol A (DGEBA) epoxy/polyamide/starch by blending at ambient temperature. The influences of external stimuli such as pH, temperature, ionic strength of the swelling media, and the type of buffer on the equilibrium swelling properties were investigated. Polymeric films showed a typical pH and temperature response such as low‐pH and low‐temperature have maximum swelling while a high‐pH and high‐temperature show almost complete deswelling. A change in the ionic strength of the swelling solution from 0.01 to 0.2 M caused a decrease in the equilibrium degree of swelling of polymeric films. Oscillatory swelling was also observed and investigated in response to changes in the pH of the solution. The morphology of selected polymeric films were explained by scanning electron microscopy (SEM) and correlated with mechanical strength.     

Interaction of water with the regenerated cellulose membrane studied by DSC

One to three endothermal peaks atributted to melting of bulk and interfacial water were observed by DSC in the regenerated cellulose — water system. The profiles of thermal effects depend on water content, time of conditioning, film pretreatment and the conditions applied during the preceding freezing-thawing cycles. The occurrence might be deduced of melting-crystallisation processes. A large amount of non-freezable strongly bounded water was also detected. Although cellulose absorbs water quickly after immersion, the structural changes consisting on ordering of polymer fraction occur during further conditioning due to increase in strength of water binding. Using the membranes in the separation module at 90°C causes weakening of these bonds. Differences between interaction of particular cellulose films with water can be detected during the first, the second and the third heating. This revised version was published online in July 2006 with corrections to the Cover Date.     

DLVO and steric contributions to bacterial deposition in media of different ionic strengths

The deposition of eight bacterial strains on Teflon and glass in aqueous media with ionic strengths varying between 0.0001 and 1 M was measured and interpreted. Two types of interactions were considered: (1) those described by the DLVO theory, which comprise van der Waals attraction and electrostatic repulsion (bacteria and surfaces are both negatively charged); and (2) steric interactions between the outer cell surface macromolecules and the substrata. As a trend, at low ionic strength (<0.001 M), deposition is inhibited by DLVO-type electrostatic repulsion, but at high ionic strength (≥0.1 M) it is dominated by steric interactions. The ionic strength at which the transition from the DLVO-controlled to the sterically controlled deposition occurs, is determined by the extension of the macromolecules into the surrounding medium, which varied between 5 and 100 nm among the bacterial strains studied. The steric interactions either promote deposition by bridging or inhibit it by steric repulsion. Between Teflon and hydrophobic bacteria, bridging is generally observed. The surface of one bacterial strain contains amphiphilic macromolecules that form bridges with Teflon but induce steric repulsion on glass. The presence of highly polar anionic polysaccharide coatings on the cell impedes attachment on both glass and Teflon. For practice, the general conclusion is that the deposition of most bacteria is: (1) strongly inhibited by DLVO-type electrostatic repulsion in aqueous environments of low ionic strength such as rain water, streams and lakes; (2) controlled by DLVO and/or steric interactions in systems as domestic waste waters and saliva; and (3) determined by steric interactions only in more saline environments as milk, urine, blood and sea water.     

A transient experiment to measure the diffusive permeability of hollow fiber membranes

A precise and rapid transient diffusion experiment has been developed to measure the diffusive permeability of hollow fibers. In this experiment a sealed hollow fiber containing a radioactive solute is exposed sequentially to several well-stirred solute-free reservoirs. This method was used to measure the diffusive permeability of collagen and Cuprophan hollow fibers in an isotonic saline solution for a spectrum of ¹⁴C labelled solutes: urea, sucrose and polyethylene glycol (PEG). To study the effect of environment on membrane permeability, collagen membranes were investigated with urea, sucrose and tritiated water in the following solutions with varying ionic strength and hydrogen ion concentration: pH2 HCl, distilled water and pH2 HCl with 0.8 M NaCl.In each environment, the membranes showed the expected decreases in diffusive permeaability with increasing molecular weight. Collagen membranes ranged from 4 (urea) to 40 (PEG) times the permeability of Cuprophan membranes. The Cuprophan data are consistent with results obtained elsewhere using scaled-down dialyzers. In response to environmental changes, the diffusive permeability of collagen membranes changed overall by a factor of 3 with the following rank: pH 2 HCl > distilled water > pH2 HCl and 0.8 M NaCl. The hydraulic permeability of these membranes changed by a factor of 2 but in a different order pH2 HCl > pH2 HCl and 0.8 M NaCl > distilled water. These permeability changes can be explained in terms of the known environmental dependence for the structure of collagen membranes and have been shown to be consistent with trends predicted by simple transport models.     

Bacterial adhesion to glass and metal-oxide surfaces

Metal oxides can increase the adhesion of negatively-charged bacteria to surfaces primarily due to their positive charge. However, the hydrophobicity of a metal-oxide surface can also increase adhesion of bacteria. In order to understand the relative contribution of charge and hydrophobicity to bacterial adhesion, we measured the adhesion of 8 strains of bacteria, under conditions of low and high-ionic strength (1 and 100 mM, respectively) to 11 different surfaces and examined adhesion as a function of charge, hydrophobicity (water contact angle) and surface energy. Inorganic surfaces included three uncoated glass surfaces and eight metal-oxide thin films prepared on the upper (non-tin-exposed) side of float glass by chemical vapor deposition. The Gram-negative bacteria differed in lengths of lipopolysaccharides on their outer surface (three Escherichia coli strains), the amounts of exopolysaccharides (two Pseudomonas aeruginosa strains), and their known relative adhesion to sand grains (two Burkholderia cepacia strains). One Gram positive bacterium was also used that had a lower adhesion to glass than these other bacteria (Bacillus subtilis). For all eight bacteria, there was a consistent increase in adhesion between with the type of inorganic surface in the order: float glass exposed to tin (coded here as Si-Sn), glass microscope slide (Si-m), uncoated air-side float glass surface (Si-a), followed by thin films of (Co(1-y-z)Fe(y)Cr(z))3O4, Ti/Fe/O, TiO2, SnO2, SnO2:F, SnO2:Sb, A1(2)O3, and Fe2O3 (the colon indicates metal doping, a slash indicates that the metal is a major component, while the dash is used to distinguish surfaces). Increasing the ionic strength from 1 to 100 mM increased adhesion by a factor of 2.0 +/- 0.6 (73% of the sample results were within the 95% CI) showing electrostatic charge was important in adhesion. However, adhesion was not significantly correlated with bacterial charge and contact angle. Adhesion (A) of the eight strains was significantly (P < 10(-25)) correlated with total adhesion free energy (U) between the bacteria and surface (A = 2162e(-1.8U)).Although the correlation was significant, agreement between the model and data was poor for the low energy surfaces (R2 = 0.68), indicating that better models or additional methods to characterize bacteria and surfaces are still needed to more accurately describe initial bacterial adhesion to inorganic surfaces.     

Photocatalytic Treatment of Desalination Concentrate Using Optical Fibers Coated With Nanostructured Thin Films: Impact of Water Chemistry and Seasonal Climate Variations

Treatment of desalination concentrate can reduce concentrate volume for disposal, increase water recovery and convert waste to resource. However, concentrate treatment is costly and energy intensive due to high concentrations of salt and recalcitrant organic matter in concentrate. Photocatalytic oxidation provides a novel energy neutral technology for concentrate treatment by degrading organic contaminants. Polymer‐assisted hydrothermal deposition method was used to synthesize innovative pure and Fe‐doped TiO₂ mixed‐phase nanocomposite thin films on side‐glowing optical fibers (SOFs). The properties of the photocatalysts‐coated SOF were characterized by surface morphology, nanostructure, crystallite size and phase and zeta potential. Photodegradation efficiency and durability of the photocatalysts treating different types of desalination concentrate was studied under natural sunlight. Synthetic solutions and reverse osmosis (RO) concentrates from brackish water and municipal wastewater desalination facilities were tested to elucidate the impact of water chemistry, operating conditions and seasonal climate variations (solar irradiation intensity and temperature) on photocatalytic efficiency. High ionic strength and divalent electrolyte ions in RO concentrate accelerated photocatalytic process, whereas the presence of carbonate species and organic matter hindered photodegradation. Outdoor testing of immobilized continuous‐flow photoreactors suggested that the catalyst‐coated SOFs can utilize a wide spectrum of natural sunlight and achieved durable photocatalytic performance.     

pH and ionic sensitive chitosan/carboxymethyl chitosan IPN complex films for the controlled release of coenzyme A

pH and ionic sensitive interpenetrating polymer network (IPN) complex films based on chitosan (CS) and carboxymethyl chitosan (CM-CS) were prepared by using glutaraldehyde as crosslinking agent. Its structure was characterized by FT-IR, which indicated that the IPN was formed. The films were studied by swelling, weight loss with time, and release of coenzyme A (CoA). It was found that the IPN films were sensitive to pH and ionic strength of the medium. The cumulative release rate of CoA decreased with CoA loading content, ionic strength or crosslinking agent increasing. The composition of the IPN films and pH of release medium also had significant effect on the release of CoA. The differences in the rates and amounts of released CoA may be attributed to the swelling behavior, the degradation of films, and interaction between drug molecule and polymer matrix. These results suggested CS/CM-CS IPN films could be used as drug delivery carrier.     

PREPARATION AND CHARACTERIZATION OF POLYSULFONE AND POLYETHERSULFONE MEMBRANES FOR CALCIUM (Ca2+) AND MAGNESIUM (Mg2+) SEPARATION BY COMPLEXATION ULTRAFILTRATION

ABSTRACT

Asymmetric ultrafiltration membranes were synthesized from locally available polysulfone and polyethersulfone polymers using aprotic solvents and organic additives by the phase inversion method. The membranes were characterized in terms of pure water permeability, separation behavior with respect to polyethylene glycols of various molecular weights and electrolytes. The suitability of using polyethyleneimine (PEI) for selective removal of calcium and magnesium salts by an ultrafiltration process was studied in terms of optimum polymer loading at reasonable permeate flux, irreversible adsorptive fouling of the macromolecular ligand on the polymer as functions of solution pH and ionic strength, and metal ion separation as a function of concentration and pressure. Direct electron microscopic observation of fresh, as well as fouled, membranes are presented.     

Bovine Serum Albumin (BSA) as an adhesive for wet cellulose

Regenerated cellulose films were laminated using very thin layers of the protein Bovine Serum Albumin (BSA) as an adhesive. The wet delamination strength was measured as functions of pH, lamination time, temperature and pressure, as well as cellulose oxidation. Drying at elevated temperature (120 °C) was required for strong adhesion. Oxidation of the cellulose membranes to introduce surface carboxyl/aldehyde groups increased the wet delamination strength by 60%, implying that the peel failures happened at the protein/cellulose interface. The wet delamination force was independent of the pH and ionic strength of solutions used to apply the BSA; whereas adhesion decreased with increasing pH of the rewetting solution. Furthermore, the swelling of the BSA interplay region was also increased at high pH. It is proposed that covalent grafting of BSA onto the oxidized cellulose, and disulfide crosslinking within the protein layer contributed to wet adhesion.     

Adsorption of anionic surfactant on porous and non-porous polyethylene terephthalate films

We study the adsorption of anionic surfactant, sodium dodecyl diphenyloxide disulfonate (SDDD) on three types of polyethylene terephthalate substrates from aqueous solutions of SDDD of different concentrations. Neutral electrolyte (KCl) was added to the solutions to vary the ionic strength. The three types of substrates were: (1) original polymer film, (2) etched non-porous film, which was obtained from pristine film by chemical etching and bears negative charge on the surface, (3) etched porous membranes, which were fabricated from pristine film by ion irradiation and subsequent chemical etching. The membranes have negative charge on the flat surface and on the inner pore walls. The comparison of original and etched nonporous films shows that the negative charge on the flat surface has weak effect on adsorption of the anionic surfactant. The comparison of etched non-porous and porous films shows that the SDDD adsorption on the inner walls of pores is much weaker than on flat surface—even in case the pore radius is significantly larger than the Debye length. This “exclusion” effect strongly depends on ionic strength of solution. For the porous films, the effect of the pore size and shape on the anionic surfactant adsorption is presented and discussed.     

Self-assembled polyelectrolyte multilayer membranes with highly improved pervaporation separation of ethanol/water mixtures

Ethanol/water pervaporation through ultrathin polyelectrolyte multilayer membranes is described. The membranes were prepared by the layer-by-layer technique, i.e. by alternating sequential adsorption of cationic and anionic polyelectrolytes on a porous support. The separation capability was optimized by variation of the chemical structure of the polyelectrolytes, by variation of pH and ionic strength of the polyelectrolyte solutions used for membrane preparation and by annealing of the polyelectrolyte membranes. It was found that the separation is mainly affected by the charge density of the polyelectrolytes which is controlled by the chemical structure and the degree of ionisation of the polar groups. Selectivity for water was highest, if polyelectrolytes of high charge density such as polyethyleneimine (PEI), polyvinylamine (PVA) and polyvinylsulfate (PVS) were used and if the pH of the polyelectrolyte solutions was equal to the mean of the pK_a values of the corresponding cationic and anionic polyelectrolyte. Best results were obtained for PVA/PVS and PEI/PVS membranes which are characterized in detail with regard to their separation behavior.     

Surface forces measurements of spin-coated cellulose thin films with different crystallinity

A systematic study of the surface forces between a cellulose sphere and cellulose thin films of varying crystallinity has been conducted as a function of ionic strength and pH. Semicrystalline cellulose II surfaces and amorphous cellulose films were prepared by spin-coating of the precursor cellulose solutions onto oxidized silicon wafers before regeneration in water. Crystalline cellulose I surfaces were prepared by spin-coating wafers with aqueous suspensions of sulfate-stabilized cellulose I nanocrystals. These preparation methods produced thin, smooth films suitable for surface forces measurements. The interaction with the cellulose I was monotonically repulsive at pH 3.5, 5.8, and 8.5 and at 0.1, 1, and 10 mM ionic strengths. This was attributed to the presence of strongly ionizable sulfur-containing groups on the cellulose nanocrystal surfaces. The amorphous film typically showed a steric interaction up to 100 nm away from the interface that was independent of the solution conditions. A range of surface forces were successfully measured on the semicrystalline cellulose II films; attractive and repulsive regimes were observed, depending on pH and ionic strength, and were interpreted in terms of van der Waals and electrostatic interactions. Clearly, the forces acting near cellulose surfaces are very dependent on the way the cellulose surface has been prepared.     

PEG-coated reverse osmosis membranes: Desalination properties and fouling resistance

This study focuses on the use of surface-coated reverse osmosis (RO) membranes to reduce membrane fouling in produced water purification. A series of crosslinked PEG-based hydrogels were synthesized using poly(ethylene glycol) diacrylate as the crosslinker and poly(ethylene glycol) acrylate, 2-hydroxyethyl acrylate, or acrylic acid as comonomers. The hydrogels were highly water permeable, with water permeabilities ranging from 10.0 to 17.8 (L μm)/(m² h bar). The hydrogels were applied to a commercial RO membrane (AG brackish water RO membrane from GE Water and Process Technologies). The water flux of coated membranes and a series-resistance model were used to estimate coating thickness; the coatings were approximately 2 μm thick. NaCl rejection for both uncoated and coated membranes was 99.0% or greater, and coating the membranes appeared to increase salt rejection, in contrast to predictions from the series-resistance model. Zeta potential measurements showed a small reduction in the negative charge of coated membranes relative to uncoated RO membranes. Model oil/water emulsions were used to probe membrane fouling. Emulsions were prepared with either a cationic or an anionic surfactant. Surfactant charge played a significant role in membrane fouling even in the absence of oil. A cationic surfactant, dodecyltrimethyl ammonium bromide (DTAB), caused a strong decline in water flux while an anionic surfactant, sodium dodecyl sulfate (SDS), resulted in little or no flux decline. In the presence of DTAB, the AG RO membrane water flux immediately dropped to 30% of its initial value, but in the presence of SDS, its water flux gradually decreased to 74% of its initial value after 24 h. DTAB-fouled membranes had lower salt rejection than membranes not exposed to DTAB. In contrast, SDS-fouled membranes had higher salt rejection than membranes not exposed to SDS, with rejection values increasing, in some cases, from 99.0 to 99.8% or higher. In both surfactant tests, coated membranes exhibited less flux decline than uncoated AG RO membranes. Additionally, coated membranes experienced little fouling in the presence of an oil/water emulsion prepared from DTAB and n-decane. For example, after 24 h the water flux of the AG RO membrane fell to 26% of its initial value, while the water flux of a PEGDA-coated AG RO membrane was 73% of its initial value.     

聚乙烯醇/聚乙烯吡咯烷酮碱性复合膜的制备及其性能

通过在不同浓度KOH溶液中进行掺杂,制备出了聚乙烯醇/聚乙烯吡咯烷酮(PVA/PVP)碱性聚合物电解质膜.详尽考察了膜的组成、微观结构、热稳定性、离子电导率和甲醇吸收率.结果表明,PVA与PVP两者具有较好的相容性,当m(PVA)∶m(PVP)=1∶0.5时,膜断面致密、均匀,未发生大尺度相分离.PVP的混入可以极大提高复合膜的电导率和热稳定性.当m(PVA)∶m(PVP)=1∶1时,复合膜的电导率可达2.01×10-3 S.cm-1.PVA/PVP/KOH膜的甲醇吸收率随温度的升高没有明显变化,100℃时其甲醇吸收率仅为同条件下Nafion 115膜的1/4.这表明该复合膜有望作为一种新型的碱性直接甲醇燃料电池用固体电解质膜且可提高膜的使用温度.