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Interactions of transition-metal-oxide nanomaterials with biological membranes have important environmental implications and applications in ecotoxicity and life-cycle assessment analysis. In this study, we quantitatively assess the impact of MnO2 nanomaterial morphology-one-dimensional (1D) nanowires, 2D nanosheets, and 3D nanoflowers-on their interaction with phospholipid vesicles as a model for biological membranes. Confocal microscopy suggests visual evidence for the interaction of undisrupted vesicles with dispersed MnO2 nanomaterials of different morphologies, and it further supports the observation that minimal dye leakage of the vesicle inner solution was detected during the interaction with MnO2 nanomaterials during the dye leakage assay. Upon titration of vesicles to dispersions of MnO2 nanowires, nanosheets, and nanoflowers, each roughly 10 times larger than the vesicles, dynamic light scattering reveals two diffusive time scales associated with aggregates in the mixture. While the longer time scale corresponds to the dispersed MnO2 control population, the appearance of a shorter timescale with vesicle addition indicates interaction between the dispersed metal oxide nanomaterials and the vesicles. The interaction is shape-dependent, being more pronounced for MnO2 nanowires than for nanosheets and nanoflowers. Furthermore, the shorter diffusive time scale is intermediate between the vesicle and nanomaterial controls, which may suggest a degree of metal oxide aggregate breakup. Vesicle adsorption isotherms and zeta potential measurements during titration corroborate vesicle attachment on the nanomaterials. Our results suggest that the dispersed nanomaterial shape plays an important role in mediating nondestructive vesicle-nanomaterial interactions and that lipid vesicles act as efficient surfactants for MnO2 nanomaterials.

Biofilm-associated infections are one of the leading causes of death in the United States. Although infections may be treated with antibiotics, the overuse of antibiotics has led to the spread of antibiotic resistance. Many natural antimicrobial compounds derived from edible plants are safe for human use and target bacteria nonspecifically. Therefore, they may impair biofilm formation with less evolutionary pressure on pathogens. Here, we explore the use of two natural antimicrobial compounds, cinnamaldehyde (CA, from cinnamon) and carvacrol (CARV, from oregano), for biofilm prevention. We have fabricated and characterized films that incorporate CA and CARV into the biodegradable, FDA-approved polymer poly(lactic-co-glycolic acid), PLGA. The addition of CA and CARV to PLGA films not only adds antimicrobial activity but also changes the surface properties of the films, making them more hydrophilic and therefore more resistant to bacterial attachment. An addition of 0.1% CA to a PLGA film significantly impairs biofilm development by Staphylococcus aureus, and 0.1% CARV in PLGA significantly decreases biofilm formation by both Escherichia coli and S. aureus. Pseudomonas aeruginosa, which is less susceptible to CA and CARV, was not affected by the addition of 0.1% CA or CARV to the PLGA coatings; however, P. aeruginosa biofilm was significantly reduced by 1.0% CA. These results indicate that both CA and CARV could potentially be used in low concentrations as natural additives in polymer coatings for indwelling devices to delay colonization by bacteria.

The effective removal of viruses by a multiwalled carbon nanotube (MWNT) filter is demonstrated over a range of solution chemistries. MS2 bacteriophage viral removal by the MWNT filter was between 1.5 and 3 log higher than that observed with a recently reported single-walled carbon nanotube (SWNT) filter when examined under similar loadings (0.3 mg/cm(2)) of carbon nanotubes (CNTs). The greater removal of viruses by the MWNT filter is attributed to a more uniform CNT-filter matrix that allows effective removal of viruses by physicochemical (depth) filtration. Viral removal by the MWNT filter was examined under a broad range of water compositions (ionic strength, monovalent and divalent salts, solution pH, natural organic matter, alginate, phosphate, and bicarbonate) and filter approach velocities (0.0016, 0.0044, and 0.0072 cm/s). Log viral removal increased as the fluid approach velocity decreased, exhibiting a dependence on approach velocity in agreement with colloid filtration theory for Brownian particles. Viral removal improved with increasing ionic strength (NaCl), from 5.06 log removal at 1 mM NaCl to greater than 6.56 log removal at 100 mM NaCl. Addition of calcium ions also enhanced viral removal, but the presence of magnesium ions resulted in a decrease in viral removal. Solution pH also played an important role in viral removal, with log removals of 8.13, 5.38, and 4.00 being documented at solution pH values of 3.0, 5.5, and 9.0, respectively. Dissolved natural organic matter (NOM) had a negligible effect on viral removal at low concentration (1 mg/L), but higher concentrations of NOM significantly reduced the viral removal by the MWNT filter, likely due to steric repulsion. Addition of alginate (model polysaccharide) also caused a marked decrease in viral removal by the MWNT filter. This highly scalable MWNT-filter technology at gravity-driven pressures presents new, cost-effective options for point-of-use filters for viral removal.

We provide the first evidence that the size (diameter) of carbon nanotubes (CNTs) is a key factor governing their antibacterial effects and that the likely main CNT-cytotoxicity mechanism is cell membrane damage by direct contact with CNTs. Experiments with well-characterized single-walled carbon nanotubes (SWNTs) and multiwalled carbon nanotubes (MWNTs) demonstrate that SWNTs are much more toxic to bacteria than MWNTs. Gene expression data show that in the presence of both MWNTs and SWNTs, Escherichia coli expresses high levels of stress-related gene products, with the quantity and magnitude of expression being much higher in the presence of SWNTs.

We investigated the impact of calcium and magnesium ions on the deposition kinetics of flagellated and nonflagellated Pseudomonas aeruginosa onto an alginate conditioning film in a radial stagnation point flow system. The bacterial deposition/adhesion behavior was related to structural changes of the alginate film in the presence of the divalent cations. Our results showed that adhesion of nonmotile bacteria was governed by cation bridging interactions between high-affinity sites at the bacterial surface and either clean or alginate-conditioned substrate surfaces. For motile bacteria, the adhesion onto clean quartz was governed by electrostatic interactions while adhesion onto alginate-conditioned quartz was dependent on the structure and viscoelastic properties of the alginate film in the presence of calcium or magnesium. We demonstrate that bacterial adhesion behavior is governed both by the effects of divalent cations on the surface properties of the bacteria and the substrate and by the type of specific interactions occurring between these two surfaces.

Early-stage aggregation kinetics studies of alginate-coated hematite nanoparticles in solutions containing alkaline-earth metal cations revealed enhanced aggregation rates in the presence of Ca2+, Sr2+, and Ba2+, but not with Mg2+. Transmission electron microscopy (TEM) imaging of the aggregates provided evidence that alginate gel formation was essential for enhanced aggregation to occur. Dynamic light scattering (DLS) aggregation results clearly indicated that a much lower concentration of Ba2+ compared to Ca2+ and Sr2+ was required to achieve a similar degree of enhanced aggregation in each system. To elucidate the relationship between the alginate's affinities for divalent cations and the enhanced aggregation of the alginate-coated hematite nanoparticles, atomic force microscopy (AFM) was employed to probe the interaction forces between alginate-coated hematite surfaces under the solution chemistries used for the aggregation study. Maximum adhesion forces, maximum pull-off distances, and the work of adhesion were used as indicators to gauge the alginate's affinity for the divalent cations and the resulting attractive interactions between alginate-coated hematite nanoparticles. The results showed that alginate had higher affinity for Ba2+ than either Sr2+ or Ca2+. This same trend was consistent with the cation concentrations required for comparable enhanced aggregation kinetics, suggesting that the rate of alginate gel formation controls the enhanced aggregation kinetics. An aggregation mechanism incorporating the gelation of alginate is proposed to explain the accelerated aggregate growth in the presence of Ca2+, Sr2+, and Ba2+.

A quartz crystal microbalance with dissipation (QCM-D) has been used to determine the adsorption rate of ampicillin-resistant linear and supercoiled plasmid DNA onto a silica surface coated with natural organic matter (NOM). The structure of the resulting adsorbed DNA layer was determined by analyzing the viscoelastic properties of the adsorbed DNA layers as they formed and were then exposed to solutions of different ionic composition. The QCM-D data were complemented by dynamic light scattering measurements of diffusion coefficients of the DNA molecules as a function of solution ionic composition. The obtained results suggest that electrostatic interactions control the adsorption and structural changes of the adsorbed plasmid DNA on the NOM-coated silica surface. The adsorption of DNA molecules to the NOM layer took place at moderately high monovalent (sodium) electrolyte concentrations. A sharp decrease in solution ionic strength did not result in the release of the adsorbed DNA, indicating that DNA adsorption on the NOM-coated silica surface is irreversible under the studied solution conditions. However, the decrease in electrolyte concentration influenced the structure of the adsorbed layer, causing the adsorbed DNA to adopt a less compact conformation. The linear and supercoiled DNA had similar adsorption rates, but the linear DNA formed a thicker and less compact adsorbed layer than the supercoiled DNA.

The mechanisms and causes of deviation from the classical colloid filtration theory (CFT) in the presence of repulsive Derjaguin-Landau-Verwey-Overbeek (DLVO) interactions were investigated. The deposition behavior of uniform polystyrene latex colloids in columns packed with spherical soda-lime glass beads was systematically examined over a broad range of physicochemical conditions, whereby both the fluid-phase effluent particle concentration and the profile of retained particles were measured. Experiments conducted with three different-sized particles in a simple (1:1) electrolyte solution reveal the controlling influence of secondary minimum deposition on the deviation from CFT. In a second series of experiments, sodium dodecyl sulfate (SDS) was added to the background electrolyte solution with the intent of masking near-neutrally charged regions of particle and collector surfaces. These results indicate that the addition of a small amount of anionic surfactant is sufficient to reduce the influence of certain surface charge inhomogeneities on the deviation from CFT. To verify the validity of CFT in the absence of surface charge heterogeneities, a third set of experiments was conducted using solutions of high pH to mask the influence of metal oxide impurities on glass bead surfaces. The results demonstrate that both secondary minimum deposition and surface charge heterogeneities contribute significantly to the deviation from CFT generally observed in colloid deposition studies. It is further shown that agreement with CFT is obtained even in the presence of an energy barrier (i.e., repulsive colloidal interactions), suggesting that it is not the general existence of repulsive conditions which causes deviation but rather the combined occurrence of "fast" and "slow" particle deposition.

A radial stagnation point flow system was used to investigate the influence of Cryptosporidium parvum surface properties on oocyst deposition kinetics onto solid surfaces. To determine the role of oocyst surface proteins in adhesion, the deposition kinetics of viable oocysts were compared with the deposition kinetics of oocysts treated (inactivated) with either heat or formalin. Results showed a significantly higher deposition rate with formalin and heat-treated oocysts compared to viable oocysts under identical solution ionic strengths. Low deposition rates and corresponding attachment efficiencies were observed with viable oocysts over the entire range of solution conditions investigated, even at high ionic strengths where DLVO theory predicts the absence of an electrostatic energy barrier. An "electrosteric" repulsion between the viable Cryptosporidium oocyst and the quartz substrate, attributed to proteins on the oocyst surface, is surmised to cause this low deposition rate. Inactivation of the oocysts with either formalin or heat resulted in increased attachment efficiencies over the entire range of ionic strengths examined. It is hypothesized that formalin and heat treatments alter the structure of surface proteins and thus reduce steric repulsion. Formalin treatment was also found to impart an increased hydrophobicity to the oocyst surface and thus greater enhancement in oocyst deposition kinetics compared to heat treatment.

A growing body of experimental evidence suggests that the deposition behavior of microbial particles (e.g., bacteria and viruses) is inconsistent with the classical colloid filtration theory (CFT). Well-controlled laboratory-scale column deposition experiments were conducted with uniform model particles and collectors to obtain insight into the mechanisms that give rise to the diverging deposition behavior of microorganisms. Both the fluid-phase effluent particle concentration and the profile of retained particles were systematically measured over a broad range of physicochemical conditions. The results indicate that, in the presence of repulsive Derjaguin-Landau-Verwey-Overbeek (DLVO) interactions, the concurrent existence of both favorable and unfavorable colloidal interactions causes significant deviation from the CFT. A dual deposition mode model is presented which considers the combined influence of "fast" and "slow" particle deposition. This model is shown to adequately describe both the spatial distribution of particles in the packed bed and the suspended particle concentration at the column effluent.

The stability and aggregation behavior of iron oxide colloids in natural waters play an important role in controlling the fate, transport, and bioavailability of trace metals. Time-resolved dynamic light scattering experiments were carried out in a study of the aggregation kinetics and aggregate structure of natural organic matter (NOM) coated hematite colloids and bare hematite colloids. The aggregation behavior was examined over a range of solution chemistries, by adjusting the concentration of the supporting electrolyte-NaCl, CaCl2, or simulated seawater. With the solution pH adjusted so that NOM-coated and bare hematite colloids were at the same zeta potential, we observed a significant difference in colloid stability which results from the stability imparted to the colloids by the adsorbed NOM macromolecules. This enhanced stability of NOM-coated hematite colloids was not observed with CaCl2. Aggregate form expressed as fractal dimension was determined for both NOM-coated and bare hematite aggregates in both NaCl and CaCl2. The fractal dimensions of aggregates formed in the diffusion-limited regime indicate slightly more loosely packed aggregates for bare hematite than theory predicts. For NOM-coated hematite, a small decrease in fractal dimension was observed when the solution composition changed from NaCl to CaCl2. For systems in the reaction-limited regime, the measured fractal dimensions agreed with those in the literature. Colloid aggregation was also studied in synthetic seawater, a mixed cation system to simulate estuarine mixing. Those results describe the important phenomena of iron oxide aggregation and sedimentation in estuaries. When compared to field data from the Mullica Estuary, U.S.A., it is shown that collision efficiency is a good predictor of the iron removal in this natural system.

A radial stagnation-point flow cell utilizing an optical microscope and an image-capturing device was used to directly observe the deposition kinetics of colloidal particles onto micropatterned glass surfaces with well-defined surface charge features. Surface charge heterogeneity was microfabricated onto glass surfaces by silanizing specified regions of the glass surface by a soft lithographic technique. At a certain combination of solution ionic strengths and particle Peclet numbers, the observed deposition rates deviated from predictions on the basis of a particle-deposition model for surfaces with macroscopic patchwise charge heterogeneity. The results are attributed to the interplay between hydrodynamic and electrostatic double-layer interactions and are explained by a phenomenon we term the “hydrodynamic bump” effect.

Recent experimental investigations suggest that interaction of colloidal particles with polymeric membrane surfaces is influenced by membrane surface morphology (roughness). To better understand the consequences of surface roughness on colloid deposition and fouling, it is imperative that models for predicting the Derjaguin−Landau−Verwey−Overbeek (DLVO) interaction energy between colloidal particles and rough membrane surfaces be developed. We present a technique of reconstructing the mathematical topology of polymeric membrane surfaces using statistical parameters derived from atomic force microscopy roughness analyses. The surface element integration technique is used to calculate the DLVO interactions between spherical colloidal particles and the simulated (reconstructed) membrane surfaces. Predictions show that the repulsive interaction energy barrier between a colloidal particle and a rough membrane is lower than the corresponding barrier for a smooth membrane. The reduction in the energy barrier is ...

A novel asymmetric clamping cell is used to measure the ζ potential of macroscopic sample surfaces. The unique design of the cell allows in-situ measurement of ζ potentials of any flat surfaces, either solids (such as glass, plastics, metals, and ceramics) or flexible sheets (like polymer films, papers, foils, and membranes), without having to cut or shape the test surfaces to fit the measuring cell dimensions. The cell enables measurement of the streaming potential through several parallel rectangular channels formed by firmly pressing a grooved spacer against the test surface. The term “asymmetric” specifically refers to the unique configuration of the channels, where one of the walls (the test surface) bears a different charging property (or, more specifically, ζ potential), compared to the other three surfaces of the channel (formed by the spacer). A mathematical formulation on the basis of Smoluchowski−Helmholtz approach reveals that the measured ζ potential in such a cell represents the average ζ po...

The influence of hydrodynamic shear on the shape of deformable molecular assemblages is studied using Monte Carlo simulations. Metropolis Monte Carlo simulations are performed to generate spherical assemblages of amphiphilic molecules by considering coarse statistical mechanical models for the various constituent subunits of the amphiphiles and by avoiding explicit consideration of the solvent molecules. The resulting assemblage is subjected to a unidirectional hydrodynamic shear, and the transition of the system to a secondary equilibrium is studied using a modified Monte Carlo simulation technique that accounts for the systematic force on the assemblage due to the hydrodynamic shear. The influence of hydrodynamic shear on the shape of the assemblage is described qualitatively through several simulation snapshots. The quantitative analysis suggests that the aggregate size, intermolecular interactions between various subunits, and shear rate govern the extent of shear-induced deformation. The three parame...

An improved theoretical model is presented for quantifying the dynamics of colloid deposition in granular porous media. The model characterizes the transient aspects ofirreversible particle deposition onto spherical collector surfaces where repulsive electrostatic forces between colloidal particles limit deposition to monolayer coverage. The transient deposition rate normally associated with particle deposition is depicted in the model by a dynamic blocking function derived from random sequential adsorption (RSA) mechanics. The RSA blocking function has a nonlinear power law dependence on surface coverage, in contrast to the linear Langmuirian blocking function used in previous dynamic deposition models for porous media. A technique involving the calculation of the jamming limit from experimental particle breakthrough curves is utilized for determining the excluded area parameter, an integral component of the dynamic blocking function. Parameter estimation and curve fitting techniques are not required by the model as all parameter values are calculated a priori using available theoretical principles. Parameter values are incorporated into the theoretical model to produce theoretical particle breakthrough curves based on both RSA and Langmuirian dynamic blocking functions. A comparison of theoretical results with experimental particle breakthrough curves demonstrates the utility of RSA mechanics as a means of describing particle blocking dynamics associated with colloid deposition in granular porous media.

L'influence de la dimension des particules sur le depot de particules de polystyrene sur un lit de particules spheriques de verre est etudiee theoriquement et experimentalement

The mechanisms and causes of deviation from the classical colloid filtration theory (CFT) in the presence of repulsive Derjaguin-Landau-Verwey-Overbeek (DLVO) interactions were investigated. The deposition behavior of uniform polystyrene latex colloids in columns packed with spherical soda-lime glass beads was systematically examined over a broad range of physicochemical conditions, whereby both the fluid-phase effluent particle concentration and the profile of retained particles were measured. Experiments conducted with three different-sized particles in a simple (1:1) electrolyte solution reveal the controlling influence of secondary minimum deposition on the deviation from CFT. In a second series of experiments, sodium dodecyl sulfate (SDS) was added to the background electrolyte solution with the intent of masking near-neutrally charged regions of particle and collector surfaces. These results indicate that the addition of a small amount of anionic surfactant is sufficient to reduce the influence of certain surface charge inhomogeneities on the deviation from CFT. To verify the validity of CFT in the absence of surface charge heterogeneities, a third set of experiments was conducted using solutions of high pH to mask the influence of metal oxide impurities on glass bead surfaces. The results demonstrate that both secondary minimum deposition and surface charge heterogeneities contribute significantly to the deviation from CFT generally observed in colloid deposition studies. It is further shown that agreement with CFT is obtained even in the presence of an energy barrier (i.e., repulsive colloidal interactions), suggesting that it is not the general existence of repulsive conditions which causes deviation but rather the combined occurrence of "fast" and "slow" particle deposition.