Biomedical subjects

Darrell Velegol

Publications and source records attributed to Darrell Velegol.

18 recordsLinked to original sources

PubMed2006

Catalytically driven colloidal patterning and transport.

We recently reported the convection and pattern formation of tracers caused by a catalytically generated electric field. The electric field arises due to the heterogeneous electrochemical reduction and oxidation of hydrogen peroxide (H2O2) on silver (Ag) and gold (Au), respectively.1 Here we describe an electrokinetic model, developed in conjunction with experiments, that explains the details of the convection and pattern formation phenomenon. The model also enables the measurement of reaction kinetic parameters that are otherwise difficult to obtain. This quantitative model serves as a platform for the modeling of other catalytic redox systems and systems with broken symmetries.

Journal Article↗

PubMed2006

Fully retarded van der Waals interaction between dielectric nanoclusters.

The van der Waals (dispersion) interaction between an atom and a cluster or between two clusters at large separation is calculated by considering each cluster as a point particle, characterized by a polarizability tensor. For the extreme limit of very large separation, the fully retarded regime, one needs to know just the static polarizability in order to determine the interaction. This polarizability is evaluated by including all many-body (MB) intracluster atomic interactions self-consistently. The results of these calculations are compared with those obtained from various alternative methods. One is to consider each cluster as a collection of many atoms and evaluate the sum of two-body interatomic interactions, a common assumption. An alternative method is to include three-body atomic interactions as a MB correction term in the total energy. A comparison of these results reveals that the contribution of the higher-than-three-body MB interactions is always attractive and non-negligible even at such a large separation, in contrast to common assumptions. The procedure employed is quite general and is applicable, in principle, to any shape or size of dielectric cluster. We present numerical results for clusters composed of atoms with polarizability consistent with silica, for which the higher-than-three-body MB correction term can be as high as 42% of the atomic pairwise sum. This result is quite sensitive to the anisotropy and orientation of the cluster, in contrast to the result found in the additive case. We also present a power law expansion of the total van der Waals interaction as a series of n-body interaction terms.

Journal Article↗

PubMed2006

Fabrication of colloidal doublets by a salting out-quenching-fusing technique.

It is well-known that high ionic strength promotes colloid aggregation. Here we show that, by controlling this aggregation process, we can produce high yields of homodoublet and heterodoublet polymer colloids. The aggregation process is started by increasing the ionic strength to roughly 250 mM KCl. After approximately the rapid flocculation time, we quench the "reaction" by mixing in a large quantity of deionized water, which dilutes the ionic strength and prevents further aggregation. At this point, the suspension consists primarily of singlet and doublet particles. Through heating above the glass transition temperature of the polymers, the doublets are fused together and remain intact even after sonication. It is also shown that heterodoublets can include a silica particle together with a polymer colloid. The salting out-quenching-fusing technique is a rapid, easy-to-perform, repeatable process for fabricating colloidal doublets from polymers and other materials.

Amidines↗

PubMed2006

Transport of rodlike colloids through packed beds.

The effect of colloid shape on filtration rates in porous media was examined by constructing particles with different aspect ratios and measuring their retention in packed beds. Spherical polystyrene latex microspheres (1.0-microm diameter) were heated, stretched to the desired aspect ratio (2:1 and 3:1, with a 1:1 control), and quickly cooled. These particles were injected into minicolumns containing glass beads (40-microm diameter) in solutions at two different ionic strengths (IS = 1 and 100 mM). The measured retentions increased with aspect ratio in both IS solutions. The zeta-potentialsfor all three aspect ratios were indistinguishable, and no charge nonuniformity was measured for any of the samples. Thus, the data supportthat changes in retention resulted from the different aspect ratios rather than from different surface chemistries. Interpretation of the retention data in terms of a collision efficiency (alpha) showed an increase with aspect ratio in both IS solutions, and for 1 mM the alpha increased from 0.011 (1:1) to 0.095 (2:1) to 0.26 (3:1). These results demonstrate for the first time the direct impact of particle shape on retention in porous media. Our findings have important implications for the transport of particles with high aspect ratios, such as rod-shaped bacteria, and for the modeling of such transport.

Colloids↗

PubMed2006

Laser trap studies of end-on E. coli adhesion to glass.

Rod-shaped Escherichia coli K12:D21 bacteria were previously found to adhere by their ends (poles) [J.F. Jones, J.D. Feick, D. Imoudu, N. Chukwumah, M. Vigeant, D. Velegol, Appl. Environ. Microbiol. 69 (2003) 6515.]. In the current study we used a Nd:YAG 1064 nm laser trap to quantify the fraction of adherent bacteria and the time scale for the adhesion to occur. For the E. coli studied, 15.9+/-3.4% of the bacteria adhered when presented end-on for 15s to a cleaned glass surface that was not treated for specific interactions. These bacteria were found to adhere either instantaneously (approximately <1s) or not at all, and the adhesion was shown to be independent of power (force) of the laser trap. Additionally, for a given bacterium, either 0 or 1 ends were adhesive, never both ends. It is hypothesized that the end-on adhesion of D21 is related to bacterial polarity that dynamically results from the division process. We studied the reattachment of cells after adhesion and subsequent removal, finding that most bacteria reattach, some at least five times. However, a small fraction of D21 did not reattach after the first removal. Bacterial cells with observable division planes were tested for end-on adhesion; none of the 18 cells studied adhered by either end. On the other hand, we examined 50 daughter cells immediately after division, and four of the cells were adhesive. End-on adhesion is shown to be an important initial adhesion strategy for the E. coli strain via a single end with adhesion occurring instantaneously. Knowledge about adherent nanodomains (here, on one end) on bacteria will lead to better predictions of sticking coefficients and bacteria transport through porous media.

Bacterial Adhesion↗

PubMed2006

Orientation of irreversible adhesion of spherical particles on prolate spheroidal collectors.

When one sphere adheres to a second sphere, the location or orientation of the adhesion on the second sphere is seldom considered. However, when a sphere adheres to a prolate spheroid, the orientation of the adhesion is sometimes critical. We have performed Brownian dynamics simulations to predict the orientation of adhesion of a sphere on a prolate spheroid. When the spheroid has a high rotational diffusion coefficient, simulations show that the spherical particle adheres near the end of the spheroid. We tested our model experimentally for two systems: (1) oppositely-charged spherical and spheroidal colloids and (2) like-charged colloidal spheres and E. coli K-12 D21 bacteria. For the latter case, the spheres have previously been shown to adhere only to one end of the bacterium. Experiments in case (1) support the results of the simulations, while data from case (2) do not agree with predictions. Case (2) data reveal that the end-on adhesion of the spheres on the bacteria is not a purely Brownian phenomenon.

Journal Article↗

PubMed2006

van der Waals forces between nanoclusters: importance of many-body effects.

van der Waals interactions between nanoclusters have been calculated with a self-consistent, coupled dipole method. The method accounts for all many-body (MB) effects. Comparison is made between the exact potential energy, V, and the values obtained with two alternative methods: the sum of two-body interactions and the sum of two-body and three-body interactions. For all cases considered, the three-body term alone does not accurately represent the MB contributions to V. MB contributions are especially large for shape-anisotropic clusters.

Journal Article↗

PubMed2005

Catalytic micropumps: microscopic convective fluid flow and pattern formation.

As innovations continue to be made in the fields of microfluidics and the colloidal assembly, new strategies for moving particles and fluids may be needed. Heterogeneous catalysis provides means of locally converting the stored chemical energy of fuels to mechanical energy. We report an ambient temperature stationary "pump" that generates a proton concentration gradient through the bipolar electrochemical decomposition of hydrogen peroxide on patterned silver-gold surfaces. The resulting electric field drives convective fluid flow and pattern formation of colloidal tracer particles at the microscopic level by a combination of electroosmotic and electrophoretic forces.

Journal Article↗

PubMed2005

Limitations of differential electrophoresis for measuring colloidal forces: a Brownian dynamics study.

Differential electrophoresis experiments are often used to measure subpiconewton forces between two spheres of a heterodoublet. The experiments have been interpreted by solving the electrokinetic equations to obtain a simple Stokes law-type equation. However, for nanocolloids, the effects of Brownian motion alter the interpretation: (1) Brownian translation changes the rate of axial separation. (2) Brownian rotation reduces the alignment of the doublet with the applied electric field. (3) Particles can reaggregate by Brownian motion after they break, forming either heterodoublets or homodoublets, and because homodoublets cannot be broken by differential electrophoresis, this effectively terminates the experiment. We tackle points 1 and 2 using Brownian dynamics simulations (BDS) with electrophoresis as an external force, accounting for convective translation and rotation as well as Brownian translation and rotation. Our simulations identify the lower particle size limit of differential electrophoresis to be about 1 microm for desired statistical accuracy. Furthermore, our simulations predict that particles around 10 nm in size and at ambient conditions will break primarily by Brownian motion, with a negligible effect due to the electric field.

Journal Article↗

PubMed2005

Differences between chemisorbed and physisorbed biomolecules on particle deposition to hydrophobic surfaces.

This study examines differences between chemisorbed and physisorbed biomolecules on bacterial adhesion to both hydrophobic and hydrophilic surfaces that are biologically nonspecific. Bacteria-sized latex microspheres were used as a simplified model in order to study these factors that affect microbial adhesion. Two biomolecules (protein A, poly-D-lysine) were covalently bound to microspheres in order to study the effect of proteins on particle filtration rates in columns packed with glass beads. When poly-D-lysine or protein A was covalently bonded to the microspheres, sticking coefficients (a) for the microspheres increased by up to an order of magnitude as compared with uncoated latex microspheres. The glass packing beads were then made hydrophobic by covalently attaching silane groups with different carbon-chain lengths (0.2, 1.2, and 2.8 nm). Sticking coefficients forthe uncoated microspheres on these silanized packing beads (alpha = 0.15 at 1 mM ionic strength; 0.76 at 100 mM) were larger than those on uncoated glass packing beads (0.02 at 1 mM; 0.15 at 100 mM). In addition, adhesion increased with ionic strength on both hydrophobic and hydrophilic surfaces. Physical adsorption gave different results. When either dextran or protein A was physically adsorbed to both the microspheres and the column, no appreciable change in adhesion was observed. Covalently attaching protein A to the microspheres increased their hydrophobicity, but sticking coefficients were large regardless of the substrate hydrophobicity as a result of biomolecule-surface interactions. This study demonstrates that, at high ionic strength, covalently attached hydrophobic species give much higher sticking coefficients for particles than do physically adsorbed species.

Adsorption↗

PubMed2005

Nanoscale functionalization and site-specific assembly of colloids by particle lithography.

Numerous studies have demonstrated the bottom-up assembly of complex structures such as colloidal crystals, close-packed aggregates, and even rings and tetramers. In this paper we produce a simple localized and nanoscale charge distribution on the surfaces of individual colloidal microspheres using our technique of "particle lithography". In this technique parts of the microspheres are masked off, while polyelectrolytes (or other molecules) cover the remaining portions of the microspheres. The effectiveness of this process is demonstrated by the accurate and reproducible production of colloidal heterodoublets composed of oppositely charged microspheres. These "colloidal molecules" have the potential for significantly higher information content than previous attempts in the literature. The particle lithography technique is advantageous because it is not limited by the resolution of photolithography or by functionalizing chemistries, and the technique opens the door for complex site-specific functionalization of particles.

Journal Article↗

PubMed2005

Designing van der Waals Forces between Nanocolloids.

van der Waals (VDW) dispersion forces are often calculated between colloidal particles by combining the Dzyaloshinskii-Lifshitz-Pitaevskii (DLP) theory with the Derjaguin approximation; however, several limitations prevent using this method for nanocolloids. Here we use the Axilrod-Teller-Muto 3-body formulation to predict VDW forces between spherical, cubic, and core-shell nanoparticles in a vacuum. Results suggest heuristics for "designing" nanocolloids to have improved stability.

Journal Article↗

PubMed2004

E. coli adhesion to silica in the presence of humic acid.

The influence of humic acid on the adhesion of Escherichia coli to silica particles or glass surfaces was investigated. After adsorbing various amounts of humic acid to the particles or surfaces, bacteria were added to the sample and allowed to adhere. For the silica particles the number of bacteria-particle couplets formed were counted from video microscopy images. For the glass surfaces, a differential electrophoresis force was applied, and the force required to detach the bacteria was quantified. These experiments showed a slight increase in the number of couplets formed in the presence of humic acid, and also showed a slight increase in the force required for detachment of the bacteria. Although an increase in adhesion number and strength was measured, the magnitude of the increase was small, indicating that humic acid plays a small role in bacterial adhesion to silica or glass surfaces.

Adhesiveness↗

PubMed2004

Importance of molecular details in predicting bacterial adhesion to hydrophobic surfaces.

Electrostatic and hydrophobic forces are generally recognized as important in bacterial adhesion. Current continuum models for these forces often wrongly predict measurements of bacterial adhesion forces. The hypothesis tested here is that even qualitative guides to bacterial adhesion often require more than continuum information about hydrophobic forces; they require knowledge about molecular details of the bacteria and substrate surface. In this study, four different strains of bacteria were adsorbed to silica surfaces hydrophobized with alkylsilanes. The thickness of the lipopolysaccharide layers varied on the different bacteria, and the lengths of the alkylsilane molecules were varied from experiment to experiment. Bacterial adhesion was assessed using column experiments and atomic force microscopy (AFM) experiments. Results show that hydrophobized surfaces have higher bacterial sticking coefficients and stronger adhesion forces than bare silica surfaces, as expected. However, adhesion decreased as the solution Debye length became longer than the alkylsilane, perhaps since the silane molecules could not "reach" the bacterial surface. Similarly, those bacteria with a long o-antigen layer had decreased adhesion, perhaps since the silane molecules could not reach surface-bound proteins on the bacteria. This study reveals that macroscopic measurements such as contact angle are not able to fully describe bacterial adhesion; rather, additional details such as the molecular length are required to predict adhesion.

Bacterial Adhesion↗

PubMed2004

Brownian sampling in an unbounded space.

As a particle undergoes translational Brownian motion in an unbounded space, the particle samples the space. Traditionally the sampling in N dimensions is quantified in terms of average squared distance traversed ( ). However, another quantitative measure of the sampled space is the total number (n) of equispaced regions (of size LN) sampled after a particle moves with a diffusion coefficient (D) for a time (t). Calculations show that the average =a(Dt/L2)b. Results are given for a and b for 1, 2, 3, and 4 dimensions.

Journal Article↗

PubMed2004

Altering surface charge nonuniformity on individual colloidal particles.

Charge nonuniformity (sigmazeta) was altered on individual polystyrene latex particles and measured using the novel experimental technique of rotational electrophoresis. It has recently been shown that unaltered sulfated latices often have significant charge nonuniformity (sigmazeta = 100 mV) on individual particles. Here it is shown that anionic polyelectrolytes and surfactants reduce the native charge nonuniformity on negatively charged particles by 80% (sigmazeta = 20 mV), even while leaving the average surface charge density almost unchanged. Reduction of charge uniformity occurs as large domains of nonuniformity are minimized, giving a more random distribution of charge on individual particle surfaces. Targeted reduction of charge nonuniformity opens new opportunities for the dispersion of nanoparticles and the oriented assembly of particles.

Journal Article↗

PubMed2003

Oriented adhesion of Escherichia coli to polystyrene particles.

The adhesion of nonflagellated Escherichia coli strain K-12 to polystyrene (PS) latex spheres or glass capillaries has been observed by using several techniques. Attention was focused on the orientation of the rod-shaped bacteria as they adhered to the surfaces in 100 mM phosphate-buffered saline. Data show that PS particles adhered to the ends of the bacteria more than 90% of the time. Moreover, the PS particles adhered to one end only, never to both. Similarly, for experiments with bacteria adhering to glass, the bacteria adhered on their ends. In order to determine whether the end of a bacterium had a different charge density from that of the middle, rotational electrophoresis experiments were used. These experiments indicated no measurable charge nonuniformity. In order to examine how strongly adhered the bacteria were to the PS particles, differential electrophoresis was used. Almost always, bacteria were found to be irreversibly adhered to the PS spheres. The cause of the oriented adhesion is not likely due to surface lipopolysaccharides (LPS), since the three strains of K-12 that were used, each having a different length of LPS, showed similar behavior. The results are discussed in terms of bacterial cell polarity. The data indicate that nanodomains on the bacterial ends are important for adhesion and that the time scale for irreversible adhesion is short.

Bacterial Adhesion↗

PubMed2002

Electrophoresis of randomly charged particles.

The technique of "rotational electrophoresis" has been developed recently to measure the charge nonuniformity on Brownian particles in a suspension. Measurements of the angular velocity in electrophoresis are interpreted with electrokinetic theory to give a standard deviation of zeta potential among N regions on a particle. A key question is how various molecular mechanisms of charging could lead to charge nonuniformity on a length scale of O (100 nm). Simple statistical physics is used to show that although Poisson charging with univalent charges cannot explain recent measurements showing significant charge nonuniformity, random charging with multivalent charges can better explain the data. In addition, the result shows that a small number of charged "visualization" molecules can be adsorbed to a particle without impacting the experimental technique of rotational electrophoresis.

Colloids↗