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PubMed1998

Preparation of Monodisperse, Micron-Sized Polystyrene Particles with Single-Stage Polymerization in Aqueous Media.

A single-stage polymerization technique, proposed for producing micron-sized polymer particles in aqueous media by Gu and Konno, was examined. Styrene was used for the monomer, potassium persulfate for the initiator, and cetyltrimethylammonium bromide and sodium dodecyl sulfate were used for the ionic surfactants to control the aggregation of the particles during the reaction. Particle-size distributions and monomer-to-polymer conversions were measured over a range of initiator concentration (2-8 mmol/dm3 H2O), stirring speed (200-400 rpm), surfactant addition time and monomer concentration (1.1-2.2 mol/dm3 H2O). Changes in the initiator concentration and stirring speed did not bring about significant effect on the particle-size distributions. On the other hand, the addition of time affected the coefficient of variation of the particle-size distribution, but it had no significant effect on the average diameter of the particles. An increase in the monomer concentration enlarged the average size without lowering the coefficient of variation of particle-size distribution. Monodisperse polystyrene particles with an average diameter of 3.3 µm and a coefficient of variation of particle size distribution 7% could be prepared with the present technique. Copyright 1998 Academic Press.

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PubMed1999

Surface Electrical Properties of Polystyrene Latex.

A polystyrene latex suspended in HCl has been studied by dielectric response and dynamic mobility measurements. The aim was to see if these data, along with previous results from other techniques, could be interpreted in a consistent way within the standard electrokinetic model to yield information about the surface electrical properties of the latex. It was found that the zeta-potentials deduced from dynamic mobility and conductivity measurements were reasonably consistent, but did not agree well with those deduced from the electrophoretic mobility. The use of a dynamic Stern layer did not improve the agreement to any great extent. It is conjectured that differences in the methods of preparation, in particular the use of centrifugation, may be responsible for some of the disagreement. The pH-dependence of the dynamic mobility was also investigated and found to be weak. The dielectric response measurements showed significant discrepancies from the predictions of the standard electrokinetic model in the kHz regime, and the dynamic Stern layer model with realistic parameters could not improve the agreement very much. However the experimental relaxation frequencies were in good agreement with the predictions of the theory. Copyright 1999 Academic Press.

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PubMed1998

Site Selectivity in the Deposition and Redeposition of Polystyrene Particles to Glass.

The site selectivity in the deposition and redeposition of negatively charged, polystyrene particles to a glass collector surface was studied under flow, by first depositing particles to the collector surface and then removing them by passing of an air-liquid interface. Using an image analysis system, the coordinates of the occupied sites were memorized and subsequently the probability of redeposition on these sites relative to deposition on other collector surface areas was determined. In low ionic strength buffers, 20 and 30 mM KNO3, redeposition probabilities on previously occupied sites were up to 51 times higher than for deposition elsewhere, while in high ionic strengths buffers (above 30 mM) redeposition probabilities were essentially similar as for deposition on other collector surface sites. It is suggested that high affinity sites for particle deposition exist on glass, on which preferential (re)deposition is mediated through attractive electrostatic interactions. Although such a suggestion is not new, this is the first time supporting evidence has been collected through redeposition experiments as described here. Copyright 1998 Academic Press.

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PubMed1999

Molecular Weight Effect on Latex Film Formation from Polystyrene Particles: A Photon Transmission Study.

The photon transmission method was used to probe the time evolution of film formation from latex particles. Two different latex films were prepared from high molecular weight (HM) and low molecular weight (LM) polystyrene particles at room temperature and were annealed at various temperatures in 2.5-min time intervals above the glass transition. The increase in the transmitted photon intensity (Itr) is attributed to the increase in "crossing density" at the junction surface. The Prager-Tirrell model was employed to interpret the increase in crossing density at the junction surface. The back and forth activation energies were measured for HM and LM films and found to be around 59 and 87 kcal/mol for a reptating polymer chain across the junction surface. Monte Carlo simulations were performed for photon transmission through a rectangular lattice. The number of transmitted photons (Ntr) was calculated as a function of the mean free path of photons. It was observed that Ntr, similar to Itr, increases as the square of the mean free path of photons is increased. Copyright 1999 Academic Press.

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PubMed1999

Study on Preparation and Morphology of Uniform Artificial Polystyrene-Poly(methyl methacrylate) Composite Microspheres by Employing the SPG (Shirasu Porous Glass) Membrane Emulsification Technique.

Fairly uniform polystyrene-poly(methyl methacrylate) (PST-PMMA) composite microspheres were prepared by employing the SPG (Shirasu Porous Glass) membrane emulsification technique. PST, PMMA, and cosurfactant (lauryl alcohol, LOH) dissolved in dichloromethane (DCM) were used as a dispersed phase, and an aqueous phase containing poly(vinyl alcohol) and sodium lauryl sulfate was the continuous phase. The effects of LOH amount on the critical pressure of emulsification (Pcr), size distribution of droplets, and morphologies of final particles were investigated. It was found that Pcr decreased with increasing LOH amount because of preferential partition of LOH on the surface of the droplets in the initial stage of emulsification. When polymer concentration or PMMA/PST ratio was low, the size distribution of droplets decreased with increasing LOH amount, whereas an inverse trend was observed when both polymer concentration and PMMA/PST ratio were high. When polymer concentration was low, PST-PMMA core-shell particles always were obtained in the absence of LOH, irrespective of the PMMA/PST ratio. In the presence of LOH, however, microdomain, hemisphere, and inverted core-shell morphologies were formed as the PMMA/PST ratio decreased from 5/5 to 1/9 (g/g). When polymer concentration was high, different morphologies such as multiplet and inverted core-core-shell were observed. Theoretical calculations of morphologies were carried out, and agreement was obtained between experimental and calculated results. Copyright 1999 Academic Press.

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PubMed1999

Chemically Modified Glucose Oxidase with Enhanced Hydrophobicity: Adsorption at Polystyrene, Silica, and Silica Coated by Lipid Monolayers.

Covalent modification of glucose oxidase from Aspergillus niger by the palmitic acid ester of N-hydroxysuccinimide at a molar ratio ester:protein of 56:1 results in the formation of the enzyme derivative with 11 attached palmitic chains. Surface hydrophobicity measurements by a fluorescent probe, 8-anilino-1-naphthalenesulfonate, indicate a drastic increase in the hydrophobicity index of glucose oxidase after such a modification. The modified glucose oxidase displays a much higher adsorption affinity for hydrophilic (silica) as well as for hydrophobic (silica coated by phosphatidyl choline and cholesterol monolayers and polystyrene latex beads) surfaces, and forms more compact surface layers compared to the native glucose oxidase. Such a difference results from a spontaneous formation of micelle-like aggregates (clusters) of the hydrophobized enzyme molecules (average size 500 nm), which come into contact with a surface. A possible structure of the glucose oxidase surface layers and the nature of the forces determining the adsorption of the enzyme on various adsorbents are discussed. Copyright 1999 Academic Press.

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PubMed1999

Migration of Polystyrene Latex Particle Bands in Density-Gradient Electrophoresis.

Electrophoretic migration of sulfated polystyrene latex particle bands was investigated in a density-gradient electrophoresis apparatus. The bands spread with time, and their velocity was found to depend on particle concentration and to decrease during the initial stages of electrophoresis. A change in pH during electrophoresis occurred, and this change may have caused variations in band velocity. Copyright 1999 Academic Press.

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PubMed1999

Atomic Force Microscopy and Wettability Study of Oxidized Patterns at the Surface of Polystyrene.

The surface properties of patterned surfaces made by a combination of photolithography and oxygen plasma treatment of polystyrene (PS) were investigated. PS and plasma-treated PS (PSox) were first characterized using X-ray photoelectron spectroscopy and the study of wetting dynamics (Wilhelmy plate method) in water and in solutions of different pH. The results indicated that the PSox surface may be viewed as covered with a polyelectrolyte-like gel, which swells depending on pH. It was then shown, using atomic force microscopy (AFM), that the adhesion force measured on PS with a silicon tip in water was higher compared with that measured on PSox. This feature allowed imaging of the oxidation patterns using the adhesion mapping mode. The origin of the pulloff force contrast, which could not be explained by combining Johnson-Kendall-Roberts theory and thermodynamic considerations, was attributed to repulsion between the tip and hydrated polymer chains present on the oxidized surface. Imaging was also performed in the lateral force mode, a higher friction being recorded on PS than on PSox. Copyright 1999 Academic Press.

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PubMed1999

Comparative Pore Structure Analysis of Dextran-Coated Polystyrene Particles.

Porous poly(styrene-divinylbenzene) (PS-DVB) particles were modified by adsorption of hydrophobically-modified dextrans, to provide chromatographic matrices for biomolecule chromatography. The dextran distribution and the pore characteristics of various coated PS-DVB beads were examined using nitrogen adsorption-desorption, mercury intrusion, and size exclusion chromatography. It was found that the adsorption of dextran does not result in homogeneous layers but rather in inhomogeneous ones. At high dextran loading and high content of hydrophobic groups in the adsorbed polymer, most of the pores of the macroporous rigid material are filled with a soft and porous dextran network being stabilized by hydrophobic interactions. According to chromatographic experiments, most of the surface was nevertheless expected to be covered at least by a thin and dense protecting layer since proteins-even those that are small enough to penetrate the dextran network-cannot interact nonspecifically with the internal pore surface. At low content of hydrophobic groups, dextran deposits preferentially as a thicker and more diffuse layer. However, the thickness of the coating is expected to be irregular and probably contributes to an increase in the roughness of the polystyrene surface. Copyright 1999 Academic Press.

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PubMed2000

Self-Assembly and Surface Structure of an Amphiphilic Graft Copolymer, Polystyrene-graft-omega-Stearyl-Poly(ethylene oxide).

Surface properties of the polystyrene-graft-omega-stearyl-poly(ethylene oxide) (PS-g-SPEO) have been characterized by X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), contact angle, and spin probe techniques. The XPS results indicate that the surface and bulk composition of the PS-g-SPEO copolymers differ remarkably from each other. The stearyl and EO components enrich at the copolymer/air interfaces due to the self-assembly of the stearyl groups. At the PS-g-SPEO-72.6 surface (the x in PS-g-SPEO-x indicates the bulk density of the SPEO in wt%), the self-assembly of the hydrophobic stearyl groups is strong enough to form a stable liquid crystalline phase as indicated by DSC. At polymer/water interfaces, PS-g-SPEO-72.6 presents a hydrophilic surface with low PEO mobility, whereas PS-g-SPEO-50.6 and PS-g-SPEO-31.0 present the hydrophobic surface with high PEO mobility. The two different types of the surfaces, with different characters in surface energy, surface mobility of PEO, and surface architecture of SPEO, will be quite valuable as models for detecting the synergistic action of the PEO chains and the stearyl groups (specific ligand for albumin binding) in protein solutions. Copyright 2000 Academic Press.

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PubMed2000

Heteroflocculation of Amidine Polystyrene Latex and Anticarsia gemmatalis Nucleopolyhedrovirus as a Model System for Studying Sunlight Protection.

Anticarsia gemmatalis nucleopolyhedrovirus (AgMNPV) is a baculovirus specific for the control of an important soybean defoliator. The baculovirus is comprised of double-stranded DNA, occluded in a proteinaceous structure called a polyhedron. Ultraviolet sunlight is the most destructive factor that affects the persistence of the virus in the field. In the present study, we use a model system wherein the pathogen is covered by another particle of opposite charge in order to test the effectiveness of a physical barrier as a protection against sunlight. Heteroflocculation experiments were carried out using two different age batches of AgMNPV and amidine polystyrene latex particles. The assessment of heteroflocculation was achieved by zeta potential and adsorption isotherm measurements, and by scanning electron microscopy. Despite the great difference in potentials between latex particles and the baculovirus, low-affinity isotherms were obtained in both pure water and 0.1 mM KCl. Adsorbed latex particles were easily washed out from the polyhedron surface. This low affinity could be attributed to the presence of a strongly repulsive hydration force of short range operating on the system. The results suggest that the failure to obtain a good physical barrier against sunlight might be attributed to the difficulty in keeping the polyhedron surface covered. Copyright 2000 Academic Press.

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PubMed2000

Adsorption and Desorption of Triton X-100 in Polystyrene Particles with Different Functionality.

A complete adsorption study of Triton X-100 onto latexes with different functionality is presented. Three surfactant-free polystyrene latices with different chemical surface groups (sulfate, carboxyl, and amidine) were prepared. The pH of the liquid phase controls the surface charge, and hence this factor can be considered an important variable in this study. The adsorption isotherms show that an increase in the surface charge yields a decrease in the amount of adsorbed surfactant. A descriptive mechanism of the adsorption process which considers the presence of holes in the layer of adsorbed surfactant is presented for explaining the experimental results. On the other hand, the adsorption isotherms have been analyzed with two classical adsorption theories, those of Langmuir and Kronberg et al. Both theories give a good description of the results, but the latter offers more information on the adsorption phenomena. Copyright 2000 Academic Press.

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PubMed2000

Initial Stage Dynamics of Bridging Flocculation of Polystyrene Latex Spheres with Polyethylene Oxide.

The kinetics of bridging flocculation of polystyrene latex (PSL) particles induced by addition of excess polyethylene oxide (PEO) in the initial stage was studied using standardized mixing flow generated in an end-over-end rotation apparatus. To clarify the effect of the rate of polymer supply, flocculation experiments were performed by changing polymer concentration (C(p)). As was found in previous investigation, the progress of flocculation is divided into two stages. The first stage is characterized by an enhancement of the rate of flocculation by polymer addition. The increase in polymer concentration results in a higher enhancement but in a shorter duration for this stage. In the second stage, the flocculation is essentially stopped due to the appearance of steric stabilization. It was found that the ultimate degree of flocculation goes through a maximum against C(p). That is, when C(p)>==1.0 ppm, the ultimate degree of flocculation decreases with increased C(p). In this region, a clear crossover from the first stage to the second stage was observed. In the extreme case, evidence of a slight setback of flocculation was confirmed, which implies the breakup of metastable bridges by the application of additional fluid shear. When C(p)<==1.0 ppm, the ultimate degree of flocculation decreases with decreased C(p). The crossover from the first stage to the second stage appears more gradual at lower C(p). These results were observed irrespective of ionic strength. This result was interpreted as the elimination of a bare surface due to the spreading of a steric layer of adsorbed polymer. The characteristic time for reconformation of the polymer at a bare colloidal surface was estimated to be a few seconds. Copyright 2000 Academic Press.

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PubMed2000

The Hybrids of Polystyrene-block-Poly(ethylene Oxide) Micelles and Sodium Dodecyl Sulfate in Aqueous Solutions: Interaction with Rh Ions and Rh Nanoparticle Formation.

The interaction of amphiphilic block copolymer, polystyrene-block-poly(ethylene oxide) (PS-b-PEO), with anionic surfactant, sodium dodecyl sulfate (SDS), in aqueous media has been studied by sedimentation in ultracentrifuge. Three well-defined populations of hybrid aggregates corresponding to micelles, micellar clusters, and supermicellar aggregates were detected in the PS-b-PEO/SDS aqueous solutions at various rotation rates. Parameters of all the micellar aggregates were characterized depending on the SDS loading. An increase in the SDS loading was found to result in an increase in block copolymer/surfactant micelle size and weight at the SDS concentration of 0.8x10(-3) mol/L and in a slight decrease of both parameters at critical micelle concentration and at higher concentration. This decrease was caused by incorporation of SDS molecules in block copolymer micelles followed by charging the PS core and repulsion between similar charges. Using dichlorotetrapyridine rhodium(III)chloride hexahydrate ([Rh(Py)(4)Cl(2)]Clx6H(2)O), ion exchange of surfactant counterions in the hybrid PS-b-PEO/SDS system for Rh cations was carried out, which allowed saturating the micellar structures with Rh species. Subsequent reduction of the Rh-containing hybrid solutions with NaBH(4) resulted in the formation of Rh nanoparticles with a diameter of 2-3 nm mainly located in the block copolymer micellar aggregates. Copyright 2000 Academic Press.

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PubMed2000

A Simple Method for Producing Micrometer-Sized Monodisperse Polystyrene Particles in Aqueous Media.

A method was developed for producing micrometer-sized, highly monodisperse polystyrene particles in single stage polymerization in aqueous media. The method employs an amphoteric surfactant, dimethyldodecylbetaine, that is added to the reaction system of styrene/K(2)S(2)O(8)/water in early stage of reaction. Polymerizations were carried out over a range of initiator concentrations (4-8 mmol/dm(3) H(2)O). The polymerization procedure could produce particles with an average diameter of 3.4 µm with a coefficient of variation of particle size distribution of 4.0%. Copyright 2000 Academic Press.

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PubMed2000

Synthesis of Highly Charged, Monodisperse Polystyrene Colloidal Particles for the Fabrication of Photonic Crystals.

We have developed a series of emulsion polymerization recipes for the synthesis of highly charged, monodisperse polystyrene colloids of diameters between 100-400 nm. These spherical colloidal particles were crosslinked with divinyl benzene and functionalized with 1-allyloxy-2-hydroxypropane sulfonate. These highly charged, monodisperse colloidal particles readily self-assemble into robust three-dimensionally ordered crystalline colloidal arrays (CCAs). These CCAs operate as photonic crystals that Bragg diffract light in the ultraviolet, visible, and infrared regions of the spectrum. Copyright 2000 Academic Press.

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PubMed2001

Sequential Adsorption of Triton X-100 and Sodium Dodecyl Sulfate onto Positively and Negatively Charged Polystyrene Latexes.

Individual and sequential adsorption of the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant Triton X-100 on cationic and anionic polystyrene latexes has been examined. Both latex samples, although charged differently (-16.2 and +11.0&mgr;C cm(-2)), must be considered hydrophobic polymer colloids. The adsorbed amounts of both surfactants on cationic and anionic latexes were found to be different as a consequence of the dissimilar interfacial properties of these two surfactants. In addition, a comparison between the two surfactants showed that SDS is more easily replaced than Triton X-100 when sequential adsorption on both latexes was studied. It was found that the electrophoretic mobility of surfactant latex complexes depends on the addition sequence order of both surfactants. In relation to colloidal stability, when a layer of a nonionic surfactant is adsorbed on the surface of latexes, the electrosteric mechanism explains the experimental results. If SDS is adsorbed the stabilization or unstabilization is a consequence of the changes in the electrical repulsion between particles. However, when both surfactants are adsorbed, the assumption of additivity is not correct; that is, the electrostatic repulsion (V(R)) and the steric repulsions (V(osm) and V(vr)) are not totally independent. Copyright 2001 Academic Press.

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PubMed2002

Novel sintering behavior of polystyrene nanolatex particles in the filming process.

The filming process of polystyrene nanolatex (NPS) particles was studied by a combination of various methods. For a constant annealing time of 1 h, the AFM images showed that the deformation and interdiffusion temperatures of NPS particles were ca. 90 and 100-110 degrees C, respectively. In spin-lattice relaxation measurements of solid state NMR, it is found that T1L, T1S, and PL increased significantly after annealing at 90 and 100 degrees C for 1 h. DSC results showed that there was a exothermic peak near Tg after annealing for 1 h at the elected temperatures below 95 degrees C; otherwise, the exothermic peak disappeared after annealing at 100 degrees C or above. The apparent density of NPS increased suddenly in the temperature range of 90-110 degrees C. The results indicated that the macromolecules are highly constrained in NPS particles, leading to higher conformational energy, with more free volume and segments less restricted, which are the driving forces for the particles sintering at a lower temperature compared to the micro-PS particles with larger diameter.

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