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Scaling procedures in colloidal electro-optics.

In a series of recent papers, we demonstrate the possibility to use the complete electro-optic saturation curves (or arbitrary part of them) to analyse the polarization mechanisms of charged colloidal particles. Scaling of the electro-optic saturation curves by field intensity permits to find the frequency range in which the functional dependence of the effects, hence the orientation mechanism remains unchanged. Similar procedure can be applied to verify the changes of this dependence with variation of particle electric parameters. When different polarization mechanisms are involved the new scale helps their analysis. The aim of the present paper is to summarize the basic applications and advantages of the scaling method in the electro-optic investigation of charged colloids.

Colloids↗

Synthesis of versatile chemical tools toward a structure/properties relationships study onto targeting colloids.

As part of a drug delivery project, four aldehydes of the type Pam-Lys(Pam)-spacer-CO-CHO were synthesized to be included in targeting colloids. Though amphiphilic, they were obtained within reasonable yields (18-55%) and with high RP-HPLC purity ( approximately 90%). Parallely, six complementary targeting peptides of the type H(2)N-NH-CH(2)-CO-spacer-YGRGDSP-NH(2) were prepared to be anchored onto colloids. Isolated yields are related to the spacer length and nature. To easily and rapidly modulate the distance between the peptide and the vesicle, every partners were elaborated on solid phase and the expected constructions were obtained by hydrazone ligation. One possible application is presented here with multilamellar vesicles targeting HUVEC cells. Preliminary results prove that the fine-tuning of the spacer length permits to optimize the recognition toward the target cells.

Aldehydes↗

Physicochemical characterization of colloidal drug delivery systems such as reverse micelles, vesicles, liquid crystals and nanoparticles for topical administration.

Topical administration of cosmetics and pharmaceuticals involves a variety of different formulations of which colloidal drug carrier systems are currently of particular interest. After a short introduction of reverse micellar solutions, liquid crystals, vesicles and nanoparticles, appropriate methods of physicochemical characterization are introduced including X-ray diffraction, laser light scattering, electron microscopy, and differential scanning calorimetry. Emphasis is laid on topical applications of the colloidal drug delivery systems (DDS) covered, with the main objective of both sustained drug release and improved stability of DDS.

Chemical Phenomena↗

Investigation of the glidant properties of compacted colloidal silicon dioxide by angle of repose and X-ray photoelectron spectroscopy.

The optimal flow-enhancing effect of a new compacted, hydrophilic colloidal silicon dioxide (AEROSIL 200 VV Pharma) on microcrystalline cellulose (Avicel PH 101) and pregelatinized starch (Starch 1500) was found to be 0.25% under gentle and 0.125% under strong mixing conditions, as measured by the angle of repose. The effect could be explained by X-ray photoelectron spectroscopy (XPS) investigations. The Si 2p signals of the silicon dioxide indicated that the coverage of the excipient surface with AEROSIL was greater for all mixtures produced under strong mixing conditions and corresponded to a higher degree of de-agglomeration of the AEROSIL aggregates. The more extensive surface coverage of Avicel PH 101 as compared to Starch 1500 could be explained by the particle morphology on the one hand and by the XPS C 1s signals on the other. Due to the different conformation of the two excipients, Avicel PH 101 offers a higher density of hydroxyl groups on its surface which are available for hydrogen bonding with the surface hydroxyl groups of hydrophilic colloidal silicon dioxide.

Cellulose↗

Labeling efficiency and biodistribution of Technetium-99m labeled nanoparticles: interference by colloidal tin oxide particles.

The interference of colloidal tin oxides on the biodistribution of (99m)Technetium radiolabeled chitosan nanoparticles has been overcome by using sodium borohydride instead of commonly used stannous salts as reducing agent for the reduction of (99m)Tc (VII) to lower valency states. Biodistribution of radiolabeled chitosan nanoparticles prepared by using stannous chloride method revealed localization of the radioactivity mainly in the liver and spleen while that of radiolabeled chitosan nanoparticles prepared by using sodium borohydride method manifested the presence of radioactivity in blood up to an extent of 10% even after 2 h. Interestingly, the reduction of radioactivity in the latter case with the progress of time was not manifested through an increase in activity in the liver. Rather, a time dependent increased accumulation of radioactive materials was observed in the stomach. From the results it has been concluded that the biodistribution is strongly influenced by the presence of colloidal particles of tin oxides and (99m)Tc labeled chitosan nanoparticles are RES evading and long circulating in blood when Tc (VII) is reduced by sodium borohydride and not by stannous chloride during radiolabeling process.

Animals↗

Comparison between the effects of TiO2 synthesized by photoassisted and conventional sol-gel methods on the photochromism of WO3 colloids.

WO3 colloids can exhibit a blue color under UV-light irradiation due to the absorption of electrons trapped at the energy levels within the forbidden gap and this coloration performance can be improved by TiO2 nanoparticles. In this work, it is found that TiO2 prepared by the photoassisted method (TiO2-P) exhibits stronger enhancement effects than that prepared by the conventional sol-gel method (TiO2-C). Several possible mechanisms have been proposed to account for this phenomenon. The migration of charge carriers toward different directions is promoted since the flat-band potential of TiO2-P colloids is more negative than that of TiO2-C and the contact between WO3 and TiO2 particles is improved in the WO3/TiO2-P system; there are more efficient TiO2 and hole scavengers (i.e., Ti3+ and/or TiO2-O2*- species) in the system containing TiO2-P; the bandgap of TiO2-P becomes narrowed, and so on. In addition, the potential applications of this process are also discussed briefly.

Absorption↗

Interaction forces between cellulose microspheres and ultrathin cellulose films monitored by colloidal probe microscopy-effect of wet strength agents.

Colloidal probe microscopy was employed to study forces between cellulose surfaces upon addition of a series of cationic copolymers in aqueous solution, as model compounds for wet strength agents. The content of quaternary ammonium groups and primary amines was systematically varied in the cationic polymers, to distinguish between the importance of electrostatical and H-bonding effects. Cellulose microspheres were glued at the apex of tipless microfabricated cantilevers and used as colloidal probes. Ultra thin cellulose films and cellulose fibres were employed as model surfaces. The cellulose films of a thickness of about 5 nm were spin-coated from cellulose solution onto silicon substrates. The root-mean-square-roughness (RMS) was 0.3-0.8 nm. The cationic model polymers were compared to Servamine, a polymer employed as standard wet strength resin in papermaking industries. Force versus separation measurements showed a detailed picture of adhesion and contact breaking. Relatively strong adhesion of the order of 0.3 mJ/m(2) was observed with Servamine within a range of approximately 10 nm. At larger distances weak bond breaking and elastic chain pulling were identified. When approaching the surface one to two small jump-in's possibly related to strong binding of Servamine and subsequent attraction could be found in the case of Servamine. In contrast, all the model copolymers showed only a weak adhesion of 8-30 micro/m(2), i.e., an order of magnitude less than that of Servamine and subsequent elastic rupture domains. The contour length, persistence length and characteristic rupture distances were calculated by means of applying the WLC model. Measurements against cellulose fibres obtained from the production process proved the relevance of the model systems.

Amines↗

Lateral separation of colloids or cells by dielectrophoresis augmented by AC electroosmosis.

Colloidal particles and biological cells are patterned and separated laterally adjacent to a micropatterned electrode array by applying AC electric fields that are principally oriented normally to the electrode array. This is demonstrated for yeast cells, red blood cells, and colloidal polystyrene particles of different sizes and zeta-potentials. The separation mechanism is observed experimentally to depend on the applied field frequency and voltage. At high frequencies, particles position themselves in a manner that is consistent with dielectrophoresis, while at low frequencies, the positioning is explained in terms of a strong coupling between gravity, the vertical component of the dielectrophoretic force, and the Stokes drag on particles induced by AC electroosmotic flow. Compared to high frequency dielectrophoretic separations, the low frequency separations are faster and require lower applied voltages. Furthermore, the AC electroosmosis coupling with dielectrophoresis may enable cell separations that are not feasible based on dielectrophoresis alone.

Cell Membrane↗

Dispersion and aggregation of nanoparticles derived from colloidal droplets under low-pressure conditions.

Formation of individually dispersed nanoparticles or compactly aggregated nanoparticles from sols via a spray-drying route at low pressure was investigated experimentally. Silica sol was used as a sample material. Effects of operating temperature, colloid size, sol concentration, pressure, pH and zeta potential of sols on the morphology of product particles were investigated. From the experimental results, it was shown that dispersed nanoparticles could be obtained at a relatively low pressure (20 Torr) and low temperature (200 degrees C). The experiment also showed that dispersed nanoparticles could be achieved by careful control of the interfacial energy (pH value) of the colloidal precursor. A possible mechanism of sol-to-dry-particle formation in the spray-drying process at low pressure is suggested, based on the experimental results and the available theories. This mechanism was able to explain the experimental results well.

Colloids↗

Preparation and colloidal stability of monodisperse magnetic polymer particles.

A previously proposed method was examined for producing monodisperse, submicrometer-sized magnetic polymer particles. The method applies soap-free emulsion polymerization during which Fe3O4 magnetic nanoparticles are heterocoagulated onto precipitated polymer nuclei. To chemically fix the magnetic particles to the polymer nuclei, vinyl groups were introduced on the Fe3O4 particles in a preliminary surface modification reaction with methacryloxypropyltrimethoxysilane, and methacryloxypropyldimethoxysilane (MPDMS) was added to reaction systems of the soap-free emulsion polymerization. The colloidal dispersion stability of magnetic polymer particles was improved by the addition of an ionic monomer, sodium p-styrenesulfonate (NaSS), during the polymerization. The polymerizations were carried out with styrene monomer and potassium persulfate initiator in ranges of NaSS concentrations (0-2.4 x 10(-3) M), NaSS addition times (60-80 min), and monomer concentrations (0.3-0.6 M) at fixed concentrations of 1.6 x 10(-2) M initiator and 1.3 x 10(-2) M MPDMS for pH 4.5 adjusted with a buffer system of [CH3COOH]/[NaOH]. The addition of NaSS during the polymerization could maintain the dispersion stability of magnetic polymer particles during the polymerization. Selection of the reaction conditions enabled the preparation of colloidally stable, submicrometer-sized magnetic polymer particles that had coefficients of variation of distribution smaller than the standard criterion for monodispersity, 10%.

Colloids↗

Stability of mixtures of charged silica, silica-alumina, and magnetite colloids.

We report experiments on the stability of aqueous mixtures of charged colloidal magnetite and charged silica and silica covered with alumina particles of similar size. First, positively charged magnetite dispersions were mixed with negatively charged silica dispersions at pH 4, at different volume ratios and low colloid volume fractions, producing mixtures which were stable over a period of weeks despite the expected electrostatic attraction between the oppositely charged particles. When magnetite particles were mixed with positively charged silica covered with alumina at pH 4 under exactly the same conditions, some of the systems separated to form a magnetite sediment. When the volume fraction of the initial dispersions was increased, the behavior of the mixtures was the opposite: positive magnetite/negative silica mixtures were unstable at intermediate volume ratios. The unexpected behavior of the mixtures was investigated by means of electrophoretic mobility, initial susceptibility, and dynamic light scattering measurements as well as sedimentation experiments.

Aluminum Oxide↗

Stability of dispersions of colloidal alumina particles in aqueous suspensions.

The colloidal stability of suspensions of alumina particles has been investigated by measuring particle size distribution, sedimentation, viscosity, and zeta potential. Alumina particles were found to be optimally dispersed at pH around 3 to 7.8 without dispersant and at pH 8.5 and beyond with dispersant. The above results corroborate zeta potential and viscosity measurement data well. The surface charge of alumina powder changed significantly with anionic polyelectrolyte (ammonium polycarboxylate, APC) and the iep shifted toward more acidic range under different dispersant conditions. It was found that the essential role played by pH and dispersant (APC) on the charge generation and shift in the isoelectric point of alumina manifests two features: (i) the stability decreases on approaching the isoelectric point from either side of pH, and (ii) the maximum instability was found at pH 9.1 for alumina only and at pH 6.8 for alumina/APC, which is close to the isoelectric points for both the system, respectively. Using the model based on the electrical double-layer theory of surfactant adsorption through shift in isoelectric points, the authors could estimate the specific free energy of interaction (7.501 kcal/mol) between particles and dispersant. The interaction energy, zeta potential, sedimentation, and viscosity results, were used to explain the colloidal stability of the suspension.

Aluminum Oxide↗

Catalytic properties of carboxylic acid functionalized-polymer microsphere-stabilized gold metallic colloids.

Polymer-microsphere-stabilized gold metallic colloids have been prepared by a novel strategy of simple and convenient reduction of the metallic salt through the stabilization of the active carboxylic acid group on the gel and surface layer of the microsphere. The nature of the interaction between the carboxylic acid and Au nanoparticles was studied in detail by XPS. Preliminary results indicate that polymer-microsphere-stabilized gold colloids are active catalysts for the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride as reductant. The catalytic properties of the stabilized catalyst for recycling were also investigated.

Adsorption↗

Interfacial assembly of a phospholipid Langmuir monolayer by electrodeposited silver colloids.

Two-dimensional nanostructured silver films were electrodeposited at the surface of a silver nitrate subphase coated by a negatively charged dimyristoylphosphatidylglycerol (DMPG) Langmuir monolayer. The modifications of the phospholipid interfacial organization generated by the growing colloidal silver film were investigated using surface pressure-time isotherms and grazing incidence X-ray diffraction experiments (GIXD). A decrease in the initial surface pressure of the DMPG monolayer is observed outside of the growing silver film, followed by a stabilization of the surface pressure when the radius of the metallic layer reaches its plateau value. This behavior is attributed to the compression of the DMPG molecules above the silver film and to the correlated relaxation and expansion of those outside the silver film area as recorded by a Wilhelmy pressure sensor. GIXD experiments further evidenced the contraction of the phospholipid monolayer above the electrochemically growing films. Indeed, the diffraction spectra show a shift in the peak position toward higher values of the in-plane component of the wave-vector transfer, indicating a closer packing of the DMPG alkyl chains. This is also in agreement with the observed loss of the chain tilt angle, suggesting that the colloidal silver film induces interfacial structuring of the DMPG monolayer.

Colloids↗

Synthesis of CdS nanoparticles in colloidal state and its possible interaction with tyrosine.

The basic objective is to develop a simpler method of preparation of the colloidal CdS nanoparticles with greater stability and to study interaction with tyrosine molecules. Average size of the particles in the colloid is found to be about 3 nm as probed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements. Effect of both sulfide enriched CdS as well as Cd(2+) enriched CdS on tyrosine is investigated both through absorbance and emission spectroscopy. Quenching of tyrosine emission followed Stern-Volmer relation and was found to be independent of temperature, indicating possible static quenching. However, Forster transfer between tyrosine and CdS can be suspected to mimic static quenching in addition to the charge transfer complexes. In the presence of Cd(2+) enriched CdS nanoparticles, the emission of tyrosine in phosphate buffer shows typical spectral broadening and a long wavelength increase in fluorescence emission. This may be attributed to the sensitized emission of CdS itself.

Cadmium Compounds↗

Mobilization of river transported colloidal aluminium upon mixing with seawater and subsequent deposition in fish gills.

During flooding events, increased concentrations of gill-reactive aluminium (Al) have been identified in estuarine water causing high Al accumulation in fish gills. By in situ filtering and ultrafiltering river water (pH 5.5-6.4, 3-5 mg L(-1) DOC) and continually mixing the size fractioned river water with seawater (30 in salinity), Al mobilization was studied in flow-through tank systems (6 in salinity) during a six-week field experiment in Western Norway. Atlantic salmon (Salmo salar L.) kept in tanks were continuously exposed to the mixtures. Based on in situ Al fractionation of the experimental waters and sampling of gills from exposed fish, results showed that Al associated with river transported colloids, probably organic material ( 8 kDa) was mobilized to low molecular mass cationic Al-species (LMM Al(i)) upon contact with seawater. Mobilized Al(i)-species deposited immediately on fish gills. During high flow conditions with increased amounts of colloidal material, the concentration of mobilized LMM Al(i) and the Al accumulation in gills of fish exposed to river water-seawater mixtures increased by a factor of 5 and 10, respectively, compared to the input river water. The concentration of mobilized LMM Al(i) and the Al accumulation in fish gills decreased with time after mixing (from 1 to 30 min) and as high runoff subsided.

Aluminum↗

Application of cross-flow ultrafiltration for the determination of colloidal abundances in suboxic ferrous-rich ground waters.

A suboxic groundwater from a sandy coastal aquifer was sampled using a new air free, large volume sampling method. Subsequent processing for size fractionation was completed with a modified cross-flow ultrafiltration (CFF) system equipped with a 1 kDa CFF membrane. By purging the CFF system with nitrogen, no oxygen was able to reach the sample. With this optimization, the sample was processed with higher than 90% recovery in terms of both iron and phosphate. Only about 4% of iron and 20% of phosphate in the filtered (0.2 microm) groundwater sample was found to be in colloidal form in the groundwater. In contrast, if no care was taken to maintain the suboxic environment of the original sample, iron was rapidly and completely oxidized and subsequently adsorbed to the CFF membrane. Other elements, such as phosphorus, were also lost to the CFF membrane to a substantial degree, and the mechanism is most likely coprecipitation with iron oxides. This study thus strongly supports the importance of maintaining ambient redox conditions during sampling and fractionation, especially for the determinations of colloid abundances in groundwater.

Colloids↗

Impact of colloidal and soluble organic material on membrane performance in membrane bioreactors for municipal wastewater treatment.

Two parallel membrane bioreactors (2 m3 each) were operated over a period of 2 years. Both pilots were optimised for nitrification, denitrification, and enhanced biological phosphorous elimination, treating identical municipal wastewater under comparable operating conditions. The only constructional difference between the pilots was the position of the denitrification zone (pre-denitrification in pilot 1 and post-denitrification in pilot 2). Despite identical modules and conditions, the two MBRs showed different permeabilities and fouling rates. The differences were not related to the denitrification scheme. In order to find an explanation for the different membrane performances, a one-year investigation was initiated and the membrane performance as well as the operating regime and characteristics of the activated sludge were closely studied. MLSS concentrations, solid retention time, loading rates, and filtration flux were found not to be responsible for the different performance of the submerged modules. These parameters were kept identical in the two pilot plants. Instead, the non-settable fraction of the sludges (soluble and colloidal material, i.e. polysaccharides, proteins and organic colloids) was found to impact fouling and to cause the difference in membrane performance between the two MBR. This fraction was analysed by spectrophotometric and size exclusion chromatography (SEC) methods. In a second step, the origin of these substances was investigated. The results point to microbiologically produced substances such as extracellular polymeric substances (EPS) or soluble microbial products (SMP).

Bioreactors↗