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Comparison of centrifugation and filtration techniques for the size fractionation of colloidal material in soil suspensions using sedimentation field-flow fractionation.

Sedimentation field-flow fractionation (SdFFF) with UV detection is used to systematically investigate the effect of traditional membrane filtration and centrifugation procedures on the isolation of specific size fractions from soil suspensions. Both procedures were used to isolate the nominal <0.45 and <0.2 microm fractions from a clay soil suspension. Results showed that the membrane filtration approach seriously underestimated the total mass of particulate matter present as compared to the centrifugation approach. This has serious implications forthe interpretation of results for "colloidal" and "soluble" fractions from soil suspensions and other environmental matrices obtained using the standard membrane approach. The results also show that sedimentation FFF has great potential as a robust and relatively mild technology for studying size distributions in the "colloidal" range for soil suspensions and other aquatic matrices.

Centrifugation↗

Hierarchical approach to model multilayer colloidal deposition in porous media.

Particle deposition is important in many environmental systems such as water and wastewater filtration, air pollution control, subsurface transport, biofilm formation and fouling, and thin film synthesis for use in remediation technologies. While continuum-level models have been developed to predict deposition dynamics in these systems, these models fail to explain transient dynamics of multilayer deposition from a mechanistic viewpoint. In this work, a multiscale approach has been developed to predict multiple layer irreversible colloidal deposition in the presence of interparticle electrostatic and van der Waals interactions in porous media. The approach combines the kinetic information obtained from the mesoscopic stochastic simulations of particle deposition with the macroscopic conservation equation describing colloidal transport. Sequential Brownian dynamics simulations are first performed by accounting for particle-particle (P-P) and particle-surface (P-S) interactions, and multilayered particle deposits are obtained. The available surface function quantifying the deposition kinetics is then obtained from the deposit microstructure. Deposition dynamics are studied at different ionic strengths and particle potentials that control the range and magnitude of interparticle interactions. Simulation results showed that the microstructure of the particle deposits formed under the influence of P-P and P-S electrostatic interactions exhibited significant variations with respect to ionic strength and could be qualitatively explained bythe interplay between the repulsive and attractive P-P and P-S interaction forces. The available surface function also varied significantly as a function of ionic strength. This basic understanding of the deposition dynamics at the mesoscale was then combined with the continuum-level transport equations to predict particle breakthrough curves in porous media. The approach is capable of capturing transient features of deposition dynamics, as demonstrated by the good agreement between the model predictions and the experimental observations.

Adsorption↗

Comparison of electrokinetic properties of colloidal fullerenes (n-C60) formed using two procedures.

In this study we report on the electrokinetic behavior of colloidal aggregates of C60fullerenes (n-C60) produced through two different techniques: solvent exchange and extended mixing with water. In the first technique, used to produce colloidal materials in several recent toxicity and transport studies, an organic solvent such as tetrahydrofuran (THF) is used to dissolve the C60 before mixing with water. The second technique is more indicative of conditions that might occur in natural aquatic systems. Both types of n-C60 were observed to be negatively charged under a variety of solution chemistries; however, the n-C60 formed using THF was more strongly charged. We conclude that n-C60 likely acquires charge through charge transfer from the organic solvent (when present) and surface hydrolysis reactions. Nevertheless, C60 is capable of acquiring charge and becoming dispersed as n-C60 in water without the aid of organic solvents, a pathway that may be important in determining the mobility of fullerenes in natural systems. These findings also show that n-C60 made using THF retains a portion of the solvent in the cluster structure, subsequently influencing the characteristics of the n-C60 and possibly requiring a re-interpretation of results from recent studies on n-C60 toxicity using THF-derived materials.

Colloids↗

Photocatalytic synthesis of copper colloids from CuII by the ferrihydrite core of ferritin.

The iron-storage protein ferritin encapsulates a nanoparticle of iron oxide. The size and properties of these nanoparticles can be adjusted by controlled oxidative hydrolysis reactions of Fe(II). This mineralized ferritin protein cage has previously been shown to act as an effective photocatalyst for reduction of Cr(VI). In the present work, we demonstrate that Fe(O)OH-mineralized ferritin catalyzes the photoreduction of Cu(II) to form a stable, air-sensitive, colloidal dispersion of Cu(0). In addition, the particle sizes of the Cu colloids can be controlled by varying the ratio of Cu(II) to ferritin. This illustrates an important principle, namely that the properties of one preformed material can be utilized for the specific synthesis of a second material, thus tailoring the desired physical properties of the final products. This procedure represents a multistep materials synthesis: the formation of a new nanomaterial from a catalytic precursor.

Catalysis↗

Intelligent colloidal hybrids via reversible pH-induced complexation of polyelectrolyte and silica nanoparticles.

We present novel intelligent colloidal polymer/silica nanocomposites, in which the complexation of cationic silica nanoparticles and a weak anionic polyelectrolyte can be manipulated simply by pH change through a hydrogen-bonding interaction and ionic complexation caused by hydrogen-transfer interactions between the constituents. Special silica particles which have nanometer size (diameter approximately 3.0 nm) and two independent proton-accepting sites were developed in this study. Both the silica and poly(acrylic acid) form transparent colloidal solutions in water, while a white turbid dispersion was obtained just after mixing the two solutions due to the complexation. The pH-induced association-dissociation behavior was confirmed by the turbidity and potentiometric titration measurements. The assembled structures of the hybrids were visualized by scanning force microscopy.

Acrylic Resins↗

Diffusion NMR spectroscopy for the characterization of the size and interactions of colloidal matter: the case of vesicles and nanoparticles.

We report the application of the pulse gradient spin-echo (PGSE) NMR technique (PGSE NMR) to the analysis of large colloidal materials, specifically vesicles formed from macromolecular amphiphiles and nanoparticles. Measurements of size and size distribution were demonstrated to be comparable to those obtained through dynamic light scattering or hydrodynamic chromatography. In comparison to these more common analytical methods, the use of PGSE NMR is particularly advantageous in that, as a spectroscopic technique, it adds chemical selectivity to the study of physical dimensions. In this way, chemically different species contemporarily present in a sample may be individually studied. In addition, we demonstrate the use of PGSE NMR to probe the existence of equilibria between macroamphiphiles present in solution and those present in vesicles or on the surface of nanoparticles. This feature in particular opens exciting possibilities for the characterization of the phase behavior and of the surface adsorption phenomena of colloids.

Colloids↗

Synthesis of colloidal Mn2+:ZnO quantum dots and high-TC ferromagnetic nanocrystalline thin films.

We report the synthesis of colloidal Mn(2+)-doped ZnO (Mn(2+):ZnO) quantum dots and the preparation of room-temperature ferromagnetic nanocrystalline thin films. Mn(2+):ZnO nanocrystals were prepared by a hydrolysis and condensation reaction in DMSO under atmospheric conditions. Synthesis was monitored by electronic absorption and electron paramagnetic resonance (EPR) spectroscopies. Zn(OAc)(2) was found to strongly inhibit oxidation of Mn(2+) by O(2), allowing the synthesis of Mn(2+):ZnO to be performed aerobically. Mn(2+) ions were removed from the surfaces of as-prepared nanocrystals using dodecylamine to yield high-quality internally doped Mn(2+):ZnO colloids of nearly spherical shape and uniform diameter (6.1 +/- 0.7 nm). Simulations of the highly resolved X- and Q-band nanocrystal EPR spectra, combined with quantitative analysis of magnetic susceptibilities, confirmed that the manganese is substitutionally incorporated into the ZnO nanocrystals as Mn(2+) with very homogeneous speciation, differing from bulk Mn(2+):ZnO only in the magnitude of D-strain. Robust ferromagnetism was observed in spin-coated thin films of the nanocrystals, with 300 K saturation moments as large as 1.35 micro(B)/Mn(2+) and T(C) > 350 K. A distinct ferromagnetic resonance signal was observed in the EPR spectra of the ferromagnetic films. The occurrence of ferromagnetism in Mn(2+):ZnO and its dependence on synthetic variables are discussed in the context of these and previous theoretical and experimental results.

Colloids↗

Coordination-induced formation of submicrometer-scale, monodisperse, spherical colloids of organic-inorganic hybrid materials at room temperature.

In this communication, we demonstrate a novel coordination-based strategy to the fabrication of submicrometer-scale, monodisperse, spherical colloids of organic-inorganic hybrid materials, carried out by mixing H2PtCl6 and p-phenylenediamine (PPD) aqueous solutions at room temperature. The particle size and polydispersity can be controlled by the molar ratio and concentration of reactants, and the optimum experimental parameters for the production of monodisperse colloids are also given.

Colloids↗

Organometallics meet colloid chemistry: a case study in three phases based on molecular carbonyl precursors containing zinc and manganese.

Two organometallic compounds containing zinc and manganese in different ratios are used as single-source precursors for the preparation of various new, bimetallic oxide materials with nanoscaled dimensions. It is shown that the materials synthesis can be performed in the solid-state, the liquid-phase, and even in the gas-phase. The molecular composition of the precursors determines the composition of the resulting materials. In addition, two novel methods for the preparation of highly crystalline metal oxide colloids are presented: The coupling between a gas-phase process and a colloidal approach, and the application of ozone as an oxidant for the transformation of metal carbonyls into oxides in the liquid phase.

Carbon Monoxide↗

Rapid determination of fumonisin B1 in food samples by enzyme-linked immunosorbent assay and colloidal gold immunoassay.

A rapid enzyme-linked immunosorbent assay (ELISA) test (microwell plate) and a membrane-based colloidal gold immunoassay in flow-through and lateral-flow formats for the rapid detection of fumonisin B1 (FB1) were developed. The rapid microwell assay can be completed within 20 min with the detection limit of 0.5 +/- 0.2 microg/L. Membrane-based colloidal gold immunoassays had a visual detection limit of 1.0 microg/L for FB1 with the detection time of <10 min. Matrix interference was eliminated by 15-fold dilutions of methanol extracts with buffer. These immunoassays can be used as quantitative or qualitative tools for the rapid detection of FB1 residues in 10-20 min on-site.

Arachis↗

Sorption and desorption of triadimefon by soils and model soil colloids.

Sorption-desorption of the azole fungicide triadimefon [1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2, 4-triazol-1-yl)-2-butanone] on eight soils and a series of single, binary, and ternary model soil colloids was determined using the batch equilibration technique. Regression analysis between Freundlich sorption coefficients (K(f)) and soil properties suggested that both clay and organic C (OC) were important in triadimefon sorption by soils, with increasing importance of clay for soils with high clay and relatively low OC contents. Triadimefon sorption coefficients on soil were not significantly affected by the concentration of electrolyte or the presence of soluble soil material in solution, but they were highly dependent on the soil:solution ratio due to the nonlinearity of triadimefon sorption on soil. Freundlich sorption isotherms slopes were very similar for all soils (0.75 +/- 0.02). Desorption did not greatly depend on the concentration at which it was determined and showed higher hysteresis for more sorptive soils. Results of triadimefon sorption on model sorbents supported that both humic acid and montmorillonite-type clay constituents contribute to triadimefon retention by soil colloids.

Adsorption↗

Amphiphilic cyclodextrin carriers embedding porphyrins: charge and size modulation of colloidal stability in heterotopic aggregates.

The interaction between the anionic 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphyrin (TPPS) and cationic vesicles formed by heptakis(2-omega-amino-O-oligo(ethylene oxide)-6-hexylthio)-beta-cyclodextrin (SC6CDNH2) has been investigated in detail through a combination of elastic light scattering (ELS), quasi-elastic light scattering (QELS), zeta potential measurements, and time-resolved fluorescence anisotropy. ELS experiments provided the first structural characterization of these cationic vesicles both in the absence and in the presence of TPPS porphyrin, modeling the system as a spherical particle described by a single thin shell form factor. The structure of mixed hetero-aggregates is modulated by charge and size of the two components as function of different porphyrin/cyclodextrin (CD) molar ratios. At the limiting molar ratio studied, the absolute value of zeta potential (/zeta/ = 12.5 mV) seems to be a reference value for the formation of stable colloidal CD vesicular aggregates at thermodynamic equilibrium. New insights on the structure of these heterotopic colloids have been obtained by analysis of rotational correlation times at different molar ratios exploiting time-resolved fluorescence anisotropy experiments. At high porphyrin loads, the anisotropy decays behave as monoexponentials and the rotational correlation times (1-2 ns) together with the r(0) values close to zero suggest the presence of small amounts of TPPS embedded in a hydrophobic environment either in monomeric or in aggregated form. At the lower porphyrin/CD molar ratios, the anisotropy decays exhibit a double-exponential behavior showing a predominant component with a slow rotational correlation time (20-25 ns) and limiting anisotropy values of approximately 0.15. This component has been assigned to molecules that are more stabilized onto the CD vesicles, that is, porphyrins embedded into the oligo-ethylene "wall" of the CD vesicles. Scanning near-field optical microscopy of the samples evaporated on glass surfaces gave further insights on the morphology and optical properties of these systems, confirming the embedding of TPPS on the vesicles and evidencing the role of the solvent.

Anions↗

Surface enhanced Raman scattering effects of silver colloids with different shapes.

By solution-based method, three kinds of silver colloids, self-assembled nanowires, triangular nanoplates and quasispherical nanoparticles, have been synthesized. TEM studies revealed that they exposed different crystal planes, such as {111} crystal planes to triangular nanoplates, mainly {100} and {111} planes to self-assembly nanowires. Hereby, do the distinct shapes and crystal planes have an impact on the surface enhanced Raman scattering (SERS)? The great differences of the SERS spectra of rhodamine B at these Ag colloids confirmed that the shapes and crystal planes of silver have great effect on Raman enhancement, especially the crystal planes.

Colloids↗

Cationic and anionic poly(N-isopropylacrylamide) based submicron gel particles: electrokinetic properties and colloidal stability.

A cationic and an anionic poly(N-isopropylacrylamide) (poly(NIPAM)) microgel latex were synthesized via batch radical polymerization under emulsifier-free conditions. The hydrodynamic properties, colloidal stability, and electrokinetic characteristics of these two samples were studied. The hydrodynamic particle size variation was discussed by considering the effect of salinity and temperature on the shrinkage of the thermally sensitive polymer domains. The colloidal stability also depended on temperature and electrolyte concentration. A stability diagram with two well-defined domains (stable and unstable) was obtained. The flow from one domain to the other was fully reversible due to the peculiar (de)hydration properties of the polymer. The electrokinetic behavior, which depends on electrical and frictional properties of the particles, was analyzed via electrophoretic mobility measurements. Results were discussed by considering both the particle structure dependence on temperature and salinity, and the electric double layer compression. In addition, the electrophoretic mobility data were analyzed using Ohshima's equations for particles covered by an ion-penetrable surface charged layer, as well as using another simpler equation for charges located on a hydrodynamic equivalent hard sphere. Differences between the properties of both latexes were justified by the presence of a hydrophilic comonomer, aminoethyl methacrylate hydrochloride (AEMH), in the cationic microgel.

Acrylamides↗

Dielectrophoresis of an inhomogeneous colloidal particle under an inhomogeneous field: a first-principles approach.

In reality, colloidal particles often possess an arbitrary inhomogeneity profile. We present a first-principles approach to dielectrophoresis of such an inhomogeneous colloidal particle under an inhomogeneous field of an oscillating electric dipole moment. For numerical simulations, we treat the inhomogeneous particle as a specific graded one with a physically motivated dielectric model and conductivity profile. We find that both multipolar interactions and spatial fluctuations inside the particle can affect the dielectrophoretic spectrum of the particle significantly.

Colloids↗

Probing molecules adsorbed at the surface of nanometer colloidal particles by optical second-harmonic generation.

It is observed that optical second-harmonic generation from molecules adsorbed at the surface of nanometer size colloidal particles occurs at angles as large as 90 degrees away from the fundamental beam direction. This phenomenon can be rigorously described by the nonlinear Rayleigh-Gans-Debye theory and used for probing molecules adsorbed on nanometer size colloidal particles.

Adsorption↗

Temperature-responsive formation of colloidal nanoparticles from poly(N-isopropylacrylamide) grafted with single-stranded DNA.

The thermal properties and temperature-responsive nanoparticle formation of poly(N-isopropylacrylamide) grafted with single-stranded DNA (PNIPAAm-g-DNA) were investigated. Copolymerization between nonamer single-stranded DNA with a vinyl group at its 5' terminus (DNA macromonomer) and NIPAAm was carried out so that the DNA macromonomer unit content should be less than 1 mol %. The turbidimetry and differential scanning calorimetry of the copolymer showed that the transition temperature increased and the enthalpy change of the phase transition decreased with increasing DNA macromonomer content in the copolymers, indicating that the DNA macromonomer behaves as a hydrophilic part in the copolymer and that the hydrophilicity is greater than that of sodium styrenesulfonate. Above the phase transition temperature, the copolymers formed colloidal nanoparticles with a dehydrated PNIPAAm core surrounded by DNA. When the formation of particles was conducted at higher temperatures, the dehydration of the copolymers proceeded such that the hydrodynamic radius (Rh) of the particles decreased. From the results of light scattering measurements, we calculated the surface area of particles occupied by one DNA (S(DNA)). The S(DNA) value decreased with increasing formation temperature, indicating that the DNA density on the particle surface increases with increasing formation temperature. The increase in the DNA density was also confirmed from the zeta-potential measurement of the particle. When MgCl2 was added to the copolymer solutions, the anionic charge of DNA was neutralized by Mg2+ so that Rh and the molecular weight of the particles increased with the increasing MgCl2 concentration. The turbidimetric detection of a target DNA was successfully demonstrated by utilizing the stability decrease of the colloidal particle upon hybridization on the particle surface.

Acrylic Resins↗

Stimuli-responsive surface crystallization of phospholipids from bimodal colloidal particles.

These studies focus on the effect of phospholipids in the presence of ionic surfactants on the behavior of poly(methylmethactrylate/n-butyl acrylate) (p-MMA/nBA) colloidal particles during film formation. With the presence of two surfactants, it is possible to obtain particles that exhibit two distinct particle sizes. The presence of hydrogenated soybean phosphatidylcholine (HSPC) and sodium dioctyl sulfosuccinate (SDOSS), which stabilize these bimodal colloidal dispersions, has a significant effect on the mobility of individual components during coalescence. Specifically, the presence of HSPC inhibits migration of SDOSS to the film-air (F-A) interface. Furthermore, the presence of electrolyte species such as aqueous CaCl2 has a very pronounced effect on film formation. When the Ca2+/HSPC ratio is 0.1/1.0, SDOSS is released to the F-A interface during coalescence. At 2.0/1.0 Ca2+/HSPC, HSPC diffuses to the F-A interface and crystalline domains consisting of HSPC are formed. This stimuli-responsive behavior is confirmed using IRIR imaging that ultimately exhibits different surface morphologies. These studies illustrate for the first time that it is possible to control the release of two different surface-active species during coalescence that form crystalline domains.

Acrylates↗