Colloidal transport of uranium in soil: Size fractionation and characterization by field-flow fractionation–multi-detection

The aim of this study was to characterize colloids associated with uranium by using an on-line fractionation/multi-detection technique based on asymmetrical flow field-flow fractionation (As-Fl-FFF) hyphenated with UV detector, multi angle laser light scattering (MALLS) and inductively coupling plasma-mass spectrometry (ICP-MS). Moreover, thanks to the As-Fl-FFF, the different colloidal fractions were collected and characterized by a total organic carbon analyzer (TOC). Thus it is possible to determine the nature (organic or inorganic colloids), molar mass, size (gyration and hydrodynamic radii) and quantitative uranium distribution over the whole colloidal phase. In the case of the site studied, two populations are highlighted. The first population corresponds to humic-like substances with a molar mass of (1500 ± 300) g mol⁻¹ and a hydrodynamic diameter of (2.0 ± 0.2) nm. The second one has been identified as a mix of carbonated nanoparticles or clays with organic particles (aggregates and/or coating of the inorganic particles) with a size range hydrodynamic diameter between 30 and 450 nm. Each population is implied in the colloidal transport of uranium: maximum 1% of the uranium content in soil leachate is transported by the colloids in the site studied, according to the depth in the soil. Indeed, humic substances are the main responsible of this transport in sub-surface conditions whereas nanoparticles drive the phenomenon in depth conditions.     

Amino-substituted amphiphilic calixarenes: self-assembly and interactions with DNA

The amphiphilic 5,11,17,23-tetramino-25,26,27,28-tetradodecyloxycalix[4]arene is shown to self-assemble as stable and well-defined Langmuir monolayers at the air-water interface. The effect of the presence of DNA in the subphase reveals interactions taking place at the interface between the positively charged surface and the negatively charged DNA, causing an expansion of the monolayers and a phase transition from a liquid-condensed to a liquid-expanded phase; a slight decrease in the stability of the monolayers is also observed. The title compound is shown to self-assemble, with the absence of a cosurfactant, as stable colloidal suspensions. Photon correlation spectroscopy, zeta-potential measurements, and atomic force microscopy reveal that these colloidal suspensions present a monodisperse size distribution and are composed of positively charged solid lipid nanoparticles (SLNs), with an average hydrodynamic diameter of 190 nm and a surface potential of +13.2 mV. The interaction of these SLNs with double-stranded DNA is demonstrated.     

Synthesis of colloidal dispersions of rhodium nanoparticles under high temperatures and high pressures

Colloidal dispersions of rhodium (Rh) nanoparticles have been synthesized by the reduction of Rh ions (III) in high-temperature and high-pressure water, ethanol, or water-ethanol mixture under the existence of the protective polymer of poly(N-vinyl-2-pyrrolidone). The possibility of the regulation of the particle size and size distribution has been tested under several solvents at various temperatures and pressures. At 473 K and 25 MPa, particularly, concentrated colloidal dispersions of Rh particles of 2.5+/-0.5 nm were synthesized from the ionic solution of ethanol ([Rh]=15 mM) within a few seconds. Dilute colloidal dispersions of Rh particles were also synthesized from the dilute ionic solution ([Rh]=1.5 mM) with a diameter of 2.0+/-0.4 nm. From the water solution, Rh particles tended to form aggregates, especially for the lower concentration solution. In the case of solutions in water and ethanol mixture, the average diameter of Rh particles tended to be larger than in ethanol solution, and their distribution became broad.     

Self-assembled, pH-sensitive retinoate nanostructures ionically complexed with PEG-grafted cationic polyelectrolytes

All-trans-retinoic acids (ATRA) are ionically complexed with cationic polyelectrolytes containing tertiary amines and self-assembled into nanoscale colloidal structures. Poly(2-(dimethylamino)ethyl methacrylate) grafted with polyethylene glycol, poly(DMAEMA-g-PEG), is used as a double hydrophilic, cationic polyelectrolyte. The polyion/ATRA complexes are formed by adding ATRA in dimethyl sulfoxide into aqueous solution of poly(DMAEMA-g-PEG). This complexation effectively suppresses the formation of undesirable drug crystallites and produces stable colloidal nanostructures having a hydrodynamic diameter of about 15?nm at a neutral pH. However, as the pH decreases below about 6, they undergo dramatic structural change into large aggregates of about 250?nm in diameter presumably due to the dissociation of ATRA from the polyelectrolyte. We expect that this pH-sensitive response of the polyion/ATRA complexes is useful for intracellular translocation at a neutral pH followed by the endosomal escape of ATRA in an acidic condition.     

Solid-liquid phase transition of tin particles observed by UHV high resolution transmission electron microscopy: pseudo-crystalline phase

Solid-liquid transition of fine tin particles having diameter of 2–10 nm is studied in-situ by high-resolution transmission electron microscopy under a ultra-high vacuum condition. Melting temperature is confirmed to decrease with the decrease of particle diameter. The particles less than the critical size, 2r _c?5 nm, are found to have a specific phase between the solid and the liquid phase. The particle in this “pseudo-crystalline” phase contains crystalline embryos in it. Particles larger than the critical size have sharp liquid-solid transition, which completed within the time resolution of our microscope observation, 33 ms upon heating or cooling process. Large solid particles have Wulff's polyhedron, while particles around the critical diameter have rather spherical shape. Structural anomaly at the critical size occurs all over the outer most surface layer slightly below the melting temperature. Origin of the “pseudo-crystalline” phase and surface pre-melting phenomena are discussed.     

Preparation and Characterization of pH-Sensitive Microgels of Poly((2-dimethylamino) ethyl methacrylate)

Summary: pH-sensitive microgels of poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) were prepared by dispersion polymerization of 2-dimethylamino ethyl methacrylate in a mixed solvent of water/ethanol. ¹HNMR, FTIR and SEM were used to confirm the chemical structure and morphological properties of the resulting microgels. Dynamic Light Scattering (DLS) was used to measure the hydrodynamic diameter of the particles. SEM micrographs showed that the microgel particles have a diameter of about 100–200 nm in dry state. Mean hydrodynamic diameter of the particles at their collapsed state at pH = 9.5 was found to be about 150 nm. DLS measurements at various pH values showed that the prepared microgels have a volume phase transition around pH = 8 at which the hydrodynamic diameter decreased from about 470 nm to around 150 nm corresponding to a 32 fold change in the mean volume of a microgel particle.     

Polyelectrolyte complexes of poly(methacryloxyethyl trimethylammonium chloride) and poly(ethylene oxide)-block-poly(sodium methacrylate) studied by asymmetrical flow field-flow fractionation and dynamic light scattering

Polyelectrolyte complex (PEC) formation between cationic poly(methacryloxyethyl trimethylammonium chloride) (PMOTAC) and anionic poly(ethylene oxide)-block-poly(sodium methacrylate) (PEO-b-PMANa) was studied by asymmetrical flow field-flow fractionation and dynamic light scattering. The influence of ionic strength and mixing ratios of the charged units of the polyelectrolytes on the complex formation was evaluated. The diffusion coefficients and the hydrodynamic diameter distributions of the free and complexed polyelectrolytes were measured. In the absence of salt, the weight averaged hydrodynamic diameters were 48 and 28 nm for PMOTAC and PEO-b-PMANa, respectively. In the presence of salt, the particles were smaller, with weight averaged hydrodynamic diameters of 44-45 and 8-10 nm, respectively. In salt-free solution, at 1:1 mixing ratio of the charged monomer units of PMOTAC and PEO-b-PMANa, polydisperse particles with diameters of 2000-4000 nm were formed. In the presence of 20, 80, and 160 mM of sodium chloride, the 1:1 complexes were relatively monodisperse particles with weight averaged hydrodynamic diameters of 93, 124, and 120 nm, respectively.     

Application of fluorescence correlation spectroscopy: a study of flocculation of rigid rod-like biopolymer (schizophyllan) and colloidal particles

The flocculation between the rod-like biopolymer Schizophyllan and two types of colloidal particles (latex with diameter 40 nm and alumina with diameter 60 nm) has been investigated by means of fluorescence correlation spectroscopy (FCS). The concentration ratio of Schizophyllan/particle q was varied in the range 0.1 approximately 20. Under conditions of pH about 5.7, 1 mmol.L(-1) NaCl, and room temperature (22+/-0.5 degrees C), the particles are strongly charged (alumina particles positively charged, latex negatively), while Schizophyllan is neutral. We observed that Schizophyllan chains flocculate with both types of particles, which suggests that the charge neutralization does not play a decisive role in these interactions. The ratio of fluorescence intensity of one floc over that of one particle, Q(f)/Q(p), and the corresponding hydrodynamic radius (r(h)) of the flocs have been measured. For a Schizophyllan-latex system, Q(f)/Q(p) reached a maximum value of 5 for q=3 indicating that the flocs contained five particles on average. The corresponding value of r(h) was r(h)=455 nm. The flocculation kinetic of latex particles with Schizophyllan was too fast to be measurable by FCS. For the Schizophyllan-alumina system, Q(f)/Q(p) was stable at about 1 in the whole studied range of q but r(h) increased with q suggesting that many Schizophyllan chains are adsorbed on individual particles. The flocculation kinetic of this system was studied by FCS and the obtained results were compatible with those of photon correlation spectroscopy.     

Preparation of sterically stabilized nanoparticles by desolvation from graft copolymers

A new method is described for the preparation of sterically stabilized nanoparticles of defined size and polydispersity which are stabilized in aqueous solution by the presence of covalently linked monomethoxy–poly (oxyethylene) (MeOPOE) chains. The nanoparticles (100–270 nm mean diameter) were prepared by a process of desolvation of a graft copolymer prepared from poly(2-aminoethylmethacrylate) (PAEMA) and MeOPOE. Reproducible desolvation was achieved by the addition of sodium phosphate buffer to the copolymer in aqueous solution to give particles which were crosslinked in situ with the addition of glutaraldehyde. The size (mean diameter) and polydispersity (Q) of the particles were determined by Photon Correlation Spectroscopy (PCS). The temperature at which the desolvation reaction was performed was found to influence the particle size; at low temperatures (5–12°C), small particles were produced (99–121 nm, Q = 0.090–0.121), whereas at much higher temperatures (40–55°C), particles as large as 224–275 nm (Q = 0.138–0.127) were generated. Other parameters such as the graft copolymer concentration, the amount of glutaraldehyde added, the pH of the sodium phosphate buffer added, and the reaction time were found to be of relative insignificance in influencing the particle size. In addition to those involved in drug delivery, our method of nanoparticle preparation may be of interest to those engaged in the preparation of particulate materials and colloidal dispersions for other specific applications (e.g. stabilized photographic emulsions).     

Effect of sodium citrate on preparation of nano-sized cobalt particles by organic colloidal process

Nano-sized cobalt particles with the diameter of 2 nm were prepared via an organic colloidal process with sodium formate, ethylene glycol and sodium citrate as the reducing agent, the solvent and the complexing agent, respectively. The effects of sodium citrate on the yield, crystal structure, particle size and size distribution of the prepared nano-sized cobalt particles were then investigated. The results show that the average particle diameter decreases from 200 nm to 2 nm when the molar ratio of sodium citrate to cobalt chloride changes from 0 to 6. Furthermore, sodium citrate plays a crucial role in the controlling of size distribution of the nano-sized particles. The size distribution of the particle without sodium citrate addition is in range from tens of nanometers to 300 or 400 nm, while that with sodium citrate addition is limited in the range of (2±0.25) nm. Moreover, it is found that the addition of sodium citrate as a complex agent could decrease the yield of the nano-sized cobalt particle. __________ Translated from Journal of South China University of Technology, 2008, 36(3) (in Chinese)     

Control of the morphology and particle size of boehmite nanoparticles synthesized under hydrothermal conditions

The spontaneous nucleation under hydrothermal conditions often leads to aggregation of crystallizing particles, which is an undesired phenomenon when the goal is the preparation of nanocrystals with narrow particle size distribution. The present paper reports on the synthesis of boehmite nanocrystals under hydrothermal conditions. An aqueous aluminum chloride salt solution was first prepared, and the pH was increased to 11 using a 5 M sodium hydroxide solution. The hydrothermal treatment was performed at 160 degrees C for different periods of time. The system yielded relatively small (15-40 nm) boehmite crystallites aggregated into larger (160 nm) particles. To avoid the aggregation, a biocompatible polymer, sodium polyacrylate (NaPa) 2100, was employed as a size-/morphology-controlling agent. Thus, stable colloidal suspensions of rounded boehmite nanoparticles having a size between 15 and 40 nm were obtained at 160 degrees C for 24 h. Further, the effect of synthesis time on the morphological features of boehmite synthesized in such a NaPa-containing system was investigated. The increase of the synthesis time from 24 to 168 h resulted in the formation of very long boehmite fibers (1000-2000 nm) with an average diameter of about 10 nm. The boehmite samples were characterized by XRD, DLS, TEM, IR, N2 adsorption, and zeta potential measurements. The colloidal stability of the obtained suspension was also studied.     

纳米玉米醇溶蛋白微球稳定的O/W型Pickering乳液

利用相分离工艺制备玉米醇溶蛋白(zein)纳米微球,微球粒径可控制在40 nm左右;经旋转蒸发制得zein溶胶体系,zein溶胶具有明显的丁达尔现象,静置数月不聚沉,Zeta电位法测得zein微球在pH值为4.0时分散性能最佳。 以纳米zein微球为固相稳定剂制备O/W型Pickering乳液,考察了zein胶体加入量、油水体积比等因素对乳液稳定性的影响。 实验结果表明,zein胶体加入量的质量分数控制为0.4%,高油水体积比将有利于Pickering乳液的长时间稳定。 基于zein分子的两亲结构和界面组装特点,提出了zein微球稳定Pickering乳液的作用机制。     

Colloidal interactions and fouling of NF and RO membranes: a review

Colloids are fine particles whose characteristic size falls within the rough size range of 1-1000 nm. In pressure-driven membrane systems, these fine particles have a strong tendency to foul the membranes, causing a significant loss in water permeability and often a deteriorated product water quality. There have been a large number of systematic studies on colloidal fouling of reverse osmosis (RO) and nanofiltration (NF) membranes in the last three decades, and the understanding of colloidal fouling has been significantly advanced. The current paper reviews the mechanisms and factors controlling colloidal fouling of both RO and NF membranes. Major colloidal foulants (including both rigid inorganic colloids and organic macromolecules) and their properties are summarized. The deposition of such colloidal particles on an RO or NF membrane forms a cake layer, which can adversely affect the membrane flux due to 1) the cake layer hydraulic resistance and/or 2) the cake-enhanced osmotic pressure. The effects of feedwater compositions, membrane properties, and hydrodynamic conditions are discussed in detail for inorganic colloids, natural organic matter, polysaccharides, and proteins. In general, these effects can be readily explained by considering the mass transfer near the membrane surface and the colloid-membrane (or colloid-colloid) interaction. The critical flux and limiting flux concepts, originally developed for colloidal fouling of porous membranes, are also applicable to RO and NF membranes. For small colloids (diameter?100 nm), the limiting flux can result from two different mechanisms: 1) the diffusion-solubility (gel formation) controlled mechanism and 2) the surface interaction controlled mechanism. The former mechanism probably dominates for concentrated solutions, while the latter mechanism may be more important for dilute solutions. Future research needs on RO and NF colloidal fouling are also identified in the current paper.     

Preparation of aqueous CdS colloids in the presence of cadmium complexonates: effect of complexonates on the size of CdS nanoparticles

The results of a systematic study of the preparation of CdS colloids in aqueous solutions containing different Cd²⁺ complexonates are presented. The effects of the ratio of the reagents and the nature and concentration of various stabilizing surfactants and Cd²⁺ complexonates, including those of some sulfur-containing compounds, on the size of the colloidal particles have been studied. Thermodynamic calculation of the expected equilibrium size of the colloidal particles as a function of the solvent composition, taking into account the increase in the solubility of the CdS phase as the particle size decreases, has been performed. Comparison of the calculated results with the experimental data shows that the size of colloidal particles is determined to a great extent by kinetic factors of their growth rather than by thermodynamic factors. It has been established that when the size of colloidal particles is less than a critical value, their dissolution by adding strong compexing agents to the system does not result in a change in the observed mean-volume size of the particles.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1739–1746, September, 1995.The authors are grateful to A. L. Chuvilin (G. K. Boreskov Institute of Catalysis, SB of the RAS) for help in preparing the electron photomicrographs.The work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-4816).     

Liquid-liquid phase-transfer of magnetic nanoparticles in organic solvents

We report a novel route for the preparation of well-defined colloidal dispersions of magnetic nanoparticles stabilized by steric repulsion in organic solvents. The usual methods standardly lead to the surfaction of multiparticle aggregates, incompatible with our long-term aim of studying and modeling the influence of magnetic dipolar interactions in colloidal dispersions which are free of aggregates, all other interactions being perfectly defined. A new and reproducible method based on a surfactant-mediated liquid-liquid phase transfer of individually dispersed gamma-Fe(2)O(3) nanoparticles from an aqueous colloidal dispersion to an organic phase is developed. The choice of the reagent and the preparation techniques is discussed. Among several solvent/surfactant pairs, the cyclohexane/dimethyldidodecylammonium bromide (DDAB) system is found to fulfill the colloidal stability criterion: aggregation does not appear, even upon aging. A complete transfer of isolated particles is observed above a threshold in DDAB concentration. The nanoparticle surface is then fully covered with adsorbed DDAB molecules, each surfactant head occupying a surface of 0.57+/-0.05 nm(2). The volume fraction of the cyclohexane-based organosols is easily tunable up to a volume fraction of 12% by modifying the volume ratio of the organic and of the aqueous phases during the liquid-liquid phase transfer.     

Irreversible adsorption of latex particles on fibrinogen covered mica

Physicochemical properties of bovine plasma fibrinogen (Fb) in electrolyte solutions were characterized. These comprised the diffusion coefficient (hydrodynamic radius), determined by the DLS method, electrophoretic mobility and the isoelectric point. The hydrodynamic radius of Fb was 12 nm for pH<5. The number of uncompensated (electrokinetic) charges on the protein N _c was calculated from the electrophoretic mobility data. It was found that for pH<5.8 the electrokinetic charge was positive, independently of the ionic strength and negative for pH>5.8. For pH=3.5 the value of N _c , was 26 for 10^?3 M. Similar electrokinetic measurements were performed for the mica substrate using the streaming potential cell. It was shown that for pH=3.5 and 10^?3 M, the zeta potential of mica remained negative (?50 mV). This promoted an irreversible, electrostatically driven adsorption of Fb, which was confirmed in experiments carried out under diffusion-controlled transport. The surface concentration of Fb on mica was determined directly by AFM counting. By adjusting the time of adsorption, Fb monolayers of desired coverage were produced. Independently, the presence of Fb on mica was determined quantitatively by the colloid enhancement method, in which negatively charged latex particles were used, having the diameter of 800 nm. It was found that for Fb coverage below 0.05 the method was more sensitive than other indirect methods. The experimental data obtained in latex deposition experiments were adequately interpreted in terms of the random site model used previously for polyelectrolytes. It was shown that adsorption sites consisted of a cluster of two Fb molecules. It was concluded that the colloid enhancement method can be successfully used for detecting the presence of proteins at solid substrates and to determine the uniformity of monolayers in the nanoscale.     

Effect of poly(ethylene oxide)-silane graft molecular weight on the colloidal properties of iron oxide nanoparticles for biomedical applications

The size, charge, and stability of colloidal suspensions of magnetic nanoparticles with narrow size distribution and grafted with poly(ethylene glycol)-silane of different molecular weights were studied in water, biological buffers, and cell culture media. X-ray photoelectron spectroscopy provided information on the chemical nature of the nanoparticle surface, indicating the particle surfaces consisted of a mixture of amine groups and grafted polymer. The results indicate that the exposure of the amine groups on the surface decreased as the molecular weight of the polymer increased. The hydrodynamic diameters correlated with PEG graft molecular weight and were in agreement with a distributed density model for the thickness of a polymer shell end-grafted to a particle core. This indicates that the particles obtained consist of single iron oxide cores coated with a polymer brush. Particle surface charge and hydrodynamic diameter were measured as a function of pH, ionic strength, and in biological buffers and cell culture media. DLVO theory was used to analyze the particle stability considering electrostatic, magnetic, steric, and van der Waals interactions. Experimental results and colloidal stability theory indicated that stability changes from electrostatically mediated for a graft molecular weight of 750 g/mol to sterically mediated at molecular weights of 1000 g/mol and above. These results indicate that a graft molecular weight above 1000 g/mol is needed to produce particles that are stable in a wide range of pH and ionic strength, and in cell culture media.     

Synthesis and aqueous solution properties of sterically stabilized pH-responsive polyampholyte microgels

Emulsion copolymerization of poly(methacrylic acid) and poly(2-(diethylamino)ethyl methacrylate) (PMAA/PDEA) yielded pH-responsive polyampholyte microgels of 200-300 nm in diameter. These microgels showed enhanced hydrophilic behavior in aqueous medium at low and high pH, but formed large aggregates of approximately 2500 nm at intermediate pH. To achieve colloidal stability at intermediate pH, a second batch of microgels of identical monomer composition were synthesized, where monomethoxy-capped poly(ethylene glycol)methacrylate (PEGMA) was grafted onto the surface of these particles. Dynamic light-scattering measurements showed that the hydrodynamic radius, Rh, of sterically stabilized microgels was approximately 100 nm at intermediate pH and increased to 120 and 200 nm at pH 2 and 10, respectively. Between pH 4 and 6, these microgels possessed mobility close to zero and a negative second virial coefficient, A2, due to overall charge neutralization near the isoelectric pH. From the Rh, mobility, and A2, cross-linked MAA-DEA microgels with and without PEGMA retained their polyampholytic properties in solution. By varying the composition of MAA and DEA in the microgel, it is possible to vary the isoelectric point of the colloidal particles. These new microgels are being explored for use in the delivery of DNA and proteins.     

Drying dissipative structures of thermosensitive gel spheres of poly (N-isopropylacrylamide). Influence of gel size

Drying dissipative patterns of de-ionized suspensions (colloidal crystal-state at high concentrations) of the thermosensitive gels of poly (N-isopropylacrylamide) with various sizes (ca. 400–1,500?nm in diameter at 20?°C) were observed at 20 and 45?°C on a cover glass, a watch glass, and a Petri glass dish. The broad rings were observed and their size decreased as gel concentration decreased. Formation of the monodispersed agglomerated particles and their ordered arrays were observed irrespective of gel size. The macroscopic flickering spoke-like patterns were observed for the gel spheres from 70 to 600?nm in diameter at 20?°C, but almost disappeared for extremely large spheres, poly(N-isopropylacrylamide)(1500-5). This work clarified the formation of the drying microscopic structures of (a) ordered rings, (b) flickering ordered spoke lines, (c) net structure, and (d) lattice-like ordered structures of the agglomerated particles. The ordered rings became rather vague as gel size increased. The large net structures formed so often for large gels. Size effect on the lattice patterns was not recognized so clearly. The role of the electrical double layers around the agglomerated particles and the interaction of the particles with the substrate surfaces during dryness are important for the ordering. The microscopic drying patterns of gel spheres were quite different from those of linear type polymers and also from typical colloidal hard spheres, though the macroscopic patterns such as broad ring formation at the edges of the dried film were similar to each other.     

Characterization of the self-assembly process of hydrophobically modified dextrin

Hydrophobized dextrin, randomly substituted by long alkyl chain (C₁₆), forms stable hydrogel nanoparticles by self-assembling in water. Hydrophobic chains, distributed along the polymer backbone, promote the formation of hydrophobic microdomains within the nanoparticles. The influence of degree of substitution with hydrophobic chains (DS_C16) on nanoparticles size, colloidal stability, density, aggregation number and nanoparticle weight was studied. Size distribution was also evaluated at different pH, urea concentration and ionic strength conditions. As shown by dynamic light scattering and transmission electron microscopy, the particles are spherical having a diameter of about 20 nm. The more substituted polymer forms more densely packed hydrophobic microdomains, such that the colloidal stability (in water and PBS buffer) of nanoparticles is increased. The knowledge of the aggregate building process and the characteristics of the nanoparticles are crucial for the design of drug delivery systems.