Advances in Colloid and Interface Science (v.226, #PA)

Preface by Yasuhisa Adachi (1).

Electrostatic interaction of soft particles by Hiroyuki Ohshima (2-16).
Theories of the electrostatic interaction between two soft particles (i.e., particles covered with an ion-penetrable surface layer of polyelectrolytes) in an electrolyte solution are reviewed. Interactions of soft particles after contact of their surface layers are particularly discussed. Interaction in a salt-free medium and the discrete-charge effect are also treated.Display Omitted
Keywords: Electrostatic interaction; Soft particle; Interdigitation; Interpenetration; Counterion only system; Discrete-charge effect;

Polymeric stabilizers for protection of soil and ground against wind and water erosion by A.B. Zezin; S.V. Mikheikin; V.B. Rogacheva; M.F. Zansokhova; A.V. Sybachin; A.A. Yaroslavov (17-23).
The article is devoted to the design, development and application of a new generation of binders for various dispersed systems, including soil, ground, sand, waste rock and others. The binders are formed by interaction of oppositely charged polyelectrolytes, both chemically stable and (bio)degradable. The fundamental aspects of interpolyelectrolyte reactions are discussed; the IPC structure and properties of the resulting interpolyelectrolyte complexes (IPCs) allow considering them as unique and universal binders. Numerous results of laboratory experiments and field trials of the IPC formulations are presented. In particular, large-scale tests have been done in the Chernobyl accident zone where the IPC binders were shown to be effective means to suppress water and wind erosion thereby preventing a spread of radioactive particles (radionuclides) from contaminated sites. Ecologically friendly IPC compositions are described, including those based on commercially available polymers; prospects for improving their efficiency and extending the range of their possible use are discussed.Display Omitted
Keywords: Interpolyelectrolyte complexes; Soil stabilization; Polymer binders;

Heteroaggregation of nanoparticles with biocolloids and geocolloids by Hongtao Wang; Adeyemi S. Adeleye; Yuxiong Huang; Fengting Li; Arturo A. Keller (24-36).
The application of nanoparticles has raised concern over the safety of these materials to human health and the ecosystem. After release into an aquatic environment, nanoparticles are likely to experience heteroaggregation with biocolloids, geocolloids, natural organic matter (NOM) and other types of nanoparticles. Heteroaggregation is of vital importance for determining the fate and transport of nanoparticles in aqueous phase and sediments. In this article, we review the typical cases of heteroaggregation between nanoparticles and biocolloids and/or geocolloids, mechanisms, modeling, and important indicators used to determine heteroaggregation in aqueous phase. The major mechanisms of heteroaggregation include electric force, bridging, hydrogen bonding, and chemical bonding. The modeling of heteroaggregation typically considers DLVO, X-DLVO, and fractal dimension. The major indicators for studying heteroaggregation of nanoparticles include surface charge measurements, size measurements, observation of morphology of particles and aggregates, and heteroaggregation rate determination. In the end, we summarize the research challenges and perspective for the heteroaggregation of nanoparticles, such as the determination of αhetero values and heteroaggregation rates; more accurate analytical methods instead of DLS for heteroaggregation measurements; sensitive analytical techniques to measure low concentrations of nanoparticles in heteroaggregation systems; appropriate characterization of NOM at the molecular level to understand the structures and fractionation of NOM; effects of different types, concentrations, and fractions of NOM on the heteroaggregation of nanoparticles; the quantitative adsorption and desorption of NOM onto the surface of nanoparticles and heteroaggregates; and a better understanding of the fundamental mechanisms and modeling of heteroaggregation in natural water which is a complex system containing NOM, nanoparticles, biocolloids and geocolloids.Display Omitted
Keywords: Heteroaggregation; Nanoparticles; Biocolloid; Geocolloid; NOM;

This paper aims to summarize recent investigations into the dispersion of fine particles, and the characterization of their interactions, in concentrated suspensions. This summary will provide a better understanding of the current status of this research, and will provide useful feedback for advanced particle processing. Such processes include the fabrication of functional nanostructures and the sustainable beneficiation of complex ores. For example, there has been increasing demand for complex ore utilization due to the noticeable decrease in the accessibility of high grade and easily extractable ores. In order to maintain the sustainable use of mineral resources, the effective beneficiation of complex ores is urgently required. It can be successfully achieved only with selective particle/mineral dispersion/liberation and the assistance of mineralogical and particle characterization.Fig. 1 Shear yield stress of nickel oxide-hematite suspension as a function of solid concentration and pH. Volume % of solid = 5, 10 [modified from ref. 3].Display Omitted
Keywords: Particle–particle interaction; Dispersion and coagulation; Electrical disintegration; Rheology; Zeta potential; Mineral separation; Scattering;

Surface science is key to innovations on microfluidics, smart materials, and future non-equilibrium systems. However, challenging issues still exist in this field. In this article, from the viewpoint of the fundamental design, we will briefly review our strategies on improving the micro-fluidic devices using the nonlinear electro- and thermo-kinetic phenomena. In particular, we will review the microfluidic applications using ICEO, the correction based on the ion-conserving Poisson–Boltzmann theory, the direct simulation on ICEO, and the new horizon such as nonlinear thermo-kinetic phenomena and the artificial cilia.Display Omitted
Keywords: Microfluidics; Induced-charge electro-osmosis; Ion-conserving Poisson–Boltzmann theory; Direct simulation; Nonlinear thermo-kinetics; Artificial cilia;

Multi-liposomal containers by A.A. Yaroslavov; A.V. Sybachin; O.V. Zaborova; A.B. Zezin; Y. Talmon; M. Ballauff; F.M. Menger (54-64).
Small unilamellar liposomes, 40–60 nm in diameter, composed of anionic diphosphatidylglycerol (cardiolipin, CL2 −) or phosphatidylcerine (PS1 −) and zwitter-ionic egg yolk lecithin (EL) or dipalmitoylphosphatidylcholine (DPPC), electrostatically complex with polystyrene microspheres, ca. 100 nm in diameter, grafted by polycationic chains (“spherical polycationic brushes”, SPBs). Polymer/liposome binding studies were carried out using electrophoretic mobility (EPM), dynamic light scattering (DLS), fluorescence, conductometry, differential scanning calorimetry (DSC), and cryogenic transmission electron microscopy (cryo-TEM) as the main analytical tools. By these means a remarkably detailed picture emerges of molecular events inside a membrane. The following are among the most important conclusions that arose from the experiments: (a) binding of liposomes to SPBs is accompanied by flip-flop of anionic lipids from the inner to the outer leaflet of the liposomal membrane along with lateral lipid segregation into “islands”. (b) The SPB-induced structural reorganization of the liposomal membrane, together with the geometry of anionic lipid molecules, determines the maximum molar fraction of anionic lipid (a key parameter designated as ν) that ensures the structural integrity of liposomes upon complexation: ν = 0.3 for liposomes with conically-shaped CL2 − and ν = 0.5 for liposomes with anionic cylindrically-shaped PS1 −. (c) The number of intact liposomes per SPB particle varies from 40 for (ν = 0.1) to 13 (ν = 0.5). (d) By using a mixture of liposomes with variety of encapsulated substances, multi-liposomal complexes can be prepared with a high loading capacity and a controlled ratio of the contents. (e) In order to make the mixed anionic liposomes pH-sensitive, they are additionally modified by 30 mol% of a morpholinocyclohexanol-based lipid that undergoes a conformational flip when changing pH. Being complexed with SPBs, such liposomes rapidly release their contents when the pH is reduced from 7.0 to 5.0. The results allow loaded liposomes to be concentrated within a rather small volume and, thereby, the preparation of multi-liposomal containers of promise in the drug delivery field.Display Omitted
Keywords: Anionic liposome; Spherical polycationic brush; Multi-liposomal complex; Flip-flop; Lateral lipid segregation; pH-sensitivity;

Bacterial membrane vesicles, an overlooked environmental colloid: Biology, environmental perspectives and applications by Masanori Toyofuku; Yosuke Tashiro; Yusuke Hasegawa; Masaharu Kurosawa; Nobuhiko Nomura (65-77).
Phospholipid vesicles play important roles in biological systems. Bacteria are one of the most abundant organisms on Earth, and bacterial membrane vesicles (MVs) were first observed 50 years ago. Many bacteria release MVs to the environment that mainly consist of the cell membrane and typically range from 20 to 400 nm in size. Bacterial MVs are involved in several biological functions, such as delivery of cargo, virulence and gene transfer. MVs can be isolated from laboratory culture and directly from the environment, indicating their high abundance in and impact on ecosystems. Many colloidal particles in the environment ranging in size from 1 nm to 1 μm have been reported but not characterized at the molecular level, and MVs remain to be explored. Hence, MVs can be considered terra incognita in environmental colloid research. Although MV biogenesis and biological roles are yet to be fully understood, the accumulation of knowledge has opened new avenues for their applications. Via genetic engineering, the MV yield can be greatly increased, and the components of MVs can be tailored. Recent studies have demonstrated that MVs have promising potential for applications such as drug delivery systems and nanobiocatalysts. For instance, MV vaccines have been extensively studied and have already been approved in Europe. Recent MV studies have evoked great interest in the fields of biology and biotechnology, but fundamental questions, such as their transport in the environment or physicochemical features of MVs, remain to be addressed. In this review, we present the current understanding of bacterial MVs and environmental perspectives and further introduce their applications.Display Omitted
Keywords: Membrane vesicle; Bacteria; Nanobiocatalysts; Nanotechnology; Biotechnology;

The physicochemical property of coagulant species plays a significant role in the coagulation process. Recent progress on speciation, stability, and coagulation mechanisms of the hydroxyl aluminum clusters formed by PACl and alum has been critically reviewed. The complicated nature on species formation, stability, and transformation of various hydrolyzed aluminum clusters formed by PACl and Alum are discussed. Based on the aspects of spontaneous hydrolysis, forced hydrolysis, and dual-hydrolysis models, the special stability of aluminum clusters that results in various coagulation behaviors is compared with the traditional salts. The coagulation behavior of the hydroxyl aluminum clusters in terms of particle aggregation and restabilization, surface adsorption and coverage, microfloc formation and kinetics, modified DLVO simulation, and finally, the coagulation model is then analyzed in detail. It is indicative that the coagulation mechanism of inorganic coagulants can be understood better with the hydroxyl clusters being tailor-made.Display Omitted
Keywords: Alum cluster; Coagulation; Hydrolysis; Modified DLVO; Speciation;

This review paper presents an overview of the formulation and functionalization of nano-/microdispersion systems composed of edible materials. We first summarized general aspects on the stability of colloidal systems and the roles of natural polyelectrolytes such as proteins and ionic polysaccharides for the formation and stabilization of colloidal systems. Then we introduced our research topics on (1) stabilization of emulsions by the electrostatic deposition using natural polyelectrolytes and (2) formulation of stable nanodispersion systems by complexation of natural polyelectrolytes. In both cases, the preparation procedures were relatively simple, without high energy input or harmful chemical addition. The properties of the nano-/microdispersion systems, such as particle size, surface charge and dispersion stability were significantly affected by the concerned materials and preparation conditions, including the type and concentration of used natural polyelectrolytes. These dispersion systems would be useful for developing novel foods having high functionality and good stability.Display Omitted
Keywords: Emulsion; Nanoparticle; Colloidal stability; Protein; Polysaccharide; Electrostatic interaction;

The dynamic behavior of polyelectrolytes just after their encounter with the surface of bare colloidal particles is analyzed, using the flocculation properties of mono-dispersed polystyrene latex (PSL) particles. Applying a Standardized Colloid Mixing (SCM) approach, effects of ionic strength and charge density of polymer chain on the rate of flocculation, the electrophoretic mobility of particle coated with polyelectrolyte, and the thickness of adsorbed polymer layer were analyzed, focusing on distinguishing features of two modes of flocculation, namely bridging formation and charge neutralization. In the case of excess polymer dosage, the bridging flocculation clearly highlights the transient behavior of polymer conformation from random-coil-like in bulk solution to increasingly flatten on the surface. The adsorption of polymer chains leads to a stagnant layer of solvent near the solid wall, which is confirmed by electrokinetic data. In the regime near optimum dosage two cases emerge. For high charge density polymer, charge neutralization is dominant and advantageous for the continuous progress of flocculation by heterogeneous double layer interaction. As a function of elapsed time after the onset of mixing, crossover from bridging to charge neutralization is found. In the case of low charge density polymer, bridging flocculation is the mechanism. Fluid mixing is concluded to have an essential role in the formation of bridges.Display Omitted
Keywords: Colloidal flocculation; Dynamics of polyelectrolyte adsorption; Proximate stagnant layer; Charge neutralization; Bridging flocculation;

The study of interpolyelectrolyte complex (IPEC) formation between cationic microgel and polyanion was presented. The size and molecular weight of cationic microgel are much larger than those of linear anionic polyelectrolyte. The resulting IPEC was divided by dynamic light scattering (DLS), static light scattering (SLS), and turbidity or spectrometry; (i) water-soluble intra-particle complexes consisting of one microgel to which linear polyelectrolytes bind; (ii) complex coacervates (inter-particle complexes composed of aggregated intra-particle complexes); and (iii) insoluble amorphous precipitates. These types depended on not only the mixing ratio of polyanion to cationic microgel but also salt concentration. This trend was discussed from IPEC's composition, thermodynamics of IPEC formation and the salt effect on intermolecular interactions which were expected in IPEC formation. The results obtained from the use of microgel in IPEC's study suggested that not only electrostatic interaction but also hydrophobic interaction play an important role in the aggregation or association of IPEC.Display Omitted
Keywords: Polyelectrolyte microgel; Intermolecular polyelectrolyte complex; Electrostatic interaction; Hydrophobic interaction; Intra-particle complex; Coacervation;