Colloid Science Research Articles

Hofmeister Effects Shine in Nanoscience.

Hofmeister effects play a crucial role in nanoscience by affecting the physicochemical and biochemical processes. Thus far, numerous wonderful applications from various aspects of nanoscience have been developed based on the mechanism of Hofmeister effects, such as hydrogel/aerogel engineering, battery design, nanosynthesis, nanomotors, ion sensors, supramolecular chemistry, colloid and interface science, nanomedicine, and transport behaviors, etc. In this review, for the first time, the progress of applying Hofmeister effects is systematically introduced and summarized in nanoscience. It is aimed to provide a comprehensive guideline for future researchers to design more useful Hofmeister effects-based nanosystems.

Multimodal Optothermal Manipulations along Various Surfaces.

Optical tweezers have provided tremendous opportunities for fundamental studies and applications in the life sciences, chemistry, and physics by offering contact-free manipulation of small objects. However, it requires sophisticated real-time imaging and feedback systems for conventional optical tweezers to achieve controlled motion of micro/nanoparticles along textured surfaces, which are required for such applications as high-resolution near-field characterizations of cell membranes with nanoparticles as probes. In addition, most optical tweezers systems are limited to single manipulation modes, restricting their broader applications. Herein, we develop an optothermal platform that enables the multimodal manipulation of micro/nanoparticles along various surfaces. Specifically, we achieve the manipulation of micro/nanoparticles through the synergy between the optical and thermal forces, which arise due to the temperature gradient self-generated by the particles absorbing the light. With a simple control of the laser beam, we achieve five switchable working modes [i.e., tweezing, rotating, rolling (toward), rolling (away), and shooting] for the versatile manipulation of both synthesized particles and biological cells along various substrates. More interestingly, we realize the manipulation of micro/nanoparticles on rough surfaces of live worms and their embryos for localized control of biological functions. By enabling the three-dimensional control of micro/nano-objects along various surfaces, including topologically uneven biological tissues, our multimodal optothermal platform will become a powerful tool in life sciences, nanotechnology, and colloidal sciences.

Journal of Modern Thermodynamics in Mechanical System

Surface thermodynamics study is the application of colloidal science to an investigative search for the nature and rate of heat transfer on the surface of any particle-particle interaction. This paper presents the theory and a designed practical methodology for the demonstration of the Combined Hamaker Coefficient. The nature and effectiveness of any interaction between two or more particles can be determined using this thermodynamic approach. Samples of blood lymphocytes and HIV particles in a serum containing antiretroviral drug particles were used. The Hamaker concept based on Van der Waal’s theory for surface energy of attraction and repulsion can be demonstrated. The interfacial work done by particles can be investigated during their combined interaction in an in-vivo experiment. The data obtained can prove that the combined Hamaker coefficient when negative is responsible for particle-particle repulsion and positive for particle-particle attraction. This implies the repulsion of the viral particle in lymphocytes and drug particles in the intervening serum. The overall change in the energy potential of all particle matter is revealed to be a concurrent area of surface thermodynamics that employs mathematical concepts and software in the designing and formulation of drugs for the management of viral infections.

Missing Piece in Colloidal Stability─Morphological Factor of Hydrophobic Nanoparticles

Hydrophobic nanoparticles (NPs) in water were considered unstable because they lack the repulsive electrostatic interaction and steric effect to prevent aggregation. In this study, porous hydrophobic NPs of two star-shaped giant molecules, POSS-(R)8, were found to be stable in water and able to retain their kinetic stability in a wide range of temperatures, pH values, and ionic strengths. Unlike the solid hydrophobic NPs that aggregate even with the negative zeta potential (ζ) induced by surface-structured hydrogen-bonded (SHB) water, the porous morphology of POSS-(R)8 NPs reduces the entropically driven hydrophobic effect to prevent aggregation. With the porous morphology, the hydrophobic NPs are stable without the hydrophilic or charged surface functional groups and demonstrate good encapsulation capability. The morphological factor of colloids is thus one of the missing pieces in the theory of colloidal stability that extends our understanding of colloidal science.

Electromagnetic Forces and Torques: From Dielectrophoresis to Optical Tweezers.

Electromagnetic forces and torques enable many key technologies, including optical tweezers or dielectrophoresis. Interestingly, both techniques rely on the same physical process: the interaction of an oscillating electric field with a particle of matter. This work provides a unified framework to understand this interaction both when considering fields oscillating at low frequencies─dielectrophoresis─and high frequencies─optical tweezers. We draw useful parallels between these two techniques, discuss the different and often unstated assumptions they are based upon, and illustrate key applications in the fields of physical and analytical chemistry, biosensing, and colloidal science.

A Time of Change

A Time of Change

Generalization of Young-Laplace, Kelvin, and Gibbs-Thomson equations for arbitrarily curved surfaces

The Young-Laplace, Kelvin, and Gibbs-Thomson equations form a cornerstone of colloidal and surface sciences and have found successful applications in many subfields of physics, chemistry, and biology. The Gibbs-Thomson effect, for example, predicts that small crystals are in equilibrium with their liquid melt at a lower temperature than large crystals and the positive interfacial energy increases the energy required to form small particles with a high curvature interface. In cases of liquids contained within porous media (confined geometry), the effect indicates decreasing the freezing/melting temperatures and the increment of the temperature is inversely proportional to the pore size. These phenomena can be reformulated for Gaussian maps of macromolecules and can be asked the following question: can one use the equations for predicting the melting temperature and shape of polymer chains in confined geometries? The answer is no, mainly because macromolecules form highly curved surfaces (Gaussian maps), and the equations hold only for simple geometries (sphere, plane, or cylinder). Here, we present general Young-Laplace, Kelvin, and Gibbs-Thomson equations for arbitrarily curved surfaces and apply them to predict temperature distribution on a few protein surfaces. Also, after increased interest toward liquid/liquid phase separation in biology, we derive generic Ostwald ripening and show that for shape-changing condensates, instead of a monotonic growing mechanism, a variety of processes are possible. Due to the generality of equations, we clarify that at appropriate internal/external pressure conditions systems, bounded by surfaces, may adopt any shape and thermal stability is strongly influenced by the geometries of confined spaces.

Unravelling the mechanisms of drugs partitioning phenomena in micellar systems via NMR spectroscopy

Despite extensive use of micelles in materials and colloidal science, their supramolecular organization as well as host–guest interactions within these dynamic assemblies are poorly understood. Small guest molecules in the presence of micelles undergo constant exchange between a micellar aggregate and the surrounding solution, posing a considerable challenge for their molecular level characterisation. In this work we reveal the interaction maps between small guest molecules and surfactants forming micelles via novel applications of NMR techniques supported with state-of-the-art analytical methods used in colloidal science. Model micelles composed of structurally distinct surfactants (block non-ionic polymer Pluronic® F-127, non-ionic surfactant Tween 20 or Tween 80, and ionic surfactant sodium lauryl sulphate, SLS) were selected and loaded with model small molecules of biological relevance (i.e. the drugs fluconazole, FLU or indomethacin, IMC) known to have different partition coefficients. Molecular level organization of FLU or IMC within hydrophilic and hydrophobic domains of micellar aggregates was established using the combination of NMR methods (1D 1H NMR, 1D 19F NMR, 2D 1H–1H NOESY and 2D 1H-19F HOESY, and the multifrequency-STD NMR) and corroborated with molecular dynamics (MD) simulations. This is the first application of multifrequency-STD NMR to colloidal systems, enabling us to elucidate intricately detailed patterns of drug/micelle interactions in a single NMR experiment within minutes. Importantly, our results indicate that flexible surfactants, such as block copolymers and polysorbates, form micellar aggregates with a surface composed of both hydrophilic and hydrophobic domains and do not follow the classical core–shell model of the micelle. We propose that the magnitude of changes in 1H chemical shifts corroborated with interaction maps obtained from DEEP-STD NMR and 2D NMR experiments can be used as an indicator of the strength of the guest-surfactant interactions. This NMR toolbox can be adopted for the analysis of broad range of colloidal host–guest systems from soft materials to biological systems.

Advances in Bioinspired Superhydrophobic Surfaces Made from Silicones: Fabrication and Application.

As research on superhydrophobic materials inspired by the self-cleaning and water-repellent properties of plants and animals in nature continues, the superhydrophobic preparation methods and the applications of superhydrophobic surfaces are widely reported. Silicones are preferred for the preparation of superhydrophobic materials because of their inherent hydrophobicity and strong processing ability. In the preparation of superhydrophobic materials, silicones can both form micro-/nano-structures with dehydration condensation and reduce the surface energy of the material surface because of their intrinsic hydrophobicity. The superhydrophobic layers of silicone substrates are characterized by simple and fast reactions, high-temperature resistance, UV resistance, and anti-aging. Although silicone superhydrophobic materials have the disadvantages of relatively low mechanical stability, this can be improved by the rational design of the material structure. Herein, we summarize the superhydrophobic surfaces made from silicone substrates, including the cross-linking processes of silicones through dehydration condensation and hydrosilation, and the surface hydrophobic modification by grafting hydrophobic silicones. The applications of silicone-based superhydrophobic surfaces have been introduced such as self-cleaning, corrosion resistance, oil-water separation, etc. This review article should provide an overview to the bioinspired superhydrophobic surfaces of silicone-based materials, and serve as inspiration for the development of polymer interfaces and colloid science.

Mathematical modeling of electrodialysis of a dilute solution with accounting for water dissociation-recombination reactions

The paper explores the limitations of electrodialysis (ED) in the range of very dilute feed solutions. The results of first principles modeling of this process are presented, taking into account water dissociation-recombination reactions (without catalytic effects). A 1D and a 2D model are formulated and applied. Both models use the equation for the rate of chemical reactions, the Nernst-Planck and Poisson equations; additionally, the Navier-Stokes equation is used in the 2D model. We show that the dissociation-recombination reactions can cause the appearance of a space charge region (SCR) in the central part of the desalination chamber (DC). In electrochemistry and colloidal science, the formation of a SCR is associated with the formation of an electrical double layer (EDL) at a charged solid surface. Our modeling predicts that in conditions where the concentrations of H+/OH− ions and salt ions in solution are comparable, a SCR can appear in the bulk solution due to the recombination of H+ and OH− ions. The latter are generated at the membrane forming the DC (water splitting). Water splitting makes impossible total desalting of aqueous solutions by conventional ED. An inversion of the salt concentration profiles is observed: the salt ions are accumulated near the membranes; a depletion region occurs in the center of the DC. Interplay between the chemical reactions and space charge is discussed.

A Hybrid Particle Swarm Optimization-Tuning Algorithm for the Prediction of Nanoparticle Morphology from Microscopic Images

Aggregated nanoparticle structures are quite ubiquitous in aerosol and colloidal science, specifically in nanoparticle synthesis systems such as combustion processes where coagulation results in the formation of fractal-like structures. In addition to their size, morphology of the particles also plays a key role in defining various physicochemical properties. Electron microscopy based images are the most commonly used tools in visualizing these aggregates, and prediction of the 3-dimensional structures from the microscopic images is quite complex. Typically, 2-dimensional features from the images are compared to available structures in a database or regression equations are used to predict 3-dimensional morphological parameters including Fractal dimension and pre-exponential factor. In this study, we propose a combination of evolutionary algorithm and forward tuning model to predict the best fit 3-dimensional structures of aggregates from their projection images. 2-dimensional features from a projection image are compared to the candidate projections generated using FracVAL code and optimized using Particle Swarm Optimization to obtain the 3-dimensional structure of the aggregate. Various 3-dimensional properties including hydrodynamic diameter and mobility diameter of the retrieved structures are then compared with the properties of the aggregate used to form the candidate projection image, to test the suitability of the algorithm. Results show that the hybrid algorithm can closely predict the 3-dimensional structures from the projection images with less than 10% difference in the predicted 3-dimensional properties including mobility diameter and radius of gyration.

Fast and high-resolution mapping of van der Waals forces of 2D materials interfaces with bimodal AFM.

High-spatial resolution mapping of van der Waals forces is relevant in several fields ranging from nanotechnology to colloidal science. The emergence of two-dimensional heterostructures assembled by van der Waals interactions has enhanced the interest of those measurements. Several AFM methods have been developed to measure the adhesion force between an AFM probe and the material of interest. However, a reliable and high-resolution method to measure the Hamaker constant remains elusive. We demonstrate that an atomic force microscope operated in a bimodal configuration enables fast, quantitative, and high-resolution mapping of the Hamaker constant of interfaces. The method is applied to map the Hamaker constant of monolayer, bilayer and multilayer MoS2 surfaces. Those interfaces are characterized with Hamaker constant and spatial resolutions of, respectively, 0.1 eV and 50 nm.

Gold Nanoparticles Synthesized Using Various Reducing Agents and the Effect of Aging for DNA Sensing.

Gold nanoparticles (AuNPs) are one of the most commonly used reagents in colloidal science and biosensor technology. In this work, we first compared AuNPs prepared using four different reducing agents including citrate, glucose, ascorbate, and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES). At the same absorbance at the surface plasmon peak of 520-530 nm, citrate-AuNPs and glucose-AuNPs adsorbed more DNA and achieved higher affinity to the adsorbed DNA. In addition, citrate-AuNPs had better sensitivity than glucose-AuNPs for label-free DNA detection. Then, using citrate-AuNPs, the effect of aging was studied by incubation of the AuNPs at 22 °C (room temperature) and at 4 °C for up to 6 months. During aging, the colloidal stability and DNA adsorption efficiency gradually decreased. In addition, the DNA sensing sensitivity using a label-free method also dropped around 4-fold after 6 months. Heating at boiling temperature of the aged citrate-AuNPs could not rejuvenate the sensing performance. This study shows that while citrate-AuNPs are initially better than the other three AuNPs in their colloid properties and sensing properties, this edge in performance might gradually decrease due to constantly changing surface properties caused from the aging effect.

Shape-Shifting Thermoresponsive Block Copolymer Nano-Objects

In this Feature Article, we review our recent progress in the design of shape-shifting thermoresponsive diblock copolymer nano-objects, which are prepared using various hydroxyl-functional (meth)acrylic monomers (e.g. 2‑hydroxypropyl methacrylate, 4‑hydroxybutyl acrylate or hydroxybutyl methacrylate) to generate the thermoresponsive block. Unlike traditional thermoresponsive polymers such as poly(N-isopropylacrylamide), there is no transition between soluble and insoluble polymer chains in aqueous solution. Instead, thermally driven transitions between a series of copolymer morphologies (e.g. spheres, worms, vesicles or lamellae) occur on adjusting the aqueous solution temperature owing to a subtle change in the partial degree of hydration of the permanently insoluble thermoresponsive block. Such remarkable self-assembly behavior is unprecedented in colloid science: no other amphiphilic diblock copolymer or surfactant system undergoes such behavior at a fixed chemical composition and concentration. Such shape-shifting nano-objects are characterized by transmission electron microscopy, dynamic light scattering, small-angle X-ray scattering, rheology and variable temperature 1H NMR spectroscopy. Potential applications for this fascinating new class of amphiphiles are briefly considered.

The effect of amino acids on bubble coalescence in aqueous solution

Many salts reduce the size of bubbles and inhibit bubble coalescence. The phenomenon occurs above the same concentration for some ion pairs (0.17 M for 1:1 salts). For other ion pairs no such effect occurs. The phenomenon remains inexplicable by standard theories of colloid science. It occurs for a range of sugar isomers and not for others. Again, why this occurs is not known. The present work extends the effect to a wider range of solutes. Amino acids were found to inhibit bubble coalescence and reduce the size of bubbles. The effect is the same as that for inorganic salts but it is dramatically more efficient. A series of amino acids: dl-Alanine, l-Arginine, l-Leucine, dl-Methionine and l-Tyrosine was studied using a bubble column evaporator (BCE). The amino acid solutions were prepared at different concentrations and beyond their solubility limits. This remarkable effect also provides new hints into how bubble interactions affect crystallisation.

Clarification of Surface Deswelling of Thermoresponsive Microgels by Electrophoresis.

Although many investigations of thermoresponsive microgels have been reported, their surface properties, which are crucial in colloid science, are still not fully understood. In this study, microgels with surface-localized charged groups were synthesized by precipitation polymerization, and their electrophoretic behaviors were analyzed using a modified version of Ohshima's equation to obtain two surface properties of the soft particles: the softness parameter and the surface charge density. This systematic evaluation allows us to discuss the thermoresponsiveness of the overall microgels and their surfaces separately. Furthermore, the validity of the surface properties obtained from electrophoresis was verified by comparing them with the results of seeded emulsion polymerization in the presence of the microgels and the force-indentation curves obtained via high-speed atomic force microscopy (HS-AFM).

Synopsis: the 300th volume of colloid and polymer science

Synopsis: the 300th volume of colloid and polymer science

The Viscosity and Self-Diffusion of Some Real Colloidal Ferrofluids

One primary concern in colloid science is understanding the relationship of its macroscopic rheology and diffusion behavior with the observed microscopic arrangements of the nanoparticles in the fluid. This manuscript addresses the study of these dynamical properties through a first-principle stochastic method. Both properties directly relate to the observed fluid structure factor, which depends on a few known material parameters. However, in the literature, this static quantity is reported up to the first prominent peak of its small momentum transfer of the scattered radiation, leading to inaccurate determination of the transport properties. Here, it is proposed to use the rescaled mean spherical approximation under the requirement of fitting the experimental data of the structure beyond the dependence of more significant wave numbers. The predicted viscosity agrees with the observed ones at a low volume fraction of particles for ferrofluids dispersed in polymer solvents. This rheological quantity is inversely related to the self-diffusion coefficient of a tracer particle.

Quantized Collision/Fusion Events of Anionic Ionosomes at a Polarized Soft Micro-Interface.

Single-entity collisional electrochemistry (SECE) can capture physicochemical information at the single entity level. In the present work, we systematically studied in-situ generation and detection of single anionic ionosomes via SECE combined with a miniaturized interface between two immiscible electrolyte solutions (ITIES). Ionosome is an ionic-bilayer encapsulated nanoscopic water cluster/droplet that carries a net charge. Discrete spiky ionic currents were observed upon collisions/fusions of individual F- or Cl- -ionosomes with a positively polarized micro-ITIES. This fusion process was proved to follow the bulk electrolysis model. With this method, some essential factors such as concentration and charge density of the hydrated anions, and the interfacial area, were revealed. It demonstrates that anionic ionosomes share a common theoretical framework with their counterparts (i. e., cationic ionosomes, like Li+ -ionosomes). This work will spur the advancements in a myriad of fields, including such as the colloid and interface science, micro- and/or nanoscale electrochemistry, and electrophysiology and brain sciences.

Polymer Colloids: Moving beyond Spherical Particles

When thinking about colloidal particles, the fist image that comes into mind is that of tiny little polystyrene spheres with a narrow size distribution. While spherical polymer colloids are one of the workhorses of colloid science, scientists have been working on the development of progressively advanced strategies to move beyond particles with spherical shapes, and prepared polymer colloids with more complex morphologies. This short review aims at providing a summary of these developments, focusing primarily on methods applicable to submicron particles, with an eye towards their applications and some discussion about advantages and drawbacks of the various approaches.