Complex Colloidal Systems Research Articles

Diagnostics of luminescent recording media based on the polarized scattering spectra of hologram sensors formed in the substance analyzed

The article is devoted to the diagnosis and identification of luminescent holographic information carriers in particular wine products using polarization holographic spectroscopy methods. For the first time, to our best knowledge, a technique has been developed for measuring and analyzing scattered polarized light (depolarization spectra) on polarization-holographic sensors formed in analyte. Polarized scattering spectra on a hologram sensor (measuring transducers) are of particular interest, since they provide information not only about the chemical composition of the media, for example, luminescence and absorption spectra, but also about particles that may be present in the analyte – the higher the anisotropy of the molecules and atoms, the greater the depolarization. Methods for measuring polarized scattering and excitation spectra carried out for various samples of holographic materials, as well as methods for processing and presenting the obtained spectral data are described. This may be of interest, since recording media, in particular wine, are complex colloidal systems. For the diagnosis, classification and identification of recording materials, it is proposed for the first time to use reflective holographic sensors (Yu.N. Denisyuk) of various physical natures (the concept of a spectral holographic portrait).

Coarse-Grained Many-Body Potentials of Ligand-Stabilized Nanoparticles from Machine-Learned Mean Forces.

Colloidal nanoparticles self-assemble into a variety of superstructures with distinctive optical, structural, and electronic properties. These nanoparticles are usually stabilized by a capping layer of organic ligands to prevent aggregation in the solvent. When the ligands are sufficiently long compared to the dimensions of the nanocrystal cores, the effective coarse-grained forces between pairs of nanoparticles are largely affected by the presence of neighboring particles. In order to efficiently investigate the self-assembly behavior of these complex colloidal systems, we propose a machine-learning approach to construct effective coarse-grained many-body interaction potentials. The multiscale methodology presented in this work constitutes a general bottom-up coarse-graining strategy where the coarse-grained forces acting on coarse-grained sites are extracted from measuring the vectorial mean forces on these sites in reference fine-grained simulations. These effective coarse-grained forces, i.e., gradients of the potential of mean force or of the free-energy surface, are represented by a simple linear model in terms of gradients of structural descriptors, which are scalar functions that are rotationally invariant. In this way, we also directly obtain the free-energy surface of the coarse-grained model as a function of all coarse-grained coordinates. We expect that this simple yet accurate coarse-graining framework for the many-body potential of mean force will enable the characterization, understanding, and prediction of the structure and phase behavior of relevant soft-matter systems by direct simulations. The key advantage of this method is its generality, which allows it to be applicable to a broad range of systems. To demonstrate the generality of our method, we also apply it to a colloid-polymer model system, where coarse-grained many-body interactions are pronounced.

Role of ionic surfactant in magnetic dynamics of self-assembled dispersions of nanoplatelets

In complex colloidal systems, interparticle interactions strongly affect the dynamics of the constituting particles. A study of the dynamical response also provides invaluable information on the character of those interactions. Here we demonstrate how tuning the electrostatic interactions by an ionic surfactant in dispersions of magnetic nanoplatelets leads to developing new dynamic modes in magnetic response spectra. The collective modes can be induced or suppressed by either varying the concentration ratio of the magnetic nanoplatelets (MP) to the surfactant or increasing the MP concentration reflecting the nanoscale characteristics of this fluid magnet.

An experimental investigation on the impact of divalent ions on the emulsification of oil: Comparison of biodegradable (green) and petroleum-based surfactants

Emulsification of oil with surfactants often yields in complex colloidal systems which require understanding their physicochemical properties prior to their use in industry. This study aims to investigate the effects of divalent ions (calcium and magnesium) on the emulsification performance of biodegradable (green) surfactants of Triton™ CG-110 (alkyl polyglycoside, APG) and GreenZyme (GZ) at two temperature conditions (25 °C and 70 °C). For this purpose, the phase behaviour, interfacial tension (IFT), stability, droplet size distribution and rheological properties of APG and GZ microemulsion were evaluated. The outcomes were then compared with the emulsification performance of petroleum-based (synthetic) surfactants of alpha-olefin sulfonate (AOS) and cetyltrimethylammonium bromide (CTAB). Furthermore, the impacts of alkalis (ethanolamine and sodium carbonate) on microemulsions and the demulsification performance of a zwitterionic demulsifier (cocobetaine) were explored. The results show that only APG and CTAB could produce water in oil (W/O) microemulsions in the presence of divalent ions. The stability of APG and CTAB microemulsions was affected by divalent ions since the water segregation rate (WSR) index of these microemulsions went up from ≈21% to ≈ 85% as salinity increased up to 15 wt%. Also, the average droplet size of these microemulsions went up from 50-64 nm to 220–255 nm as salinity increased to 9 wt%. This is because the negative charge density on the microemulsion droplet surface decreases as the salinity increases, thus the electrostatic repulsive force between the droplets becomes weaker. In addition, APG and CTAB microemulsions showed a shear thinning behaviour, and their viscosity value increased with the increase in salinity. It is speculated that the presence of divalent ions generates more friction between the molecules, which causes an increase in the viscosity of the microemulsions.

Probing Temperature Responsivity of Microgels and Its Interplay with a Solid Surface by Super-Resolution Microscopy and Numerical Simulations.

Super-resolution microscopy has become a powerful tool to investigate the internal structure of complex colloidal and polymeric systems, such as microgels, at the nanometer scale. An interesting feature of this method is the possibility of monitoring microgel response to temperature changes in situ. However, when performing advanced microscopy experiments, interactions between the particle and the environment can be important. Often microgels are deposited on a substrate, since they have to remain still for several minutes during the experiment. This study uses direct stochastic optical reconstruction microscopy (dSTORM) and advanced coarse-grained molecular dynamics simulations to investigate how individual microgels anchored on hydrophilic and hydrophobic surfaces undergo their volume phase transition with temperature. We find that, in the presence of a hydrophilic substrate, the structure of the microgel is unperturbed and the resulting density profiles quantitatively agree with simulations performed under bulk conditions. Instead, when a hydrophobic surface is used, the microgel spreads at the interface and an interesting competition between the two hydrophobic strengths,monomer-monomer vs monomer-surface,comes into play at high temperatures. The robust agreement between experiments and simulations makes the present study a fundamental step to establish this high-resolution monitoring technique as a platform for investigating more complex systems, these being either macromolecules with peculiar internal structure or nanocomplexes where molecules of interest can be encapsulated in the microgel network and controllably released with temperature.

Analysis of the dispersed composition of milk using photon correlation spectroscopy

The dispersed composition of milk and the properties of its dispersed phases significantly affect the quality of dairy products and its processing. Therefore, the problem of research and control of the dispersed composition of milk is quite important. The article describes the applicability of photon correlation spectroscopy for the analysis and diagnosis of milk dispersion composition. The dispersed composition of milk was studied by photon correlation spectroscopy on the Photocor complex spectrometer. Histograms of the distribution of the hydrodynamic radius of the particles of dispersed phase of milk with different fat content and different manufacturers are obtained. Limitations of this method were also found in the analysis of complex colloidal systems containing more than two different dispersed phases with a significant predominance of quantity of particles. It was found that the reliability of measurement results is significantly affected by the degree of dilution of the studied samples and spectroscopy modes: number of units, duration of unit and the measuring angle. As a result of the experiment the optimal parameters for measuring the dispersed phase of milk with different fat content were determined, which were: dilution ratio-2 times, the angle of the photodetector position – 120−150 °, number of units-100, duration of unit – 20 s. The obtained results are planned to be used for the development of guidelines for the introduction of photon correlation spectroscopy in the dairy industry as an express method of analysis in the concept of complete traceability of the quality and safety of dairy products

Increasing efficiency and accuracy of magnetic interaction calculations in colloidal simulation through machine learning

Calculating the magnetic interaction between magnetic particles that are positioned in close proximity to one another is a surprisingly challenging task. Exact solutions for this interaction exist either through numerical expansion of multipolar interactions or through solving Maxwell’s equations with a finite element solver. These approaches can take hours for simple configurations of three particles. Meanwhile, across a range of scientific and engineering problems, machine learning approaches have been developed as fast computational platforms for solving complex systems of interest when large data sets are available. In this paper, we bring the touted benefits of recent advances in science-based machine learning algorithms to bear on the problem of modeling the magnetic interaction between three particles. We investigate this approach using diverse machine learning systems including physics informed neural networks. We find that once the training data has been collected and the model has been initiated, simulation times are reduced from hours to mere seconds while maintaining remarkable accuracy. Despite this promise, we also try to lay bare the current challenges of applying machine learning to these and more complex colloidal systems.

Thermo-Electro-Mechanics at Individual Particles in Complex Colloidal Systems

It has been well established that thermoelectric (TE) field can arise from different Soret coefficients of salt ions in the aqueous solution under constant temperature gradient. Despite their high relevance to cellular biology and particle manipulations, understanding and controlling of TE field in complex colloidal systems that involve micro/nanoparticles, salt ions and molecules have remained challenging. In such colloidal systems, the challenge arises from the thermal interactions with charged micro/nanoparticles that distort the TE field around the particles. Herein, we provide a framework for TE field in colloidal suspensions with various ions and surfactants at the single-nanoparticle level. In particular, we reveal the spatial variation of TE field around a dielectric particle under temperature gradient to determine the thermoelectric trapping force on the particle. Our theoretical results on the trapping force predicted from the TE force profile match well with the experimental opto-thermoelectric trapping stiffness of particles in the solutions where the temperature gradient was well-controlled by a laser beam. With their insight into TE field and force in complex systems, our framework and methodology can be extended to engineer the TE field for versatile opto-thermoelectric manipulations of arbitrarily shaped particles with non-uniform surface morphology and to advance the scientific research in cellular biology.

Depletion-interaction-driven assembly of golf ball-like particles for development of colloidal macromolecules

Colloidal molecules created by clustering monodisperse particles are a significant model system of atoms and molecules in colloidal scale. To attain modelling of complex or high-molecular-weight molecules such as hyper-branched polymers and proteins, it is required to develop a new assembling system which can prepare three-dimensionally designed colloidal molecules. In this study, we proposed an approach for complex colloidal molecules created by association between golf ball-like particles and spherical particles via depletion interaction. Several golf ball-like particles joined together, which formed joined particle assemblies at the spherical particles acting as their joints in a depletant solution. The number of golf ball-like particles in a particle assembly was increased by increasing the concentration of the depletant, leading to the formation of branched colloidal chains of the golf ball-like particles. Because the golf ball-like particles in the colloidal chain flexibly rotated at their joints, the conformation of the chains varied in the depletant solution. The present results demonstrated that the golf-ball like particle that can be joined to form colloidal macromolecules with high association number and high flexibility will be a promising building block for complex colloidal model systems.

Electro-elastoviscous response of polyaniline functionalized nano-porous zeolite based colloidal dispersions

The present article discusses the typical influence of grafted conducting polymers in the mesoscale pores of dielectric particles on the static and dynamic electrorheology and electro-viscoelastic behavior of corresponding colloids. Nanocrystalline meso-nanoporous zeolite has been prepared by chemical synthesis and subsequently polyaniline (PANI) coating has been implemented. Electrorheological (ER) suspensions have been formed by dispersing the nanoparticles in silicone oil and their viscoelastic behaviors are examined to understand the nature of such complex colloidal systems under electric fields. PANI-Zeolite ER fluids demonstrate higher static electroviscous effects and yield stress potential than untreated Zeolite, typically studied in literature. Transient electro-viscous characterizations show a stable and negligible hysteresis behavior when both the fluids are exposed to constant as well as time varying electric field intensities. Further oscillatory shear experiments of frequency and strain sweeps exhibit predominant elastic behavior in case of Zeolite based ER suspensions as compared to PANI systems. Detailed investigations reveal Zeolite based ER suspensions display enhanced relative yielding as well as electro-viscoelastic stability than the PANI-Zeolite. The steady state viscous behaviors are scaled against the non-dimensional Mason number to model the system behavior for both fluids. Experimental data of flow behaviors of both the ER fluids are compared with semi-classical models and it is found that the CCJ model possesses a closer proximity than traditional Bingham model, thereby revealing the fluids to be generic pseudo-linear fluids. The present article reveals that while the PANI based fluids are typically hailed superior in literature, it is only restricted to steady shear utilities. In case of dynamic and oscillatory systems, the traditional Zeolite based fluids exhibit superior ER caliber.

Dynamic properties of polydisperse colloidal particles in the presence of thermal gradient studied by a modified Brownian dynamic model

Aggregation and migration of colloidal particles under the thermal gradient widely exists in nature and many industrial processes. In this study, dynamic properties of polydisperse colloidal particles in the presence of thermal gradient were studied by a modified Brownian dynamic model. Other than the traditional forces on colloidal particles, including Brownian force, hydrodynamic force, and electrostatic force from other particles, the electrostatic force from the asymmetric ionic diffusion layer under a thermal gradient has been considered and introduced into the Brownian dynamic model. The aggregation ratio of particles (RA), the balance time (tB) indicating the time threshold when becomes constant, the porosity (), fractal dimension (Df) and distributions of concentration (DISC) and aggregation (DISA) for the aggregated particles were discussed based on this model. The aggregated structures formed by polydisperse particles are less dense and the particles therein are loosely bonded. Also it showed a quite large compressibility as the increases of concentration and interparticle potential can significantly increase the fractal dimension. The thermal gradient can induce two competitive factors leading to a two-stage migration of particles. When , the unsynchronized aggregation is dominant and the particles slightly migrate along the thermal gradient. When , the thermophoresis becomes dominant thus the migrations of particles are against the thermal gradient. The effect of thermophoresis on the aggregate structures was found to be similar to the effect of increasing particle concentration. This study demonstrates how the thermal gradient affects the aggregation of monodisperse and polydisperse particles and can be a guide for the biomimetics and precise control of colloid system under the thermal gradient. Moreover, our model can be easily extended to other more complex colloidal systems considering shear, temperature fluctuation, surfactant, etc.

Characterisation of heterogeneity and spatial autocorrelation in phase separating mixtures using Moran’s I

In complex colloidal systems, particle-poor regions can develop within particle-rich phases during sedimentation or creaming. These particle-poor regions are overlooked by 1D profiles, which are typically used to assess particle distributions in a sample. Alternative methods to visualise and quantify these regions are required to better understand phase separation, which is the focus of this paper. Magnetic resonance imaging has been used to monitor the development of compositional heterogeneity in a vesicle-polymer mixture undergoing creaming. T2 relaxation time maps were used to identify the distribution of vesicles, with vesicle-poor regions exhibiting higher T2 relaxation times than regions richer in vesicles. Phase separated structures displayed a range of different morphologies and a variety of image analysis methods, including first-order statistics, Fourier transformation, grey level co-occurrence matrices and Moran’s I spatial autocorrelation, were used to characterise these structures, and quantify their heterogeneity. Of the image analysis techniques used, Moran’s I was found to be the most effective at quantifying the degree and morphology of phase separation, providing a robust, quantitative measure by which comparisons can be made between a diverse range of systems undergoing phase separation. The sensitivity of Moran’s I can be enhanced by the choice of weight matrices used.

Delivery by Design (DbD): A Standardized Approach to the Development of Efficacious Nanoparticle- and Microparticle-Based Delivery Systems.

The design and development of nanoparticle- and microparticle-based delivery systems for the encapsulation, protection, and controlled release of active agents has grown considerably in the agrochemical, cosmetic, food, personal care, and pharmaceutical industries. These colloidal delivery systems can be utilized to overcome problems such as poor solubility, low activity, and chemical instability of active agents, as well as to create novel functional attributes such as controlled or targeted delivery. The purpose of this article is to develop a systematic approach, referred to as "delivery-by-design" (DbD), to make the design and fabrication process more efficient and effective. Initially, a brief review of some of the challenges associated with incorporating active agents into commercial products is given, and then an overview of different kinds of simple and complex colloidal delivery systems is given. The DbD approach is then presented as a series of stages: (1) definition of the molecular and physicochemical properties of the active agent; (2) definition of the required physicochemical, sensory, and functional attributes of the end-product; (3) specification of the required attributes of the colloidal delivery system; (4) specification of particle properties and delivery system selection; (5) optimization of delivery system manufacturing process; (6) establishment and implementation of delivery system testing protocol; and (7) optimization of delivery system performance. Utilization of the DbD approach may lead to more rapid design of efficacious and economically viable colloidal delivery systems for commercial applications.

Moving charged particles in lattice Boltzmann-based electrokinetics.

The motion of ionic solutes and charged particles under the influence of an electric field and the ensuing hydrodynamic flow of the underlying solvent is ubiquitous in aqueous colloidal suspensions. The physics of such systems is described by a coupled set of differential equations, along with boundary conditions, collectively referred to as the electrokinetic equations. Capuani et al. [J. Chem. Phys. 121, 973 (2004)] introduced a lattice-based method for solving this system of equations, which builds upon the lattice Boltzmann algorithm for the simulation of hydrodynamic flow and exploits computational locality. However, thus far, a description of how to incorporate moving boundary conditions into the Capuani scheme has been lacking. Moving boundary conditions are needed to simulate multiple arbitrarily moving colloids. In this paper, we detail how to introduce such a particle coupling scheme, based on an analogue to the moving boundary method for the pure lattice Boltzmann solver. The key ingredients in our method are mass and charge conservation for the solute species and a partial-volume smoothing of the solute fluxes to minimize discretization artifacts. We demonstrate our algorithm's effectiveness by simulating the electrophoresis of charged spheres in an external field; for a single sphere we compare to the equivalent electro-osmotic (co-moving) problem. Our method's efficiency and ease of implementation should prove beneficial to future simulations of the dynamics in a wide range of complex nanoscopic and colloidal systems that were previously inaccessible to lattice-based continuum algorithms.

Interview with Daan Frenkel, Boltzmann Medallist 2016 : Simulating soft matter through the lens of statistical mechanics.

Daan Frenkel has been awarded the most important prize in the field of statistical mechanics, the 2016 Boltzmann Medal, named after the Austrian physicist and philosopher Ludwig Boltzmann. The award recognises Frenkel's seminal contributions to the statistical-mechanical understanding of the kinetics, self-assembly and phase behaviour of soft matter. The honour recognises Frenkel's highly creative large-scale simulations of soft matter capable of explaining the self-assembly of complex macromolecular systems, colloidal and biomolecular systems. Frenkel is Professor of Theoretical Chemistry at the University of Cambridge, UK and has been Editor in Chief of EPJE between 2010 and 2014. The award will be given to both Frenkel and his French colleague Yves Pomeau, during the StatPhys Conference on 20th July 2016 in Lyon, France. In this interview with Sabine Louët, Frenkel gives his views on statistical physics, which has become more relevant than ever for interdisciplinary research. He also offers some pearls of wisdom for the next generation Statistical Mechanics experts.

Core–shell fluorinated methacrylate nanoparticles with Rhodamine-B for confocal microscopy and fluorescence correlation spectroscopy applications

Abstract There is a need to develop nanosized and submicron sized stable and efficient fluorescent particles for confocal microscopy and fluorescence correlation spectroscopy, which are useful methods to study dynamics and interactions in complex colloidal systems and living cells. Fluorescent core–transparent shell fluorinated polymer nanoparticles exhibit low refractive index, close to that of water, high fluorescence efficiency, high stability and no cytotoxicity which makes them excellent probes for water based and living systems. Fluorescent core–transparent shell submicron particles were synthesized using 1H,1H-heptafluoro- n -butyl methacrylate (HFBMA) as a monomer and Rhodamine-B-isothiocyanate as a dye. The fluorescent polymeric core was surrounded by a non-fluorescent shell obtained by the seeded growth synthesis. The spherical shape of the particles was confirmed by scanning electron microscopy and the particle size in suspension was characterized by dynamic light scattering (DLS) and fluorescence correlation spectroscopy (FCS). The effect of different reaction parameters, such as initiator concentration and polymerization time on the particle size and charge density as well as their toxicity were studied. The smallest nanoparticles, of diameter d = 240 nm for the core measured by DLS, were obtained with higher initiator concentration. Repeated confocal imaging, DLS and FCS measurements after a few months up to two years confirmed high fluorescence efficiency, stability and usefulness of prepared particles as versatile systems for confocal microscopy and fluorescence correlation spectroscopy studies in water-based colloidal suspensions. The cytotoxicity tests confirmed a possible use of these nanoparticles also in living cells.

Capillary-induced giant elastic dipoles in thin nematic films

Directed and true self-assembly mechanisms in nematic liquid crystal colloids rely on specific interactions between microparticles and the topological defects of the matrix. Most ordered structures formed in thin nematic cells are thus based on elastic multipoles consisting of a particle and nearby defects. Here, we report, for the first time to our knowledge, the existence of giant elastic dipoles arising from particles dispersed in free nematic liquid crystal films. We discuss the role of capillarity and film thickness on the dimensions of the dipoles and explain their main features with a simple 2D model. Coupling of capillarity with nematic elasticity could offer ways to tune finely the spatial organization of complex colloidal systems.

New Generation Devices for Lubricant Consistency Testing

Plastic lubricants represent a large group of lubricants that are widely used. Structurally, they are complex colloidal systems and are included among non-Newtonian fluids. They consist of oil basestock, a selected thickener, and a set of improvers. A significant role in the spatial structure of lubricants is played by the intermolecular van der Waals forces between the major components, namely between the basestock and the thickener. However, the spatial structure of the thickener is largely maintained by intermolecular forces other than van der Waals forces, in particular: dipole-dipole force (Kesson effect), dipole-induced dipole attraction (Debye effect), and momentary dipole-induced dipole force (London effect). The result of these types of forces is an adequate lubricant structure, which is responsible for rheological properties and texture [1-3].

Liquid marbles supported by monodisperse poly(methylsilsesquioxane) particles.

The preparation of model, well-controlled colloidal assemblies has been a central approach to understanding and optimizing the characteristics and functionality of complex colloidal dispersion systems. This approach, which has created a significant literature and rather deep understanding for emulsions and foams, has yet to be established for the liquid marble (water-in-air) motif. In this article we report the preparation of well-controlled liquid marbles using monodisperse micron-size particles of poly(methylsilsesquioxane) (PMSQ). The low cohesive nature of the stabilizing particles, their narrow size distribution, and their hydrophobicity permit the formation of liquid marbles containing a particulate monolayer with a hexagonally close-packed (HCP) structure. The "cleaning process" by rolling of liquid marbles under a flow of air on a hydrophobic substrate was useful to obtain the monolayer structure. Moreover, the monolayer structure was only obtained from liquids with high surface energy, whereas the others were not useful even though multilayered structure was formed from liquids that have intermediate surface energy.

Nuclear magnetic relaxation induced by exchange-mediated orientational randomization: Longitudinal relaxation dispersion for spin I = 1

The frequency dependence of the longitudinal relaxation rate, known as the magnetic relaxation dispersion (MRD), can provide a frequency-resolved characterization of molecular motions in complex biological and colloidal systems on time scales ranging from 1 ns to 100 μs. The conformational dynamics of immobilized proteins and other biopolymers can thus be probed in vitro or in vivo by exploiting internal water molecules or labile hydrogens that exchange with a dominant bulk water pool. Numerous water (1)H and (2)H MRD studies of such systems have been reported, but the widely different theoretical models currently used to analyze the MRD data have resulted in divergent views of the underlying molecular motions. We have argued that the essential mechanism responsible for the main dispersion is the exchange-mediated orientational randomization (EMOR) of anisotropic nuclear (electric quadrupole or magnetic dipole) couplings when internal water molecules or labile hydrogens escape from orientationally confining macromolecular sites. In the EMOR model, the exchange process is thus not just a means of mixing spin populations but it is also the direct cause of spin relaxation. Although the EMOR theory has been used in several studies to analyze water (2)H MRD data from immobilized biopolymers, the fully developed theory has not been described. Here, we present a comprehensive account of a generalized version of the EMOR theory for spin I = 1 nuclides like (2)H. As compared to a previously described version of the EMOR theory, the present version incorporates three generalizations that are all essential in applications to experimental data: (i) a biaxial (residual) electric field gradient tensor, (ii) direct and indirect effects of internal motions, and (iii) multiple sites with different exchange rates. In addition, we describe and assess different approximations to the exact EMOR theory that are useful in various regimes. In particular, we consider the experimentally important dilute regime, for which approximate analytical results are derived. As shown by the analytical expressions, and confirmed by exact numerical calculations, the dispersion is governed by the pure nuclear quadrupole resonance frequencies in the ultraslow-motion regime, where the relaxation rate also exhibits a much stronger dependence on the electric field gradient asymmetry than in the motional-narrowing regime.