Colloidal Gels Research Articles

Leveraging polyetheramine-bisepoxide reaction in water and LCST-mediated phase separation toward microstructured poly(amino alcohol ethers) hydrogels

Herein, a two-step “mix-and-click in water” strategy has been developed to enable the preparation of microstructured hydrogels without complex equipments and elaborate synthesis. Capitalizing on the“click” characteristics of nucleophilic opening of epoxide by amines in conjunction with lower critical solution temperature (LCST)-mediated phase separation phenomenon of the in situ formed prepolymers in water, we demonstrate that a new family of microstructured poly(amino alcohol ethers) hydrogels can be prepared readily from off-the-shelf polyetheramines and bisepoxides. The occurrence and extent of phase separation exhibited by the prepolymers derived from various combinations of reactants at the gel preparation temperature have a prominent effect on the structure of the hydrogels, resulting in the versatile outcomes of formation of homogeneous colloidal gels, structurally graded colloidal gels, or colloids-in-gel hybrids. With inherent ability to host hydrophobic molecules and good cytocompatibility toward fibroblast cells in vitro, this new family of microstructured poly(amino alcohol ethers) hydrogels may be exploited further for drug delivery and tissue engineering.

Review of Microgels for Enhanced Oil Recovery: Properties and Cases of Application.

In todays’ world, there is an increasing number of mature oil fields every year, a phenomenon that is leading to the development of more elegant enhanced oil recovery (EOR) technologies that are potentially effective for reservoir profile modification. The technology of conformance control using crosslinked microgels is one the newest trends that is gaining momentum every year. This is due to the simplicity of the treatment process and its management, as well as the guaranteed effect in the case of the correct well candidate selection. We identified the following varieties of microgels: microspheres, thermo- and pH-responsible microgels, thin fracture of preformed particle gels, colloidal dispersed gels. In this publication, we try to combine the available chemical aspects of microgel production with the practical features of their application at oil production facilities. The purpose of this publication is to gather available information about microgels (synthesis method, monomers) and to explore world experience in microgel application for enhanced oil recovery. This article will be of great benefit to specialists engaged in polymer technologies at the initial stage of microgel development.

Imaging Erythrocyte Sedimentation in Whole Blood.

The erythrocyte sedimentation rate (ESR) is one of the oldest medical diagnostic tools. However, currently there is some debate on the structure formed by the cells during the sedimentation process. While the conventional view is that erythrocytes sediment as separate aggregates, others have suggested that they form a percolating gel, similar to other colloidal suspensions. However, visualization of aggregated erythrocytes, which would settle the question, has always been challenging. Direct methods usually study erythrocytes in 2D situations or low hematocrit (∼1%). Indirect methods, such as scattering or electric measurements, provide insight on the suspension evolution, but cannot directly discriminate between open or percolating structures. Here, we achieved a direct probing of the structures formed by erythrocytes in blood at stasis. We focused on blood samples at rest with controlled hematocrit of 45%, from healthy donors, and report observations from three different optical imaging techniques: direct light transmission through thin samples, two-photon microscopy and light-sheet microscopy. The three techniques, used in geometries with thickness from 150 μm to 3 mm, highlight that erythrocytes form a continuous network with characteristic cracks, i.e., a colloidal gel. The characteristic distance between the main cracks is of the order of ∼100 μm. A complete description of the structure then requires a field of view of the order of ∼1 mm, in order to obtain a statistically relevant number of structural elements. A quantitative analysis of the erythrocyte related processes and interactions during the sedimentation need a further refinement of the experimental set-ups.

2D Nanosilicate for additive manufacturing: Rheological modifier, sacrificial ink and support bath

Extrusion-based 3D printing/bioprinting is a promising approach to generate patient-specific tissue engineered grafts. However, a major challenge in extrusion-based 3D printing/bioprinting is that most currently used materials lack the versatility to be used in a wide range of applications. In this study, we introduce colloidal solutions of two-dimensional (2D) nanosilicates as a platform technology to print complex structures via three different approaches. In the first approach, we designed a shear-thinning ink composed of nanosilicates, which can be further reinforced by adding different types of water-soluble polymers. In the second approach, we demonstrated the use of nanosilicates as a sacrificial ink to design microfluidic devices for in vitro disease modelling. In the third approach, we utilized a colloidal nanosilicate gel as a support bath for 3D printing by nullifying the surface tension and gravitational forces. Due to their exceptional versatility, nanosilicate-based biomaterials could be widely adopted in the fields of additive manufacturing, tissue engineering, drug delivery, and medical devices.

The Antimicrobial Effectiveness of Chitosan and Polysaccharide of Durian Peel Extract against Mycobacterium tuberculosis Isolates

BACKGROUND: Tuberculosis (TB) disease is an infection caused by Mycobacterium tuberculosis and is transmitted through sputum droplets of sufferers or suspect TB in the air. Chitosan as an antimicrobial agent can be used in the biomedical field because it has a number of hydroxyl groups (OH) and amine groups (NH2). The chemical substance of durian peel extract (Durio zibethinus L.) contains pectin which is multifunctional and can be used in the pharmaceutical field. Chemically, pectin is a polysaccharide polymer of D-galacturonic acid linked by -1,4 glycosidic bonds which can dissolve in water to form colloidal solutions or gels. AIM: This study was to determine the antimicrobial effectiveness of chitosan and polysaccharides from durian peel extract (D. zibethinus L.) against M. tuberculosis isolates in vitro. METHODS: The research method is based on an experimental study in vitro. M. tuberculosis isolates in this research from sputum samples of patients suspected of TB in Surakarta Regional General Hospital. The stages of the research were performed that preparation chitosan gel (CG), bioformulation of CG, and polysaccharide gel (PG) durian peel extract are 5%, 10%, 15%, 20%, and 25%, and drug susceptibility testing against M. tuberculosis isolates. RESULTS: CG 10% was effective as an antimicrobial against M. tuberculosis isolates but PG durian peel extract (5%; 10%; 15%; 20%; and 25%) was not effective as an antimicrobial against M. tuberculosis isolates. The types of anti-tuberculosis drug (ATD) that was effective against M. tuberculosis isolates were ethambutol 80% and streptomycin 40%, while isoniazid and rifampicin were not effective as ATD against M. tuberculosis isolates. CONCLUSION: CG 10% was effective as an antimicrobial against M. tuberculosis isolates, while PG 25% durian peel extract was not effective as an antimicrobial against M. tuberculosis isolates. CG has the potential as an ATD based on natural bioactive ingredients for TB therapy.

Yield precursor in primary creep of colloidal gels.

Colloidal gels under constant moderate stress flow only after a prolonged solid-like deformation. Predicting the time-dependent yielding of the gels would facilitate control of their mechanical stability and transport, but early detectable signs of such delayed solid-to-fluid transition remain unknown. We show that the shear rate of colloidal gels under constant stress can forecast an eventual yielding during the earliest stage of deformation known as primary creep. The shear rate before failure exhibits a characteristic power-law decrease as a function of time, distinct from the linear viscoelastic response. We model this early-stage behavior as a series of uncorrelated local plastic events that are thermally activated, which illuminates the exponential dependence of the yield time on the applied stress. By revealing underlying viscoplasticity, this precursor to yield in the macroscopic shear rate provides a convenient tool to predict the yielding of a gel well in advance of its actual occurrence.

Hydrodynamics induce superdiffusive jumps of passive tracers along critical paths of random networks and colloidal gels.

We present a numerical study on the effect of hydrodynamic interactions (HI) on the diffusion of inert point tracer particles in several fixed random structures. As expected, the diffusion is hampered by the extra hydrodynamic friction introduced by the obstacle network. However, a non-trivial effect due to HI appears in the analysis of the van-Hove displacement probability close to the percolation threshold, where tracers diffuse through critical fractal paths. We show that the tracer dynamics can be split up into short and long jumps, the latter being ruled by either exponential or Gaussian van Hove distribution tails. While at short time HI slow down the tracer diffusion, at long times, hydrodynamic interactions with the obstacles increase the probability of longer jumps, which circumvent the traps of the labyrinth more easily. Notably, the relation between the anomalous diffusion exponent and the fractal dimension of the critical (intricate) paths is greater than one, which implies that the long-time (long-jump) diffusion is mildly superdiffuse. A possible reason for such a hastening of the diffusion along the network corridors is the hydrodynamically induced mobility anisotropy, which favours displacements parallel to the walls, an effect which has already been experimentally observed in collagen gels.

Large Impacts of Small Particles: The Effects of Active Particles on Colloidal Gels and Crystals and of Inulin Microparticles on Gut Retention in Mice

Large Impacts of Small Particles: The Effects of Active Particles on Colloidal Gels and Crystals and of Inulin Microparticles on Gut Retention in Mice

Tuning local microstructure of colloidal gels by ultrasound-activated deformable inclusions.

Colloidal gels possess a memory of previous shear events, both steady and oscillatory. This memory, embedded in the microstructure, affects the mechanical response of the gel, and therefore enables precise tuning of the material properties under careful preparation. Here we demonstrate how the dynamics of a deformable inclusion, namely a bubble, can be used to locally tune the microstructure of a colloidal gel. We examine two different phenomena of bubble dynamics that apply a local strain to the surrounding material: dissolution due to gas diffusion, with a characteristic strain rate of ∼10−3 s−1; and volumetric oscillations driven by ultrasound, with a characteristic frequency of ∼104 s−1. We characterise experimentally the microstructure of a model colloidal gel around bubbles in a Hele-Shaw geometry using confocal microscopy and particle tracking. In bubble dissolution experiments, we observe the formation of a pocket of solvent next to the bubble surface, but marginal changes to the microstructure. In experiments with ultrasound-induced bubble oscillations, we observe a striking rearrangement of the gel particles into a microstructure with increased local ordering. High-speed bright-field microscopy reveals the occurrence of both high-frequency bubble oscillations and steady microstreaming flow; both are expected to contribute to the emergence of the local order in the microstructure. These observations open the way to local tuning of colloidal gels based on deformable inclusions controlled by external pressure fields.

Unraveling gelation kinetics, arrested dynamics and relaxation phenomena in filamentous colloids by photon correlation imaging.

The fundamental understanding of the gelation kinetics, stress relaxation and temporal evolution in colloidal filamentous gels is central to many aspects of soft and biological matter, yet a complete description of the inherent complex dynamics of these systems is still missing. By means of photon correlation imaging (PCI), we studied the gelation of amyloid fibril solutions, chosen as a model filamentous colloid with immediate significance to biology and nanotechnology, upon passage of ions through a semi-permeable membrane. We observed a linear-in-time evolution of the gelation front and rich rearrangement dynamics of the gels, the magnitude and the spatial propagation of which depend on how effectively electrostatic interactions are screened by different ionic strengths. Our analysis confirms the pivotal role of salt concentration in tuning the properties of amyloid gels, and suggests potential routes for explaining the physical mechanisms behind the linear advance of the salt ions.

Microstructure and elasticity of dilute gels of colloidal discoids.

The linear elasticity of dilute colloidal gels formed from discoidal latex particles is quantified as a function of aspect ratio and modeled by confocal microscopy characterization of their fractal cluster microstructure. Colloidal gels are of fundamental interest because of their widespread use to stabilize complex fluids in industry. Technological interest in producing gels of desired moduli using the least number of particles drives formulators to produce gels at dilute concentrations. However, dilute gels self-assembled from isotropic spheres offer limited scope for rheological tunability due to the universal characteristics of their fractal microstructure. Our results show that changing the building block shape from sphere to discoid yields very large shifts in gel elasticity relative to the universal behavior reported for spheres. This shift - tunable through aspect ratio - yields up to a 100-fold increase in elastic modulus at a fixed volume fraction. From modeling the results using the theory for fractal cluster gel rheology, which is applicable at the dilute conditions of this study, we reveal that the efficient generation of elasticity by the colloidal discoids is the consequence of the combined effects of shape anisotropy on the fractal microstructure of the gel network, the anisotropy of the attractive interparticle pair potentials, and the volumetric compactness of the fractal cluster. These results extend prior characterizations of the rheology of non-spherical particulate gels by providing quantitative estimates of how the specific mechanisms of fractality, pair potential, and clustering mediate the profound effects of particle shape anisotropy on the elastic rheology of colloidal gels.

Prevention of Postoperative Adhesion with a Colloidal Gel Based on Decyl Group Modified Alaska Pollock Gelatin Microparticles

Prevention of Postoperative Adhesion with a Colloidal Gel Based on Decyl Group Modified Alaska Pollock Gelatin Microparticles

Interpenetration of fractal clusters drives elasticity in colloidal gels formed upon flow cessation

Colloidal gels are out-of-equilibrium soft solids composed of attractive Brownian particles that form a space-spanning network at low volume fractions. The elastic properties of these systems result from the network microstructure, which is very sensitive to shear history. Here, we take advantage of such sensitivity to tune the viscoelastic properties of a colloidal gel made of carbon black nanoparticles. Starting from a fluidized state at an applied shear rate 0, we use an abrupt flow cessation to trigger a liquid-to-solid transition. We observe that the resulting gel is all the more elastic when the shear rate 0 is low and that the viscoelastic spectra can be mapped on a master curve. Moreover, coupling rheometry to small angle X-ray scattering allows us to show that the gel microstructure is different from gels solely formed by thermal agitation where only two length scales are observed: the dimension of the colloidal and the dimension of the fractal aggregates. Competition between shear and thermal energy leads to gels with three characteristic length scales. Such gels structure in a percolated network of fractal clusters that interpenetrate each other. Experiments on gels prepared with various shear histories reveal that cluster interpenetration increases with decreasing values of the shear rate 0 applied before flow cessation. These observations strongly suggest that cluster interpenetration drives the gel elasticity, which we confirm using a structural model. Our results, which are in stark contrast to previous literature, where gel elasticity was either linked to cluster connectivity or to bending modes, highlight a novel local parameter controlling the macroscopic viscoelastic properties of colloidal gels.

A microstructural investigation of an industrial attractive gel at pressure and temperature.

Oil-continuous drilling fluids used in the oil and gas industry are formulated to be pseudoplastic with a relatively weak yield stress. These fluids are required to maintain their properties over wide temperature and pressure ranges yet there are few methods that can sensitively study the inherent structure and mechanical properties in the fluids under such conditions. Here we study a model oil-continuous drilling fluid formulation as a function of both temperature (up to 153 °C) and pressure (up to 1330 bar) with Diffusive Wave Spectroscopy (DWS). The system comprises a colloidal gel network of clay particles and trapped emulsion droplets. As a function of temperature the system undergoes local structural changes reflected in the DWS dynamics which are also consistent with macroscopic rheological measurements. On cycling to high pressure the system exhibits similar structural and dynamic changes with a strong hysteresis. Although multiple scattering in multicomponent non-ergodic samples does not directly yield self diffusion probe dynamics, the use of microrheology analysis here appears to be in good agreement with direct rheological measurements of the sample linear viscoelasticity at ambient pressure. Thus DWS microrheology succesfully probes irreversible changes in the structure and the mechanical response of the drilling fluid formulation under a high pressure cycle.

Stiffening colloidal gels by solid inclusions.

The elastic properties of a soft matter material can be greatly altered by the presence of solid inclusions whose microscopic properties, such as their size and interactions, can have a dramatic effect. In order to shed light on these effects we use extensive rheology computer simulations to investigate colloidal gels with solid inclusions of different sizes. We show that the elastic properties vary in a highly non-trivial way as a consequence of the interactions between the gel backbone and the inclusions. In particular, we show that the key aspects are the presence of the gel backbone and its mechanical alteration originating from the inclusions. To confirm our observations and their generality, we performed experiments on an emulsion that presents strong analogies with colloidal gels and confirms the trends observed in the simulations.

Size-selective characterization of porous media via tortuous network analysis

Particle migration through gels, glasses, and other porous media provides selectivity, storage, and delivery of macromolecules and other particles that are critical to biological cell function, drug delivery, and water filtration. Modeling migration rates of solvent-borne colloids through such materials is thus essential in understanding and engineering the structure-transport relationship. However, most of these materials comprise an amorphously structured porous network not amenable to analytical modeling. Approaches to overcoming this challenge typically bypass interrogating the porous network by abstracting it away via mean-field models or by interrogating the solid features for a coarse estimate of porosity. While such approaches reduce analytical complexity significantly, resulting models cannot reveal interconnectedness of the void network, size-specific permeability, or insight into migration mechanisms. Other approaches aim to extract a network of void paths by approximating a medium as packing of monodisperse spheres and using traditional Voronoi decomposition, giving results that are accurate only when the constituent particles are monodisperse but strongly overpredict the passable size when the medium is made up of size-polydisperse particles, as is the case for colloidal gels, additive manufacturing, soil sediment, to name some examples. We use radical Voronoi decomposition to establish a network backbone of the porous microstructure, which accurately represents morphology for any degree of constituent polydispersity. We present an algorithm for endowing this network with the accurate size and shape and, from it, systematically deducing size-specific accessible branches. The result is a detailed permeability model for porous media of arbitrary microstructure that reveals material morphology, material phase, and size-specific permeability.

SYNTHESIS AND CHARACTERIZATION OF ZEOLITE Y FROM KANKARA CLAY USING ALKALINE FUSION METHOD.

Zeolite Y was synthesized from Kankara clay, following alkaline fusion method which compared favourably with other conventional method of synthesis to obtain a high yield of zeolite Y. The raw material was hydrothermally activated with NaOH to synthesized zeolite Y. The starting materials for zeolite Y synthesis were prepared in two stages; The first stage was colloidal seed with a composition (5% of Al): 10.67 Na2O: Al2O3:10SiO2:180H2O and the second phase was the preparation of feedstock gel which was done few hours before the ageing time of the colloidal gel elapsed. The method used eliminated a lot of challenges, cost and energy of production using conditions crystallization temperature of 100oC and time of 5 h. This produced zeolite Y with a specific surface area of 686 m2/g, the SEM images demonstrated that the produced zeolites Y possessed agglomerated tetrahedral euhedral morphology. The transformation of the starting material into zeolite Y was evaluated using X-ray diffraction, scanning electron microscopy and fourier transform infra-red spectroscopy to elucidate the crystallization process of zeolites

Location of the gel-like boundary in patchy colloidal dispersions: Rigidity percolation, structure, and particle dynamics

During the past decade, there has been a hot debate about the physical mechanisms that determine when a colloidal dispersion approaches the gel transition. However, there is still no consensus on a possible unique route that leads to the conditions for the formation of a gel-like state. Based on gel states identified in experiments, Valadez-Pérez etal. [Phys. Rev. E 88, 060302(R) (2013)PLEEE81539-375510.1103/PhysRevE.88.060302] proposed rigidity percolation as the precursor of colloidal gelation in adhesive hard-sphere dispersions with coordination number 〈n_{b}〉 equal to 2.4. Although this criterion was originally established to describe mechanical transitions in network-forming molecular materials with highly directional interactions, it worked well to explain gel formation in colloidal suspensions with isotropic short-range attractive forces. Recently, this idea has also been used to account for the dynamical arrest experimentally observed in attractive spherocylinders. Then, by assuming that rigidity percolation also drives gelation in spherical colloids interacting with short-ranged and highly directional potentials, we locate the thermodynamic states where gelation seems to occur in dispersions made up of patchy colloids. To check whether the criterion 〈n_{b}〉=2.4 also holds in patchy colloidal systems, we apply the so-called bond-bending analysis to determine the fraction of floppy modes at some percolating clusters. This analysis confirms that the condition 〈n_{b}〉=2.4 is a good approximation to determine those percolating clusters that are either mechanically stable or rigid. Furthermore, our results point out that not all combinations of patches and coverages lead to a gel-like state. Additionally, we systematically study the structure and the cluster size distribution along those thermodynamic states identified as gels. We show that for high coverage values, the structure is very similar for systems that have the same coverage regardless the number or the position of the patches on the particle surface. Finally, by using dynamic Monte Carlo computer simulations, we calculate both the mean-square displacement and the intermediate scattering function at and in the neighborhood of the gel-like states.

Photo-Cross-Linkable Human Albumin Colloidal Gels Facilitate In Vivo Vascular Integration for Regenerative Medicine.

Biodegradable cellular and acellular scaffolds have great potential to regenerate damaged tissues or organs by creating a proper extracellular matrix (ECM) capable of recruiting endogenous cells to support cellular ingrowth. However, since hydrogel-based scaffolds normally degrade through surface erosion, cell migration and ingrowth into scaffolds might be inhibited early in the implantation. This could result in insufficient de novo tissue formation in the injured area. To address these challenges, continuous and microsized strand-like networks could be incorporated into scaffolds to guide and recruit endogenous cells in rapid manner. Fabrication of such microarchitectures in scaffolds is often a laborious and time-consuming process and could compromise the structural integrity of the scaffold or impact cell viability. Here, we have developed a fast single-step approach to fabricate colloidal hydrogels, which are made up of randomly packed human serum albumin-based photo-cross-linkable microparticles with continuous internal networks of microscale voids. The human serum albumin conjugated with methacrylic groups were assembled to microsized aggregates for achieving unique porous structures inside the colloidal gels. The albumin hydrogels showed tunable mechanical properties such as elastic modulus, porosity, and biodegradability, providing a suitable ECM for various cells such as cardiomyoblasts and endothelial cells. In addition, the encapsulated cells within the hydrogel showed improved cell retention and increased survivability in vitro. Microporous structures of the colloidal gels can serve as a guide for the infiltration of host cells upon implantation, achieving rapid recruitment of hematopoietic cells and, ultimately, enhancing the tissue regeneration capacity of implanted scaffolds.

Spatially uniform dynamics in equilibrium colloidal gels.

Gels of DNA nanostars, besides providing a compatible scaffold for biomedical applications, are ideal model systems for testing the physics of equilibrium colloidal gels. Here, using dynamic light scattering and photon correlation imaging (a recent technique that, by blending light scattering and imaging, provides space-resolved quantification of the dynamics), we follow the process of gel formation over 10 orders of magnitude in time in a model system of tetravalent DNA nanostars in solution, a realization of limited-valence colloids. Such a system, depending on the nanostar concentration, can form either equilibrium or phase separation gels. In stark contrast to the heterogeneity of concentration and dynamics displayed by the phase separation gel, the equilibrium gel shows absence of aging and a remarkable spatially uniform dynamics.