Capillary Assembly of Anisotropic Particles at Cylindrical Fluid-Fluid Interfaces.

The unique behavior of colloids at liquid interfaces provides exciting opportunities for engineering the assembly of colloidal particles into functional materials. The deformable nature of fluid-fluid interfaces means that we can use the interfacial curvature, in addition to particle properties, to direct self-assembly. To this end, we use a finite element method (Surface Evolver) to study the self-assembly of rod-shaped particles adsorbed at a simple curved fluid-fluid interface formed by a sessile liquid drop with cylindrical geometry. Specifically, we study the self-assembly of single and multiple rods as a function of drop curvature and particle properties such as shape (ellipsoid, cylinder, and spherocylinder), contact angle, aspect ratio, and chemical heterogeneity (homogeneous and triblock patchy). We find that the curved interface allows us to effectively control the orientation of the rods, allowing us to achieve parallel, perpendicular, or novel obliquely orientations with respect to the cylindrical drop. In addition, by tuning particle properties to achieve parallel alignment of the rods, we show that the cylindrical drop geometry favors tip-to-tip assembly of the rods, not just for cylinders, but also for ellipsoids and triblock patchy rods. Finally, for triblock patchy rods with larger contact line undulations, we can achieve strong spatial confinement of the rods transverse to the cylindrical drop due to the capillary repulsion between the contact line undulations of the particle and the pinned contact lines of the sessile drop. Our capillary assembly method allows us to manipulate the configuration of single and multiple rod-like particles and therefore offers a facile strategy for organizing such particles into useful functional materials.

"Ghost" Silica Nanoparticles of "Host"-Inherited Antibacterial Action.

We fabricated surface-rough mesoporous silica nanoparticles ("ghost" SiO2NPs) by using composite mesoporous copper oxide nanoparticles ("host" CuONPs) as templates, which allowed us to mimic their surface morphology. The "host" CuONPs used here as templates, however, had a very high antibacterial effect, with or without functionalization. To evaluate the surface roughness effect on the "ghost" SiO2NPs antibacterial action, we functionalized them with (3-glycidyloxypropyl)trimethoxysilane (GLYMO) to permit additional covalent coupling of 4-hydroxyphenylboronic acid (4-HPBA). The diol groups on the bacterial membrane can form reversible covalent bonds with boronic acid (BA) groups on the "ghost" SiO2NPs surface and bind to the bacteria, resulting in a very strong amplification of their antibacterial activity, which does not depend on electrostatic adhesion. The BA-functionalized "ghost" SiO2NPs showed a very significant antibacterial effect as compared to smooth SiO2NPs of the same surface coating and particle size. We attribute this to the "ghost" SiO2NPs mesoporous surface morphology, which mimics to a certain extent those of the original mesoporous CuONPs used as templates for their preparation. We envisage that the "ghost" SiO2NPs effectively acquire some of the antibacterial properties from the "host" CuONPs, with the same functionality, despite being completely free of copper. The antibacterial effect of the functionalized "ghost" SiO2NPs/GLYMO/4-HPBA on Rhodococcus rhodochrous (R. rhodochrous) and Escherichia coli (E. coli) is much higher than that of the nonfunctionalized "ghost" SiO2NPs or the "ghost" SiO2NPs/GLYMO. The results indicate that the combination of rough surface morphology and strong adhesion of the particle surface to the bacteria can make even benign material such as silica act as a strong antimicrobial agent. Additionally, our BA-functionalized nanoparticles ("ghost" SiO2NPs/GLYMO/4-HPBA) showed no detectable cytotoxic impact against human keratinocytes at particle concentrations, which are effective against bacteria.

Controlling the Antimicrobial Action of Surface Modified Magnesium Hydroxide Nanoparticles.

Magnesium hydroxide nanoparticles (Mg(OH)2NPs) have recently attracted significant attention due to their wide applications as environmentally friendly antimicrobial nanomaterials, with potentially low toxicity and low fabrication cost. Here, we describe the synthesis and characterisation of a range of surface modified Mg(OH)2NPs, including particle size distribution, crystallite size, zeta potential, isoelectric point, X-ray diffraction (XRD), dynamic light scattering (DLS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM). We explored the antimicrobial activity of the modified Mg(OH)2NPs on the microalgae (C. reinhardtii), yeast (S. cerevisiae) and Escherichia coli (E. coli). The viability of these cells was evaluated for various concentrations and exposure times with Mg(OH)2NPs. It was discovered that the antimicrobial activity of the uncoated Mg(OH)2NPs on the viability of C. reinhardtii occurred at considerably lower particle concentrations than for S. cerevisiae and E. coli. Our results indicate that the antimicrobial activity of polyelectrolyte-coated Mg(OH)2NPs alternates with their surface charge. The anionic nanoparticles (Mg(OH)2NPs/PSS) have much lower antibacterial activity than the cationic ones (Mg(OH)2NPs/PSS/PAH and uncoated Mg(OH)2NPs). These findings could be explained by the lower adhesion of the Mg(OH)2NPs/PSS to the cell wall, because of electrostatic repulsion and the enhanced particle-cell adhesion due to electrostatic attraction in the case of cationic Mg(OH)2NPs. The results can be potentially applied to control the cytotoxicity and the antimicrobial activity of other inorganic nanoparticles.

Strongly Enhanced Antibacterial Action of Copper Oxide Nanoparticles with Boronic Acid Surface Functionality.

Copper oxide nanoparticles (CuONPs) have been widely recognized as good antimicrobial agents but are heavily regulated due to environmental concerns of their postuse. In this work, we have developed and tested a novel type of formulation for copper oxide (CuONPs) which have been functionalized with (3-glycidyloxypropyl)trimethoxysilane (GLYMO) to allow further covalent coupling of 4-hydroxyphenylboronic acid (4-HPBA). As the boronic acid (BA) groups on the surface of CuONPs/GLYMO/4-HPBA can form reversible covalent bonds with the diol groups of glycoproteins on the bacterial cell surface, they can strongly bind to the cells walls resulting in a very strong enhancement of their antibacterial action which is not based on electrostatic adhesion. Scanning electron microscopy and transmission electron microscopy imaging revealed that 4-HPBA-functionalized CuO nanoparticles could accumulate more on the cell surface than nonfunctionalized ones. We demonstrate that the CuONPs with boronic acid surface functionality are far superior antibacterial agents compared to bare CuONPs. Our results showed that the antibacterial impact of the 4-HPBA-functionalized CuONPs on Rhodococcus rhodochrous and Escherichia coli is 1 order of magnitude higher than that of bare CuONPs or CuONPs/GLYMO. We also observed a marked increase of the 4-HPBA-functionalized CuONPs antibacterial action on these microorganisms at shorter incubation times compared with the bare CuONPs at the same conditions. Significantly, we show that the cytotoxicity of CuONPs functionalized with 4-HPBA as an outer layer can be controlled by the concentration of glucose in the media, and that the effect is reversible as glucose competes with the sugar residues on the bacterial cell walls for the BA-groups on the CuONPs. Our experiments with human keratinocyte cell line exposure to CuONPs/GLYMO/4-HPBA indicated lack of measurable cytotoxicity at particle concentration which are effective as an antibacterial agent for both R. rhodochrous and E. coli. We envisage that formulations of CuONPs/GLYMO/4-HPBA can be used to drastically reduce the overall CuO concentration in antimicrobial formulations while strongly increasing their efficiency.

Self-grafting copper oxide nanoparticles show a strong enhancement of their anti-algal and anti-yeast action.

We have developed and tested copper oxide nanoparticles (CuONPs) grafted with (3-glycidyloxypropyl)trimethoxysilane (GLYMO) and coupled with 4-hydroxyphenylboronic acid (4-HPBA), which provides a very strong boost of their action as anti-algal and anti-yeast agents. The boronic acid terminal groups on the surface of the CuONPs/GLYMO/4-HPBA can form reversible covalent bonds with the diol groups of glycoproteins and carbohydrates expressed on the cell surface where they bind and accumulate, which is not based on electrostatic adhesion. Results showed that, the impact of the 4-HPBA grafted CuONPs on microalgae (C. reinhardtii) and yeast (S. cerevisiae) is several hundred percent higher than that of bare CuONPs and CuONPs/GLYMO at the same particle concentration. SEM and TEM imaging revealed that 4-HPBA-functionalized CuONPs nanoparticles can accumulate more on the cell walls than non-functionalized CuONPs. We found a marked increase of the 4-HPBA functionalized CuONPs action on these microorganisms at shorter incubation times compared with the bare CuONPs at the same conditions. We also showed that the anti-algal action of CuONPs/GLYMO/4-HPBA can be controlled by the concentration of glucose in the media and that the effect is reversible as glucose competes with the diol residues on the algal cell walls for the HPBA groups on the CuONPs. Our experiments with human cell lines incubated with CuONPs/GLYMO/4-HPBA indicated a lack of measurable loss of cell viability at particle concentrations which are effective as anti-algal agents. CuONPs/GLYMO/4-HPBA can be used to drastically reduce the overall CuO concentration in anti-algal and anti-yeast formulations while strongly increasing their efficiency.

Structuring and calorie control of bakery products by templating batter with ultra melt-resistant food-grade hydrogel beads.

We report the use of a temperature insensitive, food-grade hydrogel to reduce the caloric density of pancakes that were prepared at temperatures much higher than the boiling point of water. This cheap, facile method utilises a mixed agar-methylcellulose hydrogel, which was blended to produce a slurry of hydrogel microbeads. The pancake batter was mixed with a controlled volume percentage of slurry of hydrogel beads and cooked. From bomb calorimetry experiments, the composites were found to have a reduced caloric density that reflects the volume percentage of hydrogel beads mixed with the batter. Using this procedure, we were able to reduce the caloric density of pancakes by up to 23 ± 3% when the volume percentage of hydrogel beads initially used was 25%. The method is not limited to pancakes and could potentially be applied to various other food products. The structure and morphology of the freeze-dried pancakes and pancake-hydrogel composites were investigated and pores of a similar size to the hydrogel beads were found, confirming that the gel beads maintained their structure during the cooking process. There is scope for further development of this method by the encapsulation of nutritionally beneficial or flavour enhancing ingredients within the hydrogel beads.

Colloid particle formulations for antimicrobial applications.

Colloidal particles are being extensively studied in various antimicrobial applications due to their small size to volume ratio and ability to exhibit a wide spectrum of antibacterial, antifungal, antialgal and antiviral action. The present review focuses on various nanoparticles (NPs) of inorganic, organic and hybrid materials, and discusses some of the methods for their preparation as well as mechanisms of their antimicrobial action. We consider the antimicrobial applications of metal oxide nanoparticles (ZnO, MgO, CuO, Cu2O, Al2O3, TiO2, CeO2 and Y2O3), metal nanoparticles (NPs), such as copper, silver and gold, metal hydroxide NPs such as Mg(OH)2 as well as hybrid NPs made from biodegradable materials, such as chitosan, lignin and dextran, loaded with other antimicrobial agents. Recent developments for targeted delivery of antimicrobials by using colloid antibodies for microbial cell shape and surface recognition are also discussed. We also consider recent advances in the functionalization of nanoparticles and their potential antimicrobial applications as a viable alternative of conventional antibiotics and antiseptic agents which can help to tackle antimicrobial resistance. The review also covers the recently developed environmentally benign NPs (EbNPs) as a "safer-by-design" green chemistry solution of the post use fate of antimicrobial nanomaterials.

Attachment of composite porous supra-particles to air-water and oil-water interfaces: theory and experiment.

We developed and tested a theoretical model for the attachment of fluid-infused porous supra-particles to a fluid-liquid interface. We considered the wetting behaviour of agglomerated clusters of particles, typical of powdered materials dispersed in a liquid, as well as of the adsorption of liquid-infused colloidosomes at the liquid-fluid interface. The free energy of attachment of a composite spherical porous supra-particle made from much smaller aggregated spherical particles to the oil-water interface was calculated. Two cases were considered: (i) a water-filled porous supra-particle adsorbed at the oil-water interface from the water phase, and, (ii) an oil-filled porous supra-particle adsorbed at the oil-water interface from the oil-phase. We derived equations relating the three-phase contact angle of the smaller "building block" particles and the contact angle of the liquid-infused porous supra-particles. The theory predicts that the porous supra-particle contact angle attached at the liquid interface strongly depends on the type of fluid infused in the particle pores and the fluid phase from which it approaches the liquid interface. We tested the theory by using millimetre-sized porous supra-particles fabricated by evaporation of droplets of polystyrene latex suspension on a pre-heated super-hydrophobic surface, followed by thermal annealing at the glass transition temperature. Such porous particles were initially infused with water or oil and approached to the oil-water interface from the infusing phase. The experiment showed that when attaching at the hexadecane-water interface, the porous supra-particles behaved as hydrophilic when they were pre-filled with water and hydrophobic when they were pre-filled with hexadecane. The results agree with the theoretically predicted contact angles for the porous composite supra-particles based on the values of the contact angles of their building block latex particles measured with the Gel Trapping Technique. The experimental data for the attachment of porous supra particles to the air-water interface from both air and water also agree with the theoretical model. This study gives important insights about how porous particles and particle aggregates attach to the oil-water interface in Pickering emulsions and the air-water surface in particle-stabilised aqueous foams relevant in ore flotation and a range of cosmetic, pharmaceutical, food, home and personal care formulations.

Preparation and attachment of liquid-infused porous supra-particles to liquid interfaces.

We prepared model porous composite supra-particles and investigated the effect of the initial infused fluid phase on their attachment at the liquid-fluid interface. We used a simple method for fabrication of millimetre-sized spherical porous supra-particles from much smaller monodisperse latex microparticles as building blocks by evaporation of a polystyrene sulphate latex suspension on a hot super-hydrophobic surface. We annealed the dried supra-particles at the polymer's glass transition temperature to fuse partially their latex particle building blocks. Spherical porous supra-particles were produced above 40 wt% initial concentration of the latex particles in the suspension, which had a rough surface, with a porous and amorphous structure. We controlled the supra-particle size by varying the initial volume of the latex suspension drop, the latex particle concentration and the drop evaporation temperature. This preparation technique allowed limited control over the porosity of the supra-particles by varying the initial concentration of the latex particle suspension, the rate of evaporation and the annealing temperature. We characterised the surface morphology and the inner structure of supra-particles by SEM imaging. We report for the first time results of an MRI study of supra-particles attached to an air-water or an oil-water interface, which indicated that only the surface layer of the building block particles attaches to the liquid interface while the pore fluid was not displaced by the outer fluid. We observed that supra-particles infused with water had different wettability and attachment positions at the oil-water interface compared with the same particles infused with oil. Similarly, the infusion of the porous supra-particles with water led to a different attachment at the air-water interface compared to the attachment of the same supra-particle when dry. The fundamental importance of this result is that the porous particles (or colloid particle agglomerates) may give an oil-in-water or water-in-oil Pickering emulsion depending on whether they are initially impregnated with oil or water. The results of this study are relevant for particle-stabilised emulsions and foams in a range of pharmaceutical, food and cosmetic formulations as well as ore flotation.

Adsorption of carboxylic modified latex particles at liquid interfaces studied by the gel trapping technique.

We have studied how carboxylic modified latex (CML) microparticles adsorb at liquid surfaces and the preferred type of emulsion they can stabilise depending on the particle size and the surface density of carboxylic groups. We measured the particle contact angle by using the gel trapping technique (GTT) for CML particles adsorbed at air-water and oil-water interfaces. Using this method we obtained scanning electron microscopy (SEM) micrographs of polydimethylsiloxane (PDMS) replicas of the liquid interface with the particles, where the PDMS replicates the non-polar phase and measured the particle contact angle. We discovered that the particle wettability correlates well with the surface density of the carboxylic groups but is not very sensitive to the presence of electrolyte in the aqueous phase and the value of the particle zeta potential. We demonstrated that CML microparticles with a high surface density of COOH groups stabilise oil-in-water (O/W) emulsions while those with the lowest coverage of COOH groups favour the formation of water-in-oil (W/O) emulsions. We found that this corresponds to a change of the CML particle contact angle from lower than 90° to higher than 90° upon decrease of the surface density of COOH groups. The findings confirm that the surface density of polar groups has a much bigger effect on the particle wettability and the preferred emulsion than the particle surface charge and zeta potential. Our results on the type of stabilised Pickering emulsion agree with other experimental studies with different particle materials. We propose an alternative explanation for the link between the particle contact angle and the type of stabilised Pickering emulsion.

Self-assembly of two-dimensional colloidal clusters by tuning the hydrophobicity, composition, and packing geometry.

We study the structure of binary monolayers of large (3 µm diameter) very hydrophobic (A) and large (3 µm diameter) hydrophilic (B) or small (1 µm diameter) hydrophilic (C) silica particles at an octane-water interface. By tuning the composition and packing geometry of the mixed monolayer, we find that a rich variety of two-dimensional hexagonal superlattices of mixed A/B or A/C clusters are formed, stabilized by short-ranged electrostatic induced dipole interactions. The cluster structures obtained are in excellent agreement with zero temperature calculations, indicating that the self-assembly process can be effectively controlled.

Two-dimensional colloidal alloys.

We study the structure of mixed monolayers of large (3 µm diameter) and small (1 µm diameter) very hydrophobic silica particles at an octane-water interface as a function of the number fraction of small particles ξ. We find that a rich variety of two-dimensional hexagonal super-lattices of large (A) and small (B) particles can be obtained in this system due to strong and long-range electrostatic repulsions through the nonpolar octane phase. The structures obtained for the different compositions are in good agreement with zero temperature calculations and finite temperature computer simulations.

Novel film-calliper method of measuring the contact angle of colloidal particles at liquid interfaces.

A simple and reliable film-calliper method of measuring the particle contact angle at the water-air (oil) interface in real time has been developed. Its applicability to submicrometer and micrometer latex and silica particles is demonstrated.

Effect of electrolyte in silicone oil-in-water emulsions stabilised by fumed silica particles.

Partially hydrophobised fumed silica particles are used to make silicone oil-in-water emulsions at natural pH of the aqueous phase. The stability and rheological properties of the emulsions and suspensions are studied at NaCl concentrations in the range 0-100 mM. It is found that all emulsions are very stable to coalescence irrespective of the NaCl concentration. However, a strong effect of electrolyte on the creaming and rheological properties is observed and linked to the particle interactions in aqueous suspensions. The creaming rate and extent are large at low electrolyte concentrations but both abruptly decrease at salt concentrations exceeding the critical flocculation concentration of the suspension (approximately 1 mM NaCl). The drastic improvement of the stability to creaming is attributed to the formation of a visco-elastic three-dimensional network of interconnected particles and emulsion droplets.

Emulsification of partially miscible liquids using colloidal particles: nonspherical and extended domain structures.

We present microscopy studies of particle-stabilized emulsions with unconventional morphologies. The emulsions comprise pairs of partially miscible fluids and are stabilized by colloids. Alcohol-oil mixtures are employed; silica colloids are chemically modified so that they have partial wettability. We create our morphologies by two distinct routes: starting with a conventional colloid-stabilized emulsion or starting in the single-fluid phase with the colloids dispersed. In the first case temperature cycling leads to the creation of extended fluid domains built around some of the initial fluid droplets. In the second case quenching into the demixed region leads to the formation of domains which reflect the demixing kinetics. The structures are stable due to a jammed, semisolid, multilayer of colloids on the liquid-liquid interface. The differing morphologies reflect the roles in formation of the arrested state of heterogeneous and homogeneous nucleation and spinodal decomposition. The latter results in metastable, bicontinuous emulsions with frozen interfaces, at least for the thin-slab samples, investigated here.

Wetting phenomena at the CO2/water/glass interface.

A novel high-pressure apparatus and technique were developed to measure CO2/water/solid contact angles (theta) in situ for pressures up to 204 bar. For two glass substrates with different hydrophilicities, theta increased significantly with CO2 pressure. As the pressure was increased, an increase in the cohesive energy density of CO2 caused the substrate/CO2 and water/CO2 interfacial tensions (gamma) to decrease, whereas the water/substrate gamma value increased. theta for the more hydrophobic substrate was predicted accurately from the experimental water/CO2 gamma value and an interfacial model that included only long-range forces. However, for the more hydrophilic substrate, short-range specific interactions due to capping of the silanol groups by physisorbed CO2 resulted in an unusually large increase in the water/substrate gamma value, which led to a much larger increase in theta than predicted by the model. A novel type of theta hysteresis was discovered in which larger theta values were observed during depressurization than during pressurization, even down to ambient pressure. Effective receding angles were observed upon pressurization, and effective advancing angles were observed upon depressurization on the basis of movement of the three-phase contact line. The greater degree of hysteresis for the more hydrophilic silica can be attributed in part to the capping of silanol groups with CO2. The large effects of CO2 on the various interfacial energies play a key role in the enhanced ability of CO2, relative to many organic solvents, to dry silica surfaces as reported previously on the basis of FTIR spectroscopy (Tripp, C. P.; Combes, J. R. Langmuir 1998, 14, 7348-7352).

Structure and stability of silica particle monolayers at horizontal and vertical octane-water interfaces.

Monolayers of silica particles at horizontal and vertical octane-water interfaces have been studied by microscopy. It is found that their structure and stability depend strongly on the particle hydrophobicity. Very hydrophobic silica particles, with a contact angle of 152 degrees measured through the water, give well-ordered monolayers at interparticle distances larger than 5 particle diameters which are stable toward aggregation and sedimentation. In contrast, monolayers of less-hydrophobic particles are disordered and unstable. Two-dimensional particle sedimentation has been observed in the case of vertical monolayers. The results have been analyzed with a simple two-particle model considering the sedimentation equilibrium as a balance between the long-range electrostatic repulsion through the oil, the gravity force, and the capillary attraction due to deformation of the fluid interface around particles. The value of the charge density at the particle-octane interface, 14.1 muC/m(2), found for the most hydrophobic particles is reasonable. It drastically decreases for particles with lower hydrophobicity, which is consistent with the order-disorder transition in monolayer structure reported by us before. The pair interactions between particles at a horizontal octane-water interface have been analyzed including the capillary attraction due to undulated three-phase contact line caused by nonuniform wetting (the contact angle hysteresis). The results are in agreement with the great stability of very hydrophobic silica particle monolayers detected experimentally, even at low pH at the point of zero charge of the particle-water interface, and with the aggregated structure of hydrophilic particle monolayers.