Eric Hughes

Microfluidic preparation and self diffusion PFG-NMR analysis of monodisperse water-in-oil-in-water double emulsions

Monodisperse water-in-oil-in-water (WOW) double emulsions have been prepared using microfluidic glass devices designed and built primarily from off the shelf components. The systems were easy to assemble and use. They were capable of producing double emulsions with an outer droplet size from 100 to 40 μm. Depending on how the devices were operated, double emulsions containing either single or multiple water droplets could be produced. Pulsed-field gradient self-diffusion NMR experiments have been performed on the monodisperse water-in-oil-in-water double emulsions to obtain information on the inner water droplet diameter and the distribution of the water in the different phases of the double emulsion. This has been achieved by applying regularization methods to the self-diffusion data. Using these methods the stability of the double emulsions to osmotic pressure imbalance has been followed by observing the change in the size of the inner water droplets over time.

A simple, inexpensive, and precise magic angle spinning speed controller

Certain magic-angle spinning heteronuclear dipolar recoupling experiments using rotor-synchronized pulse trains require very precise control of the sample-spinning rate. An inexpensive spinning speed controller for use in magic-angle solid-state NMR experiments is described which can control the spinning rate to within +/- 0.2 Hz. The apparatus is based on a simple micro-controller and is self-contained. Experimental results are presented that show the importance of good spinning speed control.

Structure, diffusion, and permeability of protein-stabilized monodispersed oil in water emulsions and their gels: a self-diffusion NMR study

Self-diffusion NMR is used to investigate monodispersed oil in water emulsions and the subsequent gel formed by removing the water through evaporation. The radius of the oil droplets in the emulsions is measured using a number of diffusion methods based on the measurement of the mean squared displacement of the oil, water, and tracer molecules. The results are consistent with the known size of the emulsions. Bragg-like reflections due to the restricted diffusion of the water around the oil droplets are observed due to the low polydispersity of the emulsions and the dense packing. The resulting data are fitted to a pore glass model to give the diameter of both the pools of interstitial water and the oil droplets. In the gel, information on the residual three-dimensional structure is obtained using the short time behavior of the effective diffusion coefficient to give the surface to volume ratio of the residual protein network structure. The values for the surface to volume ratio are found to be consistent with the expected increase of the surface area of monodisperse droplets forming a gel network. At long diffusion observation times, the permeability of the network structure is investigated by diffusion NMR to give a complete picture of the colloidal system considered.

Monocomponent hexa- and dodecaethylene glycol succinyl-tocopherol esters: Self-assembly structures, cellular uptake and sensitivity to enzyme hydrolysis

We have chemically synthesized two water-soluble forms of tocopherol succinate linked via an ester bond to hexaethylene glycol and dodecaethylene glycol. The self-assembly structure of the former in water is vesicular, whereas the latter forms elongated micelles. We treated Caco-2 cells with these compounds in these physical forms, in addition to a mixed micelle form. The intact compounds were taken up into the cells, influenced by both the chain length and the physical structure. In addition, the tocopherol derivatives were also metabolized into tocopherol succinate and tocopherol inside the cell. The total hydrolysis and uptake into the cells was two-fold higher from tocopherol hexaethylene glycol succinate in the form of mixed micelles than in vesicular form as assessed by analyzing intracellular tocopherol and tocopherol succinate. The longer polyethylene glycol chain gave a higher intracellular tocopherol succinate/tocopherol ratio. The major intracellular esterase in Caco-2 cells is carboxyl esterase 1 (EC 3.1.1.1), and in silico modelling studies show that the position of docking and hence the site of hydrolysis is influenced by the chain length. The in silico prediction is consistent with the in vitro data, since a longer chain length is predicted to favour hydrolysis of the ester bond between the succinate and polyethylene glycol moieties.

Decoupling of Mass Transport Mechanisms in the Stagewise Swelling of Multiple Emulsions

This contribution reports on the mass transport kinetics of osmotically imbalanced water-in-oil-in-water (W1/O/W2) emulsions. Although frequently studied, the control of mass transport in W1/O/W2 emulsions is still challenging. We describe a microfluidics-based method to systematically investigate the impact of various parameters, such as osmotic pressure gradient, oil phase viscosity, and temperature, on the mass transport. Combined with optical microscopy analyses, we are able to identify and decouple the various mechanisms, which control the dynamic droplet size of osmotically imbalanced W1/O/W2 emulsions. So, swelling kinetics curves with a very high accuracy are generated, giving a basis for quantifying the kinetic aspects of transport. Two sequential swelling stages, i.e., a lag stage and an osmotically dominated stage, with different mass transport mechanisms are identified. The determination and interpretation of the different stages are the prerequisite to control and trigger the swelling process. We show evidence that both mass transport mechanisms can be decoupled from each other. Rapid osmotically driven mass transport only takes place in a second stage induced by structural changes of the oil phase in a lag stage, which allow an osmotic exchange between both water phases. Such structural changes are strongly facilitated by spontaneous water-in-oil emulsification. The duration of the lag stage is pressure-independent but significantly influenced by the oil phase viscosity and temperature.

Rapid sphere sizing using a Bayesian analysis of reciprocal space imaging data

Dispersed systems are important in many applications in a wide range of industries such as the petroleum, pharmaceutical and food industries. Therefore the ability to control and non-invasively measure the physical properties of these systems, such as the dispersed phase size distribution, is of significant interest, in particular for concentrated systems, where microscopy or scattering techniques may not apply or with very limited output quality. In this paper we show how reciprocal space data acquired using both 1D magnetic resonance imaging (MRI) and 2D X-ray micro-tomographic (X-ray μCT) data can be analysed, using a Bayesian statistical model, to extract the sphere size distribution (SSD) from model sphere systems and dispersed food foam samples. Glass spheres-in-xanthan gels were used as model samples with sphere diameters (D) in the range of 45μm⩽D⩽850μm. The results show that the SSD was successfully estimated from both the NMR and X-ray μCT with a good degree of accuracy for the entire range of glass spheres in times as short as two seconds. After validating the technique using model samples, the Bayesian sphere sizing method was successfully applied to air/water foam samples generated using a microfluidics apparatus with 160μm⩽D⩽400μm. The effect of different experimental parameters such as the standard deviation of the bubble size distribution and the volume fraction of the dispersed phase is discussed.

KINETICS OF DESORPTION OF WATER, ETHANOL, ETHYL ACETATE, AND TOLUENE FROM A MONTMORILLONITE

Desorption processes of low-molecular-weight compounds from the surface of smectites into the gas phase determine a number of processes, e.g. those involved in drug delivery and the release of herbicides. The desorption has not been investigated thoroughly and is not well understood. The present study was undertaken in order to understand better the factors influencing these desorption mechanisms. Starting with a very pure standard (Na+-rich) montmorillonite (Kunipia-F), which was exchanged against cations with different hydration properties (Ca2+, Li+, phenyltrimethylammonium, hexyltrimethyl-ammonium), the experiments explored the rate of desorption of volatiles with different chemical functionalities (water, ethanol, ethyl acetate, and toluene). The desorption was monitored by thermogravimetry and differential scanning calorimetry under isothermal conditions, and by ramping the temperature at a constant rate. The experiments were compared with numerical calculations based on finite-element methods and with analytical models. These data point to a two-step mechanism where the desorption follows the curve of the equilibrium desorption isotherms of those molecules on the montmorillonite. The bulk-like volatiles (i.e. volatiles with release kinetics close to that of the bulk liquids) were desorbed in a first step. With a decrease in the degree of coverage of the volatile on the montmorillonite, the desorption was increasingly dominated by the strength of interaction between the volatile and the interlayer cations of the montmorillonite.