Effects of interesterified lipid design on the short/medium chain fatty acid hydrolysis rate and extent (in vitro).

Short/medium chain fatty acids have well known health effects such as gut immune regulation and ketogenesis. The ability to realise these health effects is potentially limited by their rapid gastro-intestinal lipolysis. It was proposed that synthesising novel interesterified lipids via an interesterification reaction to generate a combination of short/medium and long chain fatty acids would modulate their gastrointestinal digestion. Using in vitro gastric and gastro-intestinal digestion models, the effect of the fatty acid chain length and interesterification on the rate and extent of lipolysis was analysed. Overall, "pure" (consisting of a single fatty acid) lipids of ≤C8 underwent rapid lipolysis releasing three fatty acids after intestinal hydrolysis while lipids of ≥C10 released two fatty acids after intestinal hydrolysis. The most interesting observation is that the extent of gastric lipolysis of C4 fatty acids was much lower when they were interesterified with longer chain fatty acids compared to that with the pure C4 triglyceride. Tributyrin underwent ∼60% lipolysis by gastric lipase as indicated by a decrease in total fatty acid release during SIF lipolysis after pre-exposure to rabbit gastric lipase (RGL) in SGF. In comparison, the C4-C8 interesterified lipid exhibited only a 18.1% decrease, and the C4-C18:1 interesterified lipid a 6.1% decrease in total fatty acid release in SGF-SIF. These results suggest that interesterification modulates the digestion of butyric acid from within the stomach to later in the intestine. This study reveals that the design of interesterified lipids alters the timing, but not the extent of short chain fatty acid delivery in the gastrointestinal tract. Such understanding has likely benefits for designing novel interesterified lipids which may have unique applications in various dietary and therapeutic modalities.

Impact of Protein Gel Porosity on the Digestion of Lipid Emulsions.

The present study sought to understand how the microstructure of protein gels impacts lipolysis of gelled emulsions. The selected system consisted of an oil-in-water (o/w) emulsion embedded within gelatin gels. The gelatin-gelled emulsions consisted of a discontinuous network of aggregated emulsion droplets (mesoscale), dispersed within a continuous network of gelatin (microscale). The viscoelastic properties of the gelled emulsions were dominated by the rheological behavior of the gelatin, suggesting a gelatin continuous microstructure rather than a bicontinuous gel. A direct relationship between the speed of fat digestion and gel average mesh size was found, indicating that the digestion of fat within gelatin-gelled emulsions is controlled by the ability of the gel's microstructure to slow lipase diffusion to the interface of fat droplets. Digestion of fat was facilitated by gradual breakdown of the gelatin network, which mainly occurred via surface erosion catalyzed by proteases. Overall, this work has demonstrated that the lipolysis kinetics of gelled emulsions is driven by the microstructure of protein gels; this knowledge is key for the future development of microstructures to control fat digestion and/or the delivery of nutrients to different parts of the gastrointestinal tract.

Vitamin E and vitamin E acetate absorption from self-assembly systems under pancreas insufficiency conditions.

We determined the bioavailability of vitamin E from self-assembly structures in patients with diagnosed chronic pancreas insufficiency. Vitamin E solubilized in dispersed inverted bicontinuous cubic phase and in micellar formulation was delivered directly to the small intestine by tube-feeding. A cross-over study with randomization of 6 subjects and 2 treatments including a combined dose of 18 mg (27 IU) of vitamin E (RRR-[5,7-methyl-((2)H6)]-α-tocopherol) and 27 mg (27 IU) vitamin E acetate (RRR-[5-methyl-(2)H3]-α-tocopheryl acetate) was applied over a time period of 1 h. Plasma samples were collected for 56 h and analyzed by liquid chromatography-mass spectrometry. Appearance of labeled tocopherols originating from the treatment started at 25 h and reached Cmax (0.6-4.6 µM depending on subject) in the 7-9 h window. From the Tmax onwards, both forms of tocopherols diminished slowly to 30-50% of their maxima within 56 h. Strong inter-individual variation was observed in the plasma appearance curves (relative standard deviation varied between 38-45%). No significant discrimination was found between the absorption of free or acetylated forms of deuterated α-tocopherol confirming that application of acetylated α-tocopherol provides the same bioavailability as free α-tocopherol. This observation is valid in both dispersed inverted bicontinuous cubic phase and micellar formulations. Furthermore, since the area-under-the-curve values from cubic phase and from micellar formulations are similar, the cubic phase formulation could represent an alternative delivery system for lipophilic micronutrients in conditions or studies where polysorbate-based micelles cannot be generated.

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.

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.

Study of liquid crystal space groups using controlled tilting with cryogenic transmission electron microscopy.

We developed a method that enables differentiation between liquid crystalline-phase particles corresponding to different space groups. It consists of controlled tilting of the specimen to observe different orientations of the same particle using cryogenic transmission electron microscopy. This leads to the visualization of lattice planes (or reflections) that are present for a given structure and absent for the other one(s) and that give information on liquid crystalline structures and their space groups. In particular, we show that we can unambiguously distinguish among particles having the inverted micellar cubic (space group Fd(3)m, 227), the inverted bicontinuous gyroid (space group Ia(3)d, 230), the inverted bicontinuous diamond (space group Pn(3)m, 224), and the inverted bicontinuous primitive cubic structure (space group Im(3)m, 229).