Formulation of monodisperse water-in-oil emulsions encapsulating calcium ascorbate and ascorbic acid 2-glucoside by microchannel emulsification

The aim of this study was to investigate the effects of the emulsifying conditions and emulsifier type on production of water-in-oil (W/O) emulsions encapsulating ascorbic acid derivatives by microchannel (MC) emulsification. The ascorbic acid derivatives added in a dispersed aqueous phase are calcium ascorbate (AA-Ca) and ascorbic acid 2-glucoside (AA-2G). The continuous phase used was decane, soybean oil or their mixture, containing 5% (w/w) tetraglycerin monolaurate condensed ricinoleic acid ester or sorbitan trioleate. A hydrophobized silicon MC array plate (model: MS407) with a channel depth of 7μm was used for MC emulsification. The use of MC emulsification enabled successful encapsulation of AA-Ca and AA-2G in monodisperse W/O emulsion droplets with coefficients of variation (CV) less than 7%. Their average droplet diameter (dav) increased with increasing the continuous-phase viscosity that is similar or higher than the dispersed-phase viscosity. The dav and CV of the resultant monodisperse W/O emulsions were unaffected by the dispersed-phase flow rate below critical values of 1.2-1.6mLh-1 when using decane as the continuous-phase medium.

Approaches to the synthesis of peptide substituted frameworks

The 1,3 dipolar cycloaddition between carbonyl ylids (generated from cyclobutene epoxides flanked by esters) and norbornyl alkenes – the ACE reaction – offers a facile method for the construction of polynorbornyl molecular frameworks. This reaction has, as described in this dissertation, underpinned the construction of molecular frameworks that have peptides and amino acids attached. Such highly rigid peptide-frameworks are of use in the field of peptidomimetics; the template molecule governs the final positioning of any attached groups such that a precise arrangement of amino acids can be achieved without the need to construct entire proteins. In the course of any ACE reaction the ester flanked cyclobutene epoxide is transformed to a 1,3 dipole, the esters serve to stablise this reactive intermediate and are as a consequence incorporated in the reaction product. Modification of these esters provides pseudo-equatorial points for peptide attachment. These methyl esters were replaced with tert-butyl esters to provide pseudo-axial attachment points that could be selectively addressed. The optimal strategy for peptide-framework construction involved direct condensation of carboxyl protected amino acids to bicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid as well as condensation of amino acids to cyclobutene epoxides derived from this acid. The ACE reaction of (±) bicycloheptene-2-endo-carboxylic acid derivatives with cyclobutene epoxides synthesised from such racemic acid derivatives provided a mixture of enantiomers and meso compounds. In order to control the position of the attachment points – and hence the final location of the attached peptides – the ACE reaction required chiral starting materials. Accordingly, all peptidoframeworks were derived from the chiral (2S)-(-)-bicycloheptene carboxylic acid. The ACE reaction of this (S)-norbornene with the (S)-epoxide provided a peptide framework in which the attached amino acids were positioned pseudo-axially. Deprotection of the amino acid allowed peptide chain building in the pseudo-axial direction. Using this strategy a framework with an alanine residue and a triglycine peptide was synthesised. By combining this strategy with the ter-butyl ester variant a framework with pseudo-axial alanine and pseudo-equatorial glycine residues was manufactured.

Fatty acid-benzendiol derivatives and methods of making and using thereof

Disclosed are compounds comprising a benzenediol derivative bound to one or more fatty acids. Also disclosed are nutritional supplements, pharmaceutical formulations, delivery devices, and foodstuffs comprising the disclosed compounds. Methods of using the disclosed compounds and compositions to improve health are also disclosed.

Hydroxyoctadecadienoic acids: Oxidised derivatives of linoleic acid and their role in inflammation associated with metabolic syndrome and cancer

Linoleic acid (LA) is a major constituent of low-density lipoproteins. An essential fatty acid, LA is a polyunsaturated fatty acid, which is oxidised by endogenous enzymes and reactive oxygen species in the circulation. Increased levels of low-density lipoproteins coupled with oxidative stress and lack of antioxidants drive the oxidative processes. This results in synthesis of a range of oxidised derivatives, which play a vital role in regulation of inflammatory processes. The derivatives of LA include, hydroxyoctadecadienoic acids, oxo-​octadecadienoic acids, epoxy octadecadecenoic acid and epoxy-keto-octadecenoic acids. In this review, we examine the role of LA derivatives and their actions on regulation of inflammation relevant to metabolic processes associated with atherogenesis and cancer. The processes affected by LA derivatives include, alteration of airway smooth muscles and vascular wall, affecting sensitivity to pain, and regulating endogenous steroid hormones associated with metabolic syndrome. LA derivatives alter cell adhesion molecules, this initial step, is pivotal in regulating inflammatory processes involving transcription factor peroxisome proliferator-activated receptor pathways, thus, leading to alteration of metabolic processes. The derivatives are known to elicit pleiotropic effects that are either beneficial or detrimental in nature hence making it difficult to determine the exact role of these derivatives in the progress of an assumed target disorder. The key may lie in understanding the role of these derivatives at various stages of development of a disorder. Novel pharmacological approaches in altering the synthesis or introduction of synthesised LA derivatives could possibly help drive processes that could regulate inflammation in a beneficial manner. Chemical Compounds: Linoleic acid (PubChem CID: 5280450), 9- hydroxyoctadecadienoic acid (PubChem CID: 5312830), 13- hydroxyoctadecadienoic acid (PubChem CID: 6443013), 9-oxo-​octadecadienoic acid (PubChem CID: 3083831), 13-oxo-​octadecadienoic acid (PubChem CID: 4163990), 9,10-epoxy-12-octadecenoate (PubChem CID: 5283018), 12,13-epoxy-9-keto-10- trans -octadecenoic acid (PubChem CID: 53394018), Pioglitazone (PubChem CID: 4829).

Synthesis and structure of an intramolecularly coordinated diaryltelluronic acid and its dimethyl ester

The oxidation of the telluroxane cluster (8Me₂NC₁₀H₆Te)₆O₈(OH)₂ (4) or the diaryl ditelluride (8-Me₂NC₁₀H₆Te)(₂) (7) using H₂O₂ provided the diarylditelluronic acid [8-Me₂NC₁₀H₆Te(O)(OH)₂]₂(O) (6), which is the second member of this compound class and the first one to contain an intramolecularly coordinated substituent. Attempts at recrystallizing 6 from Methanol provided the partial ester [8-Me₂NC₁₀H₆Te(O)(OH)(OMe)]₂(O) (8). In addition structural motifs of known diaryltelluronic acids were compared using DFT calculations.

Characterisation of lipase fatty acid selectivity using novel omega-3 pNP-acyl esters

 Lipases have applications for the industrial processing of lipids, including concentrating and/or modifying fish oil derived omega-3 fatty acids, widely used as nutritional supplement and functional food ingredients. A range of para-nitrophenol (pNP) acyl esters were synthesised as a means to rapidly screen lipases for fatty acid selectivity using spectrophotometric detection. The chosen esters were based primarily on the most abundant fatty acids present in anchovy and tuna oils. pNP derivatives of C16:1 n-7, C18:1 n-9 (OA), C18:2 n-6 (LA), C18:3 n-3 (ALA), C20:5 n-3 (EPA) and C22:6 n-3 (DHA) were synthesised. Storage stability of these pNP derivatives was shown to be at least 6 months and all pNP derivatives, including those of EPA and DHA, were shown to be stable throughout the conditions of the assay. We applied the new assay substrates for the determination of fatty acid selectivity of five widely utilised lipases. Results showed that the lipase from Candida rugosa was the most selective in terms of omega-3 specificity, preferentially hydrolysing all other medium– long chain substrates. Lipases from Rhizomucor miehei and Thermomyces lanuginosa also showed selectivity, with a significant preference for saturated fatty acids. Candida Antarctica lipase B and Aspergillus niger lipase were the least selective.