Recent Advances in the Deoxydehydration of Vicinal Diols and Polyols

Deoxydehydration (DODH) is one of the most promising tools to reduce the oxygen content of biomass (sugars and polyols) and provide analogues of platform chemicals that are derived from fossil resources. This reaction converts a vicinal diol into an alkene and is typically catalyzed by high‐oxidation‐state metal‐oxo compounds in the presence of a stoichiometric reductant, with examples of both homogeneous and heterogeneous systems. This minireview will highlight the developments in this field over the past 5 years and focus on efforts to solve the problems that currently prevent DODH being performed on a commercial scale, including the nature of the reductant, substrate scope and selectivity, and catalyst recovery and expense.     

Molecular associations in acacia gums

The tendency of polysaccharides to associate in aqueous solution has long been recognised. Molecular associations can profoundly affect their performance in a given application due to its influence on the molecular weight, shape and size. This will ultimately determine how the molecules will interact with each other, with other molecules and with water. There are several factors, such as hydrogen bonding, hydrophobic association, ion mediated association, electrostatic interaction, concentration dependence and the presence of proteinaceous components, which affect this behaviour. Our objective is to highlight the role of the proteinaceous component, present in acacia gum, to promote associations when the gum is subjected to various processing treatments such as maturation, spray drying and irradiation. The results demonstrate the ability of the proteinaceous component to promote hydrophobic associations which influence the size and proportion of the arabinogalactan high molecular weight component (AGP). Heat treatment in solid state (maturation) increases the hydrophobic character of the gum and hence its emulsification performance. Spray drying also involves aggregation through hydrophobic association but changes the surface properties of peptide moieties to become more hydrophilic compared to the association promoted by the maturation treatment in the solid state. Irradiation induced cross-linking, in the presence of unsaturated gas, was used to introduce C–C bonds into the carbohydrate moiety and thus confirms the hydrophobic association prompted by the heat used in the maturation and spray drying. This association can be reversed by treatments, such as filtration or high pressure homogenisation. The results reported here reconcile the contradiction about structure of gum arabic proposed by the wattle-blossom and twisted hairy rope models and shows that the AGP fraction is basically an aggregated fraction made up of AG units stabilized by low molecular weight highly proteinaceous components.

Selective oxo functionalization of the uranyl ion with 3d metal cations

The linear uranyl dication [UO2]2+ can be bound in one of two coordination sites in the ditopic Pacman-shaped pyrrolic macrocyle H4L. Incorporation of Mn2+, Fe2+, or Co2+ cations in the second donor compartment affords the first uranyl complexes with a transition-metal-functionalized oxo group.     

Rapid discovery of potent siRNA-containing lipid nanoparticles enabled by controlled microfluidic formulation

The discovery of potent new materials for in vivo delivery of nucleic acids depends upon successful formulation of the active molecules into a dosage form suitable for the physiological environment. Because of the inefficiencies of current formulation methods, materials are usually first evaluated for in vitro delivery efficacy as simple ionic complexes with the nucleic acids (lipoplexes). The predictive value of such assays, however, has never been systematically studied. Here, for the first time, by developing a microfluidic method that allowed the rapid preparation of high-quality siRNA-containing lipid nanoparticles (LNPs) for a large number of materials, we have shown that gene silencing assays employing lipoplexes result in a high rate of false negatives (~90%) that can largely be avoided through formulation. Seven novel materials with in vivo gene silencing potencies of >90% at a dose of 1.0 mg/kg in mice were discovered. This method will facilitate the discovery of next-generation reagents for LNP-mediated nucleic acid delivery.     

Complexation of bovine serum albumin and sugar beet pectin: Stabilising oil-in-water emulsions

In a previous study (Langmuir 28 (2012) 10164-10176.), we investigated the complexation of bovine serum albumin (BSA) with sugar beet pectin (SBP). A pH-composition phase diagram was established and structural transitions in relation to the phase diagram during complexation were identified. The present study examines the implications of these interactions on the emulsifying performance of BSA/SBP mixtures. Middle-chain triglycerides (MCTs) in water emulsions were prepared using conditions corresponding to different regions of the phase diagram. At high pHs and in the stable region of mixed individual soluble polymers where complexation is absent, there is no improved emulsifying performance, compared with the individual protein and polysaccharide. For these mixtures, the emulsion characteristics are controlled by the major component in the solutions, as determined by the competitive adsorption of the two components at the oil-water interface. At low pHs and low BSA/SBP ratios, and so mainly within the stable region of intramolecular soluble complexes, BSA/SBP mixtures greatly improve the stability of emulsions. Here, stabilisation is controlled by the cooperative adsorption of the two components at the oil-water interface. Through electrostatic complexation BSA promotes the adsorption of SBP on to interfaces to form a thick steric layer around emulsion droplets and thus providing better stability. At low pHs and high BSA/SBP ratios, that is, mainly within the unstable region of intermolecular insoluble complexes, emulsions prepared are extremely unstable due to bridging flocculation between emulsion droplets.     

A simple and robust LC-MS/MS method for quantification of free 3-nitrotyrosine in human plasma from patients receiving on-pump CABG surgery

We have developed a simple, sensitive, and robust liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) method to determine free 3-nitrotyrosine concentrations in human plasma of patients receiving on-pump coronary artery bypass grafting surgery. A one-step solid-phase extraction protocol was optimized to enrich the analyte at low nanomolar concentrations. The processed samples were analyzed by LC-MS/MS with a 2.1 × 100 mm Kinetex PFP column and a triple quadrupole mass spectrometer. The method was validated for 3-nitrotyrosine concentrations close to real patient plasma levels. The relative standard deviations or relative errors of the intraday and interday determinations were all within 10%. Limit of detection and limit of quantitation were determined to be 0.034 nM and 0.112 nM, respectively, while lower limit of quantitation was below 0.625 nM. No deterioration of the column performance was noticed after running a large number of patient samples. The results showed that the 3-nitrotyrosine concentrations in coronary sinus plasma samples were elevated after cardiopulmonary bypass (CPB) procedure. The pre-CPB and post-CPB concentrations of 3-nitrotyrosine in patient plasmas were 1.494 ± 0.107 nM and 2.167 ± 0.177 nM (mean ± SEM), respectively. Application of this method to more patients in clinical studies may help validate 3-nitrotyrosine as a meaningful biomarker for nitrosative stress and link patient characteristics, clinical outcomes, and cardioprotective treatments to endogenous nitrosative stress levels.     

Terminal Location Problem: A Case Study Supporting the <Emphasis Type="Italic">Status Quo</Emphasis>

This paper applies a single-facility location model to the distribution network covered by the Brantford, Ontario branch of Thibodeau-Finch Transport Ltd. The model is used to determine whether or not the present terminal location should be maintained for the current demand structure and for a projected demand structure. Optimal locations are obtained for both demand structures using a distance function that is tailored to the actual road network over which the firm's vehicles travel. It is found that the transportation costs associated with the optimal locations are sufficiently close to those with the present location to conclude that Thibodeau-Finch should not consider relocation among its strategic options. The paper includes relevant data for verifying the conclusions drawn in support of the status quo.