Unlocking Potentially Therapeutic Phytochemicals in Capadulla () from Guyana Using Untargeted Mass Spectrometry-Based Metabolomics.

is thought to have a wide variety of therapeutic phytochemicals that allegedly improve libido and cure impotence. Although a few biomarkers have been identified with potential antinociceptive and cytotoxic properties, an untargeted mass spectrometry-based metabolomics approach has never been undertaken to identify therapeutic biofingerprints for conditions, such as erectile dysfunction, in men. This study executes a preliminary phytochemical screening of the woody vine of two ecotypes of with renowned differences in therapeutic potential for erectile dysfunction.

Antimicrobial Activity of Amphiphilic Triazole-Linked Polymers Derived from Renewable Sources.

Conventional engineered polymers are strong, stable, and can interact desirably within the human body in implants and medical devices. However, bacterial colonization of medical devices and implants constructed from these materials results in numerous hospital acquired infections (HAI) and deaths each year. Polytriazole based plastics containing triazole rings and fatty acid derivatives have been synthesized from biological sources without catalysts or solvents.

Vegetable oil derived solvent, and catalyst free "click chemistry" thermoplastic polytriazoles.

Azide-alkyne Huisgen "click" chemistry provides new synthetic routes for making thermoplastic polytriazole polymers-without solvent or catalyst. This method was used to polymerize three diester dialkyne monomers with a lipid derived 18 carbon diazide to produce a series of polymers (labelled C18C18, C18C9, and C18C4 based on monomer chain lengths) free of residual solvent and catalyst. Three diester dialkyne monomers were synthesized with ester chain lengths of 4, 9, and 18 carbons from renewable sources.

Influence of structure on chemical and thermal stability of aliphatic diesters.

Ester group interactions with each other and with the atoms between them were investigated in order to determine dependence of chemical and thermal stabilities of aliphatic diesters on structure. Novel glycol-derived diesters with chemical formula (C17H33COO)2C(n)H(2n) were used as model systems. Chemical stability was determined using (1)H NMR and FTIR, and thermal stability and weight-loss kinetics were examined using nonisothermal TGA.

Relationships between molecular structure and kinetic and thermodynamic controls in lipid systems. Part I: propensity for oil loss of saturated triacylglycerols.

Pure saturated triacylglycerols (TAGs) in canola oil were used as model systems to analyse oil loss in structured oil both from thermodynamic and kinetic perspectives. Two important parameters which effectively and predictively measure the relative propensity of a solid network to lose/hold oil were defined: (1) the rate of oil loss, K, which is a quantified representation of the kinetics of oil loss and (2) the initial amount of oil susceptible to be lost, i.e.

Relationships between molecular structure and kinetic and thermodynamic controls in lipid systems. Part III. Crystallization and phase behavior of 1-palmitoyl-2,3-stearoyl-sn-glycerol (PSS) and tristearoylglycerol (SSS) binary system.

The phase behavior of 1-palmitoyl-2,3-distearoyl-sn-glycerol (PSS)/tristearoylglycerol (SSS) binary system was investigated in terms of polymorphism, crystallization and melting behavior, microstructure and solid fat content (SFC) using widely different constant cooling rates. Kinetic phase diagrams were experimentally determined from the DSC heating thermograms and analyzed using a thermodynamic model to account for non-ideality of mixing. The kinetic phase diagram presented a typical eutectic behavior with a eutectic point at the 0.

Relationships between molecular structure and kinetic and thermodynamic controls in lipid systems. Part II: Phase behavior and transformation paths of SSS, PSS and PPS saturated triacylglycerols--effect of chain length mismatch.

The kinetic phase behavior and phase transformation paths of purified tristearoylglycerol (SSS), 3-palmitoyl-1,2-distearoyl-sn-glycerol (PSS) and 1,2-dipalmitoyl-3-stearoyl-sn-glycerol (PPS) were investigated in terms of polymorphism, crystallization and melting. The details of the phase transformation paths were obtained using the heating cycles of two sets of experiments: (a) cooling rate was varied and heating rate fixed and (b) cooling rate was fixed and heating rate varied. Kinetic effects were manifest in all measured properties, underscoring the complexity of the phase transformation paths for each TAG, and the intricate thermodynamics-molecular relationships.

Lubricating and waxy esters, I. Synthesis, crystallization, and melt behavior of linear monoesters.

Four pure jojoba wax-like esters (JLEs), having carbon chain length of 36, 40 (two isomers) and 44, were prepared by Steglish esterification of fatty acids (or acid chlorides) with fatty alcohols at room temperature. Calorimetric and diffraction data was used to elucidate the phase behavior of the esters. The primary thermal parameters (crystallization and melting temperatures) obtained from the DSC of the symmetrical molecules correspond well with the carbon numbers of the JLEs.

A facile synthesis of lipid stabilized gold nanoparticles: a step towards biodegradable biosensors.

A new class of polylactone was successfully synthesized and utilized for the encapsulation and stabilization of gold nanoparticles. Core/shell nanoparticle architecture, in which a layer of this polymer surrounds the nanoparticle core have been investigated both as a means to improve the stability and surface chemistry and as a way of accessing unique physical properties that are not possible from one nano-material alone. Given the fact that only few systems has so far been developed for the encapsulation of nanoparticles, our success in using a new biodegradable biopolymer with inbuilt functionality reveals the robustness of this work.

Quantification of oil binding capacity of structuring fats: A novel method and its application.

A robust, well-defined and reproducible method to accurately measure the oil binding capacity (OBC) of structuring fats was developed. The method was validated using two oil/fat model systems, i.e.

The binary phase behavior of 1,3-dilauroyl-2-stearoyl-sn-glycerol and 1,2-dilauroyl-3-stearoyl-sn-glycerol.

The binary phase behavior of purified 1,3-dilauroyl-2-stearoyl-sn-glycerol (LSL) and 1,2-dilauroyl-3-stearoyl-sn-glycerol (LLS) was investigated at a slow (0.1 degrees C/min) and a relatively fast (3.0 degrees C/min) cooling rate in terms of melting and crystallization, polymorphism, solid fat content (SFC), hardness and microstructure.

Functional thermoplastics from linear diols and diisocyanates produced entirely from renewable lipid sources.

An unsaturated terminal diol, 1,18-octadec-9-endiol (ODEDO), and a saturated terminal diol, 1,9-nonanediol (NDO), were synthesized from oleic acid. The feasibility of utilizing these new diols for the production of thermoplastic polyurethanes (TPUs) was demonstrated by reacting them with a fatty acid-derived diisocyanate, 1,7-heptamethylene diisocyanate (HPMDI), and a commercially available petroleum-derived diisocyanate, 1,6-hexamethylene diisocyanate (HDI). One type of phase structure was obtained for both TPUs in this study, owing to the similarity between the ODEDO and NDO molecular structure.

Self-assembled nanostructures of oleic acid and their capacity for encapsulation and controlled delivery of nutrients.

A simple preparation method for a nutrient delivery system is presented using nanostructures of oleic acid embedded in canola oil by a two step synthesis procedure. Oleic acid nanostructures in the form of micelles and vesicles were initially prepared and their ability to encapsulate vitamin-C, used as a model nutrient, was evaluated. Dynamic Light Scattering (DLS) analysis and Transmission Electron Microscopy (TEM) confirmed the formation of micelles and vesicles with diameters of 150 nm and 540 nm respectively.

Evidence of critical cooling rates in the nonisothermal crystallization of triacylglycerols: a case for the existence and selection of growth modes of a lipid crystal network.

The isoconversional method, a model-free analysis of the kinetics of liquid-solid transformations, was used to determine the effective activation energy of the nonisothermal crystallization of melts of pure and complex systems of triacylglycerols (TAGs). The method was applied to data from differential scanning calorimetry (DSC) measurements of the heat of crystallization of purified 1,3-dilauroyl-2-stearoyl-sn-glycerol (LSL) and commercially available cocoa butter melts. The method conclusively demonstrated the existence of specific growth modes and critical rates of cooling at specific degrees of conversion.

Fatty acid-derived diisocyanate and biobased polyurethane produced from vegetable oil: synthesis, polymerization, and characterization.

A new linear saturated terminal diisocyanate was synthesized from oleic acid via Curtius rearrangement, and its chemical structure was identified by FTIR, (1)H and (13)C NMR, and MS. The feasibility of utilizing this new diisocyanate for the production of polyurethanes (PUs) was demonstrated by reacting it with commercial petroleum-derived polyols and canola oil-derived polyols, respectively. The physical properties of the PUs prepared from fatty acid-derived diisocyanate were compared to those prepared from the same polyols with a similar but petroleum-derived commercially available diisocyanate: 1,6-hexamethylene diisocyanate.

The binary phase behavior of 1,3-dicaproyl-2-stearoyl-sn-glycerol and 1,2-dicaproyl-3-stearoyl-sn-glycerol.

The phase behavior of a binary system constituted of purified 1,3-dicaproyl-2-stearoyl-sn-glycerol (CSC) and 1,2-dicaproyl-3-stearoyl-sn-glycerol (CCS) was investigated at a very slow (0.1 degrees C/min) and a relatively fast (3.0 degrees C/min) cooling rate using differential scanning calorimetry (DSC), low resolution NMR, X-ray diffraction (XRD), and polarized light microscopy (PLM).

Synthesis and characterization of highly functionalized symmetric aromatic hexa-ol intermediates from oleic acid.

A novel highly functionalized aromatic hexa-ol was synthesized by palladium-catalyzed cyclotrimerization of an alkyne fatty acid ester followed by LAH reduction. This polyol product is a novel monomer made from a renewable lipid raw material for the production of polyurethanes, polyesters and polyamides.

Sequential interpenetrating polymer networks produced from vegetable oil based polyurethane and poly(methyl methacrylate).

Sequential interpenetrating polymer networks (IPNs) were prepared using polyurethane produced from a canola oil based polyol with primary terminal functional groups and poly(methyl methacrylate) (PMMA). The properties of the material were studied and compared to the IPNs made from commercial castor oil using dynamic mechanical analysis, differential scanning calorimetry, as well as tensile measurements. The morphology of the IPNs was investigated using scanning electron microscopy and transmission electron microscopy.

Physical properties of sequential interpenetrating polymer networks produced from canola oil-based polyurethane and poly(methyl methacrylate).

Sequential interpenetrating polymer networks (IPNs) were prepared using polyurethane (PUR) synthesized from canola oil-based polyol with terminal primary functional groups and poly(methyl methacrylate) (PMMA). The properties of the material were evaluated by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and modulated differential scanning calorimetry (MDSC), as well as tensile properties measurements. The morphology of the IPNs was investigated using scanning electron microscopy (SEM) and MDSC.

Synthesis of aromatic triols and triacids from oleic and erucic acid: separation and characterization of the asymmetric and symmetric isomers.

Hexasubstituted benzene derivatives, aromatic triols 4, 9 and triacids 5, 10 have been synthesized from oleic and erucic acid derivatives followed by a cyclotrimerization step catalyzed by palladium-on-carbon (Pd/C) and chlorotrimethylsilane (TMSCl). The asymmetric isomer, which is the main product, was isolated from its symmetric isomer by flash chromatography. All the products were fully characterized by IR, (1)H NMR, (13)C NMR and mass spectrometry.

Crystallization and phase behavior of fatty acid esters of 1,3 propanediol III: 1,3 propanediol dicaprylate/1,3 propanediol distearate (CC/SS) and 1,3 propanediol dicaprylate/1,3 propanediol dipalmitate (CC/PP) binary systems.

The phase behavior of the 1,3 propanediol dicaprylate/1,3 propanediol distearate (CC/SS) and the 1,3 propanediol dicaprylate/1,3 propanediol dipalmitate (CC/PP) binary systems were investigated using different techniques. The two systems presented essentially the same overall features. XRD measurements detected CC-CC, PP-PP and SS-SS bilayers which crystallized in beta forms but no mixed bilayers for all mixtures.

Physical properties of canola oil based polyurethane networks.

A new generation polyol (generation-II) with significantly higher triol content and higher hydroxyl value was synthesized from canola oil by introducing a mild solvent (ethyl acetate) and a more efficient reductive reagent (zinc) to the previous synthetic procedure (Narine, S. S.; Yue, J.

Crystallization and phase behavior of 1,3-propanediol esters II. 1,3-propanediol distearate/1,3-propanediol dipalmitate (SS/PP) and 1,3-propanediol distearate/1,3-propanediol dimyristate (SS/MM) binary systems.

Polymorphic influences on the phase behavior of two types of binary mixtures of saturated monoacid 1,3-propanediol esters (PADEs), dipalmitate/distearate (PP/SS) and dimyristate/distearate (MM/SS) were examined by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and by solid fat content (SFC), hardness and microscopy measurements. Three stacking modes have been found in the PP/SS binary system. Mixed SS-PP bilayers were detected in all mixtures, SS-SS bilayers in x(PP)=0.

Crystallization and phase behavior of fatty acid esters of 1,3-propanediol I: pure systems.

Six pure fatty acid esters of 1,3-propanediol (PADE) molecules were investigated. A careful analysis of XRD, DSC as well as SFC results has allowed the determination of their structure and phase behavior. Two beta polymorphs were observed for C10-C18 and three beta polymorphs for C8.

Physical properties of polyurethane plastic sheets produced from polyols from canola oil.

Polyurethane (PUR) plastic sheets were prepared by reacting polyols synthesized from canola oil with aromatic diphenylmethane diisocyanate. The properties of the material were measured by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) as well as tensile properties measurements. The effect of stoichiometric balance (i.