Synthetic and Biological Studies of Sesquiterpene Polygodial: Activity of 9‐Epipolygodial against Drug‐Resistant Cancer Cells

Polygodial, a terpenoid dialdehyde isolated from Polygonum hydropiper L., is a known agonist of the transient receptor potential vanilloid 1 (TRPV1). In this investigation a series of polygodial analogues were prepared and investigated for TRPV1‐agonist and anticancer activities. These experiments led to the identification of 9‐epipolygodial, which has antiproliferative potency significantly exceeding that of polygodial. 9‐Epipolygodial was found to maintain potency against apoptosis‐resistant cancer cells as well as those displaying the multidrug‐resistant (MDR) phenotype. In addition, the chemical feasibility for the previously proposed mechanism of action of polygodial, involving the formation of a Paal–Knorr pyrrole with a lysine residue on the target protein, was demonstrated by the synthesis of a stable polygodial pyrrole derivative. These studies reveal rich chemical and biological properties associated with polygodial and its direct derivatives. These compounds should inspire further work in this area aimed at the development of new pharmacological agents, or the exploration of novel mechanisms of covalent modification of biological molecules with natural products.     

Strain‐induced deformation mechanisms of polylactide plasticized with acrylated poly(ethylene glycol) obtained by reactive extrusion

This work aimed at identifying the tensile deformation mechanisms of an original grade of plasticized polylactide (pPLA) obtained by reactive extrusion. This material had a glass transition temperature of 32.6 °C and consisted of a polylactide (PLA) matrix grafted with poly(acryl‐poly(ethylene glycol)) (poly(Acryl‐PEG)) inclusions. pPLA behaved like a rubber‐toughened amorphous polymer at 20 °C, and its tensile behavior evolved toward a rubbery semicrystalline polymer with increasing temperature. The drawing of pPLA involved orientation of amorphous and crystalline chains, crystallization, and destruction of crystals. It was found that crystal formation and crystal destruction were in competition below 50 °C, resulting in a constant or slightly decreasing crystallinity with strain. Increasing temperature enhanced crystal formation and limited crystal destruction, resulting in an increased crystallinity with the strain level. Drawing yielded a transformation of the initial spherical poly(Acryl‐PEG) inclusions into ellipsoids oriented in the tensile direction. This mechanism may engender the formation of nanovoids within the inclusions due to a decreased density, assumed to be responsible for the whitening of the specimen. © 2015 Society of Chemical Industry     

Synthesis of economically viable biodiesel from waste frying oils (WFO)

In present communication, waste frying oil (WFO) has been used as a feedstock for biodiesel synthesis. WFO, procured from a local Indian restaurant possessed an acid value of 0.84 mg KOH/g, which is low enough for single step transesterification reaction. Biodiesel (fatty acid methyl esters) was washed after transesterification reaction and the yield got lowered substantially (from 96% to 86.36%) after water washing owing to loss of esters. 30:100 vol% (methanol to oil), 0.6 wt% NaOCH₃, 60°C temperature and 600 rpm agitation in 1 h reaction time was found to be optimum for transesterification reaction. ¹H NMR spectrum showed a high conversion (95.19%) of fatty acids in WFO to biodiesel in 2 h reaction time. Almost complete conversion (99.68%) was attained in 2 h reaction time. © 2011 Canadian Society for Chemical Engineering     

Synthesis and characterizations of poly(ethylene-co-vinylalcohol)-grafted-poly(3-hydroxybutyrate-co-hydroxyvalerate) copolymers

Poly(ethylene-co-vinylalcohol)-grafted-poly(3-hydroxybutyrate-co-hydroxyvalerate) (EVOH-g-PHBV) was prepared by a catalyzed grafting of PHBV onto immiscible EVOH. These reactions were performed at high temperature in the molten state. The choices of Tin(II) bis(2-ethylhexanoate) (Sn(Oct)₂) and 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), as catalyst, were justified by a first study in an internal mixer. The catalyst quantity, reaction temperature and reaction time were optimized to apply them in the conditions of a reactive extrusion process with a co-rotating twin screw extruder. High reaction temperature, from 180 °C to 220 °C, associated to intensive mixing led to efficient grafting of PHBV onto EVOH, compatible with short residence times required.Rheological, thermal and morphological analyses were conducted to characterize the obtained copolymers. Molecular weights were determined by SEC. SEM imaging were made on cryo-fractured surfaces of blends extruded with and without catalyst. In most of reaction conditions, a compatible blend was obtained with a fine micro phase separation. Grafted copolymers were only obtained when well defined and controlled conditions are applied.     

Mechanical reinforcement of a high-performance aluminium alloy AA5083 with homogeneously dispersed multi-walled carbon nanotubes

Dense and homogeneous multi-walled carbon nanotube/metal composites are prepared by powder metallurgy. The distribution of the nano-reinforcements in the matrix is studied by scanning electron microscopy and Raman spectroscopy. The mechanical properties of the composites are determined by means of static tensile tests and Vickers micro-hardness measurements. We show that a homogeneous dispersion of the nanotubes at the micron scale is required in order to improve the mechanical properties of the metal matrix composite. This can be achieved using ball-milling through the mechanisms of plastic deformation and cold-welding. Accordingly, we report significant improvements to the mechanical properties of composites prepared with a high-performance aluminium alloy AA5083 matrix.     

Water retention and gas relative permeability of two industrial concretes

This experimental study aims at identifying the water retention properties of two industrial concretes to be used for long term underground nuclear waste storage structures. Together with water retention, gas transfer properties are identified at varying water saturation level, i.e. relative gas permeability is assessed directly as a function of water saturation level S_w. The influence of the initial de-sorption path and of the subsequent re-saturation are analysed both in terms of water retention and gas transfer properties. Also, the influence of concrete microstructure upon water retention and relative gas permeability is assessed, using porosity measurements, analysis of the BET theory from water retention properties, and MIP. Finally, a single relative gas permeability curve is proposed for each concrete, based on Van Genuchten–Mualem's statistical model, to be used for continuous modelling approaches of concrete structures, both during drying and imbibition.     

8-oxoguanine DNA glycosylases: one lesion, three subfamilies

Amongst the four bases that form DNA, guanine is the most susceptible to oxidation, and its oxidation product, 7,8-dihydro-8-oxoguanine (8-oxoG) is the most prevalent base lesion found in DNA. Fortunately, throughout evolution cells have developed repair mechanisms, such as the 8-oxoguanine DNA glycosylases (OGG), which recognize and excise 8-oxoG from DNA thereby preventing the accumulation of deleterious mutations. OGG are divided into three subfamilies, OGG1, OGG2 and AGOG, which are all involved in the base excision repair (BER) pathway. The published structures of OGG1 and AGOG, as well as the recent availability of OGG2 structures in both apo- and liganded forms, provide an excellent opportunity to compare the structural and functional properties of the three OGG subfamilies. Among the observed differences, the three-dimensional fold varies considerably between OGG1 and OGG2 members, as the latter lack the A-domain involved in 8-oxoG binding. In addition, all three OGG subfamilies bind 8-oxoG in a different manner even though the crucial interaction between the enzyme and the protonated N7 of 8-oxoG is conserved. Finally, the three OGG subfamilies differ with respect to DNA binding properties, helix-hairpin-helix motifs, and specificity for the opposite base.     

Malachite green derivatives for two-photon RNA detection

The design, preparation and characterisation of a library of malachite green (MG) derivatives for two-photon RNA labelling is described. Some of these MG derivatives exhibit an increased affinity for an MG-aptamer, as well as improved two-photon sensitivity when compared to the classical malachite green chloride. The underlying mechanisms and potential benefits for in vivo RNA visualisation are discussed.     

Modelling of solid formation by heterogeneous reactions through a multicomponent transport model of diluted ionic species: Simulation of barite fouling in a geothermal heat exchanger

A general model is proposed in order to describe the growth of a deposit by heterogeneous reactions. The hydrodynamics in the fluid is described by a multicomponent transport model for ionic species diluted in a solvent and heat transfer is taken into account in both liquid and solid domains. The boundary condition at the interface where the reaction takes place is described thoroughly. It involves the reaction kinetics and gives access to the velocity of the interface, ie, the mass rate of the solid deposit. The model is then applied to the case of barite crystallization in a heat exchanger. The liquid phase is therefore composed of two ionic species Ba²⁺ and SO₄²⁻ diluted in water. The solid phase is modelled as a homogeneous barite deposit. The fully dynamic CFD simulation of the model is made using Comsol Multiphysics, in a cylindrical pipe. The solid growth is analyzed over time and space in terms of the relevant variables of the model.     

Interlaboratory study on lipid oxidation during accelerated storage trials with rapeseed and sunflower oil analyzed by conjugated dienes as primary oxidation products

Accelerated storage tests are frequently used to assess the oxidative stability of foods and related systems due to its reproducibility. Various methods and experimental conditions are used to measure lipid oxidation. Differences between laboratories make it necessary to determine the repeatability and reproducibility of oxidation tests performed under the same conditions. The objective of the present interlaboratory study was to evaluate the outcome of a storage test for two different bulk oils, sunflower oil (SFO) and rapeseed oil (RSO), during a period of 9 weeks at 20°C, 30°C, 40°C, and 60°C. Sixteen laboratories were provided with bottled oils and conducted the storage tests according to a detailed protocol. Lipid oxidation was monitored by the formation of conjugated dienes (CD) and the activation energy (E_a) was determined for comparative purposes and statistically evaluated. An increase in CD formation was observed for both oils when the storage temperature was increased in all laboratories. The E_a,1 ranged from 47.9 to 73.3 kJ mol⁻¹ in RSO and from 27.8 to 62.6 kJ mol⁻¹ in SFO, with average values of 58.2 and 46.8 kJ mol⁻¹, respectively. The reproducibility coefficients were 10.9% and 18.2% for RSO and SFO, respectively. Practical applications: In order to compare results on oxidative stability of foods derived from different studies, the reproducibility of storage tests and methods employed to evaluate the oxidation level should be considered. This study provides fundamental data on the reproducibility of lipid oxidation under accelerated storage conditions and defines important parameters to be considered for the conduction of experiments.