Structural and Catalytic Studies of a Trimethyltin Vanadate Coordination Polymer

The organotin vanadate [Me₃SnVO₃] (1) has been prepared and characterised in the solid state by powder X-ray diffraction (XRD), thermogravimetric analysis, multinuclear magic-angle spinning (MAS) NMR, IR and Raman spectroscopy. The phase purity and structure of microcrystalline 1 were confirmed by carrying out a full Rietveld structural refinement at ambient temperature and from conventional powder XRD. ⁵¹V and ¹¹⁹Sn MAS NMR data for compound 1 were in agreement with the predicted structure, showing two equally-abundant, nonequivalent Me₃Sn groups and two equally-abundant, nonequivalent vanadium atoms. The compound was applied as a catalyst for the liquid-phase epoxidation of olefins at 55 °C using tert-butyl hydroperoxide (tBuOOH) as the oxidant. The reaction rate for the different substrates followed the order cis-cyclooctene > (R)-(+)-limonene ≅ trans-2-octene > cyclododecene > styrene > 1-octene; the corresponding epoxides were the only observed products. Leaching tests indicated that the catalytic epoxidation of cyclooctene was mainly heterogeneous in nature. This paper is dedicated to Professor Ian Manners and his scientific accomplishments.     

Combustion properties of Brazilian natural wood species

This paper investigates the combustion characteristics of 12 wood species natural to Brazil. A mass loss cone calorimeter was used to obtain the properties associated with (i) heat release rate (HRR), peak HRR, and total heat released; (ii) total mass loss and mass loss rate; (iii) average effective heat of combustion; and (iv) time to ignition, time of pyrolysis and temperature of ignition. The samples used in this work were as follows: (i) prepared in accordance to ISO 5660‐1:2002; (ii) oven dried; (iii) irradiated with a constant heat flux of 50 kW/m²; and (iv) exhibit wood fiber orientation in a plane orthogonal to the flux incidence. Finally, the paper explores the possibility of linking the obtained combustion properties with the density and classes of selected wood species. Copyright © 2014 John Wiley & Sons, Ltd.     

Biofilms of Listeria monocytogenes produced at 12 °C either in pure culture or in co-culture with Pseudomonas aeruginosa showed reduced susceptibility to sanitizers

The biofilm-forming ability of 21 Listeria monocytogenes isolates, previously pulsotyped and corresponding to 16 strains, from different origins was evaluated using the Calgary Biofilm Device, at 37 °C. Biofilms of 4 selected strains were also produced either on pure cultures or on co-cultures with Pseudomonas aeruginosa (PAO1), at 12 °C and at 37 °C. For these biofilms, the minimum biofilm eradication concentrations (MBECs) of 4 commercial dairy sanitizers (1 alkyl amine acetate based--T99, 2 chlorine based--T66 and DD, and 1 phosphoric acid based--BP) were determined. Listeria monocytogenes biofilms grown, either at 37 °C or 12 °C, were able to achieve similar cell densities by using different incubation periods (24 h and 7 d, respectively). In co-culture biofilms, P. aeruginosa was the dominant species, either at 37 °C or at 12 °C, representing 99% of a total biofilm population of 6 to 7 log CFU/peg. Co-culture biofilms were generally less susceptible than L. monocytogenes pure cultures. More interestingly, the biofilms produced at 12 °C were usually less susceptible to the sanitizers than when produced at 37 °C. Single or co-culture biofilms of L. monocytogenes and PAO1, particularly produced at 12 °C, retrieved MBEC values for agents T99 and BP that were, at times, above the maximum in-use recommended concentrations for these agents. The results presented here reinforce the importance of the temperature used for biofilm formation, when susceptibility to sanitizers is being assessed. PRACTICAL APPLICATION: Since most food plants have cold wet growth niches in production and storage areas, susceptibility testing should be performed on biofilms produced at refrigeration temperatures. Moreover, the efficiency of the sanitizers used in food industries should be performed on mixed culture biofilms, since in field conditions these will predominate. The results presented here highlight the importance of the temperature used for biofilm formation, when susceptibility to disinfectants is being assessed, as biofilms produced at lower temperature were less susceptible to sanitizers.     

Graphene for tough and electroconductive alumina ceramics

A simple, fast and upscalable method is described to produce graphene/alumina (G/Al₂O₃) composites by spark plasma sintering (SPS) with a significant improvement on both mechanical and electrical properties of monolithic Al₂O₃. Graphene oxide (GO) was mixed with Al₂O₃ using a colloidal method obtaining an excellent dispersion of GO in the alumina matrix. The material was consolidated by SPS that allowed, in one-step, the in situ reduction of the GO during the sintering process. A detailed Raman analysis was found to be very useful to study the orientation of the graphene in the composite and to evaluate and optimise its thermal reduction. Graphene platelets acted as elastic bridges avoiding crack propagation and providing this material with a crack bridging reinforcement mechanism. A very low graphene loading (0.22 wt%) led to a 50% improvement on the mechanical properties of the alumina and to an increase of the electrical conductivity up to eight orders of magnitude.     

Influence of drying conditions on the gelling properties of the 7S and 11S soy protein fractions

Soy protein fractions rich in β-conglycinin (7S) or glycinin (11S) were freeze dried or spray dried at temperatures of 120, 150 or 180 °C. The fractions were characterized for their particle size distribution, sorption isotherms and by scanning differential calorimetry. The gelling capacity of the protein fractions was studied at pH values of 3 and 7 using oscillatory measurements, mechanical properties and water holding capacity. The rheological measurements showed that viscous modulus (G″) predominated at low temperatures and the elastic modulus (G′) at high temperatures. At pH 3, the G′–G″ crossover occurred at lower temperatures when compared to pH 7. This behaviour was more accentuated for the 11S fractions due to its capacity to form stronger gels. An increase of drying temperature led to a displacement of the gel point to higher temperatures and decreased the elasticity modulus or gelling capacity of protein fractions. These results were confirmed by the mechanical properties, since at higher temperatures the gels were more fragile and brittle, especially when formed at pH 7.     

Investigation of cure kinetics in epoxy/multiwalled carbon nanotube nanocomposites

With the increased interest in thermoset resin nanocomposites, it is important to understand the effects of the material on nanoscale characteristics. In this study, a curing reaction of an epoxy resin, which contained 0.25, 0.50, or 1.00 wt % of multiwalled carbon nanotubes (MWCNTs), at different heating rates was monitored by differential scanning calorimetry; cure kinetics were also evaluated to establish a relationship between crosslinking (network formation) and mechanical properties. MWCNT concentrations above 0.25 wt % favored crosslinking formation and decreased the activation energy (E_a) in the curing reaction. Examination of the kinetic mechanism suggests that the MWCNT locally restricted the spatial volume and favored the formation of nodular morphology in the resin, especially for high MWCNT concentrations. The MWCNT exhibited some entanglement in the matrix, which hindered a more pronounced effect on the mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39857.     

Synthesis of Benzophenones and in vitro Evaluation of Their Anticancer Potential in Breast and Prostate Cancer Cells

Breast and prostate cancers are frequently treated with chemotherapy. Several novel chemicals are being reported for this purpose, particularly synthetic and natural benzophenones. This work reports the synthesis of substituted 2-hydroxybenzophenones through 1,4-conjugate addition/intramolecular cycloaddition/dehydration of nitromethane on key intermediate chromones. Structures were extensively studied by means of 2D NMR spectroscopy and single-crystal XRD. Their cytotoxicity was evaluated in vitro in two breast cancer cell lines (MDA-MB-231 and T47-D) and one prostate cancer cell line (PC3). The most potent compound exhibited good cytotoxic effects against the three cancer cell lines (IC₅₀ values ranging from 12.09 to 26.49 μm ) and induced cell-cycle retardation only on prostate cancer cells, which suggested that it might exert cell-type-specific effects.