High-Thermal-Conductivity Aluminum Nitride Ceramics: The Effect of Thermodynamic, Kinetic, and Microstructural Factors

Improvement in the thermal conductivity of aluminum nitride (AlN) can be realized by additives that have a high thermodynamic affinity toward alumina (Al₂O₃), as is clearly demonstrated in the aluminum nitride-yttria (AlN-Y₂O₃) system. A wide variety of lanthanide dopants are compared at equimolar lanthanide oxide:alumina (Ln₂O₃: Al₂O₃, where Ln is a lanthanide element) ratios, with samaria (Sm₂O₃) and lutetia (Lu₂O₃) being the dopants that give the highest- and lowest-thermal-conductivity AlN composites, respectively. The choice of the sintering aid and the dopant level is much more important than the microstructure that evolves during sintering. A contiguous AlN phase provides rapid heat conduction paths, even at short sintering times. AlN contiguity decreases slightly as the annealing times increase in the range of 1–1000 min at 1850°C. However, a substantial increase in thermal conductivity results, because of purification of AlN grains by dissolution-reprecipitation and bulk diffusion. Removal of grain-boundary phases, with a concurrent increase in AlN contiguity, occurs at high annealing temperatures or at long times and is a natural consequence of high dihedral angles (poor wetting) in liquidphase-sintered AlN ceramics.     

Epoxidized linolenic acid salts as multifunctional additives for the thermal stability of plasticized PVC

Calcium and zinc salts of epoxidized linolenic acid were synthesized and used as multifunctional additives, to minimize or prevent the reaction of epoxidized soybean oil (ESO) with liberated hydrochloric acid (HCl) during the thermal degradation of poly(vinyl chloride) (PVC) in particular. These metal epoxy salts were incorporated as thermal stabilizers for both diisodecyl phthalate and ESO–plasticized PVC blends that underwent thermal degradation studies at 170°C. The overall performance of these metal epoxy salts was examined by thermal gravimetric analysis and visual color retention of the PVC blends. The weight loss profiles of the metal salt stabilized PVC were comparable to those of blends containing metal stearates. There were, however, vast improvements in color retention of the plasticized PVC using these novel additives. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41736.     

Optimization of Mixing and Mass Transfer in In-line Multi-Jet Ozone Contactors Using Computational Fluid Dynamics

Typical ozone mixing and mass transfer calculations are lumped approaches based on ideal operating conditions and can misrepresent behavior in real-life installations. This article models the effect of local hydrodynamics and mixing on the overall mass transfer of ozone into water with the aid of multiphase computational fluid dynamics (CFD). CFD models were validated with measured data from a pipeline ozone contactor installation which was optimized for more rapid, uniform mixing and mass transfer. Results emphasize the sensitivity of mixing quality to nozzle placement, size, orientation and spacing relative to main pipeline diameter and flows.     

Recovery of polyphenols from camu-camu (Myrciaria dubia H.B.K. McVaugh) depulping residue by cloud point extraction

In this study the potential of cloud point extraction formed by a non-ionic surfactant was used in order to separate polyphenols from industrial residues of camu-camu. The effects of operational conditions of the cloud point extraction (CPE) on the polyphenol recovery and volumetric ratio were investigated. The results showed a maximum recovery of 95.71% that was obtained using 7.0 wt% Triton X-114, native pH (3.25), and 80 wt% polyphenol extract at 30 °C. The use of cloud point extraction was successful to recover the polyphenols from agroindustrial residue since it is a simple as well as of low-cost technique.     

Combined spectroscopic/computational studies on Fe- and Mn-dependent superoxide dismutases: insights into second-sphere tuning of active site properties

Superoxide dismutases (SODs) are metalloenzymes that protect aerobic organisms from oxidative damage mediated by the superoxide radical. While the Fe- and Mn-dependent SODs from E. coli possess virtually identical protein folds and active-site geometries, they are strictly metal specific. To explore the origin of this extraordinary metal-ion specificity and to elucidate the mechanisms by which these enzymes tune the geometric and electronic properties, and thus the reactivity, of their active-site metal ions, we utilized a combination of spectroscopic and computational methods to study the native enzymes, their metal-substituted derivatives, and several mutant proteins. Results from our research described in this Account reveal that second-sphere residues are critically involved in controlling both thermodynamic and kinetic properties of the Fe- and MnSOD active sites.     

Synthesis and evaluation of 1-amino-6-halo-β-carbolines as antimalarial and antiprion agents

Malaria is one of the world's most devastating parasitic diseases, causing almost one million deaths each year. Growing resistance to classical antimalarial drugs, such as chloroquine, necessitates the discovery of new therapeutic agents for successful control of this global disease. Here, we report the synthesis of some 6-halo-β-carbolines as analogues of the potent antimalarial natural product, manzamine A, retaining its heteroaromatic core whilst providing compounds with much improved synthetic accessibility. Two compounds displayed superior activity to chloroquine itself against a resistant Plasmodium falciparum strain, identifying them as promising leads for future development. Furthermore, in line with previous reports of similarities in antimalarial and antiprion effects of aminoaryl-based antimalarial agents, the 1-amino-β-carboline libraries were also found to possess significant bioactivity against a prion-infected cell line.     

Synthesis and Evaluation of the Anticancer and Trypanocidal Activities of Boronic Tyrphostins

Molecules containing an (cyanovinyl)arene moiety are known as tyrphostins because of their ability to inhibit proteins from the tyrosine kinase family, an interesting target for the development of anticancer and trypanocidal drugs. In the present work, (E)‐(cyanovinyl)benzeneboronic acids were synthesized by Knoevenagel condensations without the use of any catalysts in water through a simple protocol that completely avoided the use of organic solvents in the synthesis and workup process. The in vitro anticancer and trypanocidal activities of the synthesized boronic acids were also evaluated, and it was discovered that the introduction of the boronic acid functionality improved the activity of the boronic tyrphostins. In silico target fishing with the use of a chemogenomic approach suggested that tyrosine‐phosphorylation‐regulated kinase 1a (DYRK1A) was a potential target for some of the designed compounds.     

The Acrylation of Glycerol: A Precursor to Functionalized Lipids

With the objective of expanding the number of functionalized lipids available, the reactive vinyl group of acrylic acid was introduced to triacylglycerol by esterification of glycerol. Didecanoylacryloylglycerol was synthesized from decanoic and acrylic acids and glycerol using K₂O as catalyst. 2 g (21.7 mmol) glycerol, 11.3 g (65.4 mmol) decanoic acid, 6.2 g (86.1 mmol) acrylic acid, 60 ml hexane, and 400 mg K₂O were added to 300-ml closed stainless steel reactor and maintained at 200 °C for 5 h. The resulting product, designated DDA, was isolated at about 40% yield based on the acylglycerol products. The other products included tridecanoylglycerol, diacryloyldecanoylglycerol, and the diacylglycerols of these acids. DDA was then converted to functionalized lipids by the Michael addition and Heck reaction. The Michael addition of thiophenol and 4-bromothiophenol yielded the corresponding linear thioethers whereas and Heck reaction products from bromobenzene and bromoanisole yielded triacylglycerols containing trans-cinnamic acid and trans-(4-methoxy)cinnamic acid, respectively.