Kinetic Study of Radical Polymerization VIII. A Comprehensive Study of Solution Copolymerization of Vinyl Acetate and Methyl Acrylate by 1H‐NMR Spectroscopy

Radical copolymerization reaction of vinyl acetate (VA) and methyl acrylate (MA) was performed in a solution of benzene‐d₆ using benzoyl peroxide (BPO) as the initiator at 60°C. Kinetic studies of this copolymerization reaction were investigated by on‐line ¹H‐NMR spectroscopy. Individual monomer conversions vs. reaction time, which was followed by this technique, were used to calculate the overall monomer conversion, as well as the monomer mixture and the copolymer compositions as a function of time. Monomer reactivity ratios were calculated by various linear and nonlinear terminal models and also by simplified penultimate model with r _2(VA)=0 at low and medium/high conversions. Overall rate coefficient of copolymerization was calculated from the overall monomer conversion vs. time data and k _p  . k _t ^?0.5 was then estimated. It was observed that k _p  . k _t ^?0.5 increases with increasing the mole fraction of MA in the initial feed, indicating the increase in the polymerization rate with increasing MA concentration in the initial monomer mixture. The effect of mole fraction of MA in the initial monomer mixture on the drifts in the monomer mixture and copolymer compositions with reaction progress was also evaluated experimentally and theoretically.     

Synthesis of mesoporous functional hematite nanofibrous photoanodes by electrospinning

Iron(III) oxide (hematite, Fe₂O₃) nanofibers, as visible light‐induced photoanode for water oxidation reaction of a water splitting process, were fabricated through electrospinning method followed by calcination treatment. The prepared samples were characterized with scanning electron microscopy, and three‐electrode galvanostat/potentiostat for evaluating their photoelectrochemical (PEC) properties. The diameter of the as‐spun fibers is about 300 nm, and calcinated fibers have diameter less than 110 nm with mesoporous structure. Optimized multilayered electrospun α‐Fe₂O₃ nanostructure mats showed photocurrent density of 0.53 mA/cm² under dark and visible illumination conditions at voltage 1.23 V and constant intensity (900 mW/cm²). This photovoltaic performance of nanostructure mats makes it suitable choice for using in the PEC water splitting application as an efficient photoanode. This method, if combined with appropriate flexible conductive substrate, has the potential for producing flexible hematite solar fuel generators. Copyright © 2015 John Wiley & Sons, Ltd.     

Clonal structure and variation in virulence of Salmonella enteritidis isolated from mice, chickens, and humans

The clonal analysis of a diverse collection of Salmonella Enteritidis indicates that most strains belong to a single multilocus genotype (i.e., ET-3) regardless of phage type, geographic origin, or time of isolation that spanned over 2 decades (1978 to 2004). Attachment and invasion assays, however, indicate that, among ET-3 isolates, there is a distinct invasive bacterial subpopulation that is more readily recovered from eggs and clinical cases in humans than from chicken cecal samples. These observations support the hypothesis that the specialized ability of S. Enteritidis to infect the avian reproductive tract and contaminate eggs has been critical in its emergence as a frequent cause of human illness.     

A numerical study on the effect of static magnetic field on the hemodynamics of magnetic fluid in biological porous media

Journal of Thermal Analysis and Calorimetry - High interstitial fluid pressure in the tumor is among the most important barriers to drug delivery. The use of the static magnetic field is one of the...     

Mechanism for reduction catalysis by metal oxo: hydrosilation of organic carbonyl groups catalyzed by a rhenium(V) oxo complex

The rhenium oxo complex [Re(O)(hoz)2][TFPB], 1 (where hoz = 2-(2'-hydroxyphenyl)-2-oxazoline(-) and TFPB = tetrakis(pentafluorophenyl)borate) catalyzes the hydrosilation of aldehydes and ketones under ambient temperature and atmosphere. The major organic product is the protected alcohol as silyl ether. Isolated yields range from 86 to 57%. The reaction requires low catalyst loading (0.1 mol %) and proceeds smoothly in CH2Cl2 as well as neat without solvent. In the latter condition, the catalyst precipitates at the end of reaction, allowing easy separation and catalyst recycling. Re(O)(hoz)(H), 3, was prepared, and its involvement in an ionic hydrosilation mechanism was evaluated. Complex 3 was found to be less hydridic than Et3SiH, refuting its participation in catalysis. A viable mechanism that is consistent with experimental findings, rate measurements, and kinetic isotope effects (Et3SiH/Et3SiD = 1.3 and benzaldehyde-H/benzaldehyde-D = 1.0) is proposed. Organosilane is activated via eta2-coordination to rhenium, and the organic carbonyl adds across the coordinated Si-H bond [2 + 2] to afford the organic reduction product.