Modeling of diffusional limitations in styrene acrylonitrile random bulk copolymerization

Diffusional limitations (the gel, glass, and cage effects) are manifested in several bulk free radical homopolymerizations as well as in random copolymerizations. These are associated with decreases of several orders of magnitude of the rate constants of termination, propagation, and initiation (the initiator efficiency), respectively. These phenomena have been modeled earlier using the free volume theory for the diffusivities of primary radicals, macro‐radicals, and monomer molecules, and have been applied to homopolymerizations. In this study, a similar model is developed for random bulk copolymerizations. The parameters of the model are fitted using isothermal data on styrene acrylonitrile random copolymerization carried out in small ampoules. Thereafter, best‐fit global correlations have been developed for this system. This enables the model to be used for studying non‐isothermal copolymerizations, as well as for carrying out optimization of industrial reactors, where non‐isothermal conditions are a norm. POLYM. ENG. SCI., 55:2098–2110, 2015. © 2014 Society of Plastics Engineers     

In situ efficiency of filters in residential central HVAC systems

High-efficiency filtration in residential forced-air heating, ventilation, and air conditioning (HVAC) systems protects equipment and can reduce exposure to particulate matter. Laboratory tests provide a measure of the nominal efficiency, but they may not accurately reflect the in situ efficiency of the filters because of variations in system conditions and changes in filter performance over time. The primary focus of this paper is to evaluate the effective filtration efficiency, which is inclusive of any loading and system impacts, in 21 occupied residential homes through in-duct concentration measurements. We considered the role of filter media by testing both electret and non-electret media, as well as the role of loading by considering new and used filters. The results show that filters with higher nominal efficiency generally had higher effective filtration efficiency in the same home. In terms of performance change, there is no significant difference in efficiency between initial and 3-month non-electret filters, but the efficiency of electret filters generally decreased over time. However, both nominal efficiency and performance change were vastly overshadowed by the wide variety in loading and system conditions across homes, making it hard to predict filter efficiency in a given home without in situ measurements.     

Estimates of pollutant temporal and spatial variability in commercial buildings from the joint urban 2003 field experiments

In this paper, we report on the indoor concentrations from a suite of full-scale outdoor tracer-gas point releases conducted in the downtown area of Oklahoma City in 2003. A point release experiment consisted of releases of sulfur hexafluoride (SF₆) in multiple buildings and from different outdoor locations. From the measurements, we are able to estimate the concentration variations indoors for a building operating under “typical” operating conditions. The mean indoor spatial coefficients of variation are 30% to 45% from a daytime outdoor release are around 80% during an outdoor evening release. Having estimates of the spatial coefficient of variation provides stakeholders, including first responders, with the likely range of concentrations in the building when little is known about the building characteristics and operating behavior, such as developing urban-scale hazard and consequence analyses. We show differences in indoor measurements at different distances to the release points, floors of the building, and heating, ventilation, and air conditioning system (HVAC) operation. We also show estimates at different time resolutions. The statistics show that in the studied medium to large commercial buildings, spatial differences would result in peak indoor concentrations in certain parts of the buildings that may be substantially higher than the building average. To our knowledge, very few tracer gas measurements have been conducted in buildings of this scope, particularly with measurements on multiple floors and within a floor. The resulting estimates of spatial variability provide a unique opportunity for hazard assessment, and comparison to multi-zone models.     

Characterization of a Tryptophan 6-Halogenase from Streptomyces albus and Its Regioselectivity Determinants

Tryptophan halogenases are found in diverse organisms and catalyze regiospecific halogenation. They play an important role in the biosynthesis of halogenated indole alkaloids, which are biologically active and of therapeutic importance. Here, a tryptophan 6-halogenase (SatH) from Streptomyces albus was characterized by using a whole-cell reaction system in Escherichia coli. SatH showed substrate specificity for chloride and bromide ions, leading to regiospecific halogenation at the C6-position of l -tryptophan. In addition, SatH exhibited higher performance in bromination than that of previously reported tryptophan halogenases in the whole-cell reaction system. Through structure-based protein mutagenesis, it has been revealed that two consecutive residues, A78/V79 in SatH and G77/I78 in PyrH, are key determinants in the regioselectivity difference between tryptophan 6- and 5-halogenases. Substituting the AV with GI residues switched the regioselectivity of SatH by moving the orientation of tryptophan. These data contribute to an understanding of the key residues that determine the regioselectivity of tryptophan halogenases.