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.     

Synthesis and physicochemical characteristics of polymolybdenum(VI) phenylsiloxanes by means of different methods

Interaction of molybdenyl(VI) bis(acetylacetonate) with polyphenylsiloxane in xylene and under mechanochemical activation conditions has been investigated. The interaction in solution proceeds with splitting of the siloxane bond and formation of polymolybdenum(VI) phenylsiloxane with different silicon/metal ratios. The fractions with the silicon/metal ratio < 2 are characterized with high degree of crystallinity and low solubility, whereas those with the ratio > 2 are amorphous. The interaction of the above reagents under mechanical activation conditions proceeds with the formation of soluble polymers similar to those obtained in a solution with the silicon/molybdenum ratio equal to 2.6. The crystal chemistry parameters of the fraction obtained in solution with the ratio Si/Mo equals to 1:2 have been calculated on the basis of the X-ray diffraction analysis data using the Debye–Shearer equation. It has been demonstrated that the chain cross section found using the Miller–Boyer method coincides with that calculated geometrically on the basis of literature data on bond lengths and angles. It is shown that the interaction of molybdenyl(VI) bis(acetylacetonate) with polyphenylsiloxane takes place in solution more deeply than under the conditions of mechanochemical activation and is accompanied by the process of separation siloxanes connection. This leads to the formation of a fraction with smaller ratio of substances than the initial ratio.     

Cell-Free Synthesis of Selenoproteins in High Yield and Purity for Selective Protein Tagging

The selenol group of selenocysteine is much more nucleophilic than the thiol group of cysteine. Selenocysteine residues in proteins thus offer reactive points for rapid post-translational modification. Herein, we show that selenoproteins can be expressed in high yield and purity by cell-free protein synthesis by global substitution of cysteine by selenocysteine. Complete alkylation of solvent-exposed selenocysteine residues was achieved in 10 minutes with 4-chloromethylene dipicolinic acid (4Cl-MDPA) under conditions that left cysteine residues unchanged even after overnight incubation. Gd^III−Gd^III distances measured by double electron–electron resonance (DEER) experiments of maltose binding protein (MBP) containing two selenocysteine residues tagged with 4Cl-MDPA-Gd^III were indistinguishable from Gd^III−Gd^III distances measured of MBP containing cysteine reacted with 4Br-MDPA tags.