Vapor-liquid nucleation in two dimensions: on the intriguing sign switch of the errors of the classical nucleation theory.

A nucleation study of a two-dimensional (2D) Lennard-Jones (LJ) system is done using the aggregation-volume-bias Monte Carlo with umbrella sampling method. The results obtained from this simulation study was compared to those predicted by the classical nucleation theory (CNT). It was found that the nucleation free energy obtained for this 2D LJ system was underestimated by CNT; however, this result is significantly different from that found for the 3D LJ system where CNT overestimates the free energy. These results are generally in agreement with previous studies on these systems. While both errors can be traced to the incorrect description of the smallest clusters by the theory, structural analysis reveals striking differences between 2D and 3D clusters, leading to a possible source for this observed sign switch. In particular, the radius of gyration data indicates that for the 3D LJ system, clusters formed at the beginning are fractal and the cluster growth is accompanied by an increase of the dimensionality, whereas clusters in 2D show little sign of this dimensionality transition.

Prescribed burns and wildfires in Colorado: impacts of mitigation measures on indoor air particulate matter.

Wildfires and prescribed burns are receiving increasing attention as sources of fine particulate matter (PM2.5). The goal of this research project was to understand the impact of mitigation strategies for residences impacted by scheduled prescribed burns and wildfires. Pairs of residences were solicited to have PM2.5 concentrations monitored inside and outside of their houses during four fires. The effect of using air cleaners on indoor PM2.5 was investigated, as well as the effect of keeping windows closed. Appropriately sized air cleaners were provided to one of each pair of residences; occupants of all of the residences were asked to keep windows shut and minimize opening of exterior doors. Additionally, residents were asked to record all of the activities that may be a source of particulate matter, such as cooking and cleaning. Measurements were made during one prescribed burn and three wildfires during the 2002 fire season. Outdoor 24-hr average PM2.5 concentrations ranging from 6 to 38 microg/m3 were measured during the fires, compared with levels of 2-5 microg/m3 during background measurements when no fires were burning. During the fires, PM2.5 was < 3 microg/m3 inside all of the houses with air cleaners installed. This corresponds with a decrease of 63-88% in homes with the air cleaners operating when compared with homes without air cleaners. In the homes without the air cleaners, measured indoor concentrations were 58-100% of the concentrations measured outdoors.

Protein engineering of the archetypal nitroarene dioxygenase of Ralstonia sp. strain U2 for activity on aminonitrotoluenes and dinitrotoluenes through alpha-subunit residues leucine 225, phenylalanine 350, and glycine 407.

Naphthalene dioxygenase (NDO) from Ralstonia sp. strain U2 has not been reported to oxidize nitroaromatic compounds. Here, saturation mutagenesis of NDO at position F350 of the alpha-subunit (NagAc) created variant F350T that produced 3-methyl-4-nitrocatechol from 2,6-dinitrotoluene (26DNT), that released nitrite from 23DNT sixfold faster than wild-type NDO, and that produced 3-amino-4-methyl-5-nitrocatechol and 2-amino-4,6-dinitrobenzyl alcohol from 2-amino-4,6-dinitrotoluene (2A46DNT) (wild-type NDO has no detectable activity on 26DNT and 2A46DNT). DNA shuffling identified the beneficial NagAc mutation G407S, which when combined with the F350T substitution, increased the rate of NDO oxidation of 26DNT, 23DNT, and 2A46DNT threefold relative to variant F350T. DNA shuffling of NDO nagAcAd also generated the NagAc variant G50S/L225R/A269T with an increased rate of 4-amino-2-nitrotoluene (4A2NT; reduction product of 2,4-dinitrotoluene) oxidation; from 4A2NT, this variant produced both the previously uncharacterized oxidation product 4-amino-2-nitrocresol (enhanced 11-fold relative to wild-type NDO) as well as 4-amino-2-nitrobenzyl alcohol (4A2NBA; wild-type NDO does not generate this product). G50S/L225R/A269T also had increased nitrite release from 23DNT (14-fold relative to wild-type NDO) and generated 2,3-dinitrobenzyl alcohol (23DNBA) fourfold relative to wild-type NDO. The importance of position L225 for catalysis was confirmed through saturation mutagenesis; relative to wild-type NDO, NDO variant L225R had 12-fold faster generation of 4-amino-2-nitrocresol and production of 4A2NBA from 4A2NT as well as 24-fold faster generation of nitrite and 15-fold faster generation of 23DNBA from 23DNT. Hence, random mutagenesis discovered two new residues, G407 and L225, that influence the regiospecificity of Rieske non-heme-iron dioxygenases.

Effects of ceiling-mounted HEPA-UV air filters on airborne bacteria concentrations in an indoor therapy pool building.

The purpose of this study was to assess the effectiveness of a new generation of high-volume, ceiling-mounted high-efficiency particulate air (HEPA)-ultraviolet (UV) air filters (HUVAFs) for their ability to remove or inactivate bacterial aerosol. In an environmentally controlled full-scale laboratory chamber (87 m3), and an indoor therapy pool building, the mitigation ability of air filters was assessed by comparing concentrations of total bacteria, culturable bacteria, and airborne endotoxin with and without the air filters operating under otherwise similar conditions. Controlled chamber tests with pure cultures of aerosolized Mycobacterium parafortuitum cells showed that the HUVAF unit tested provided an equivalent air-exchange rate of 11 hr(-1). Using this equivalent air-exchange rate as a design basis, three HUVAFs were installed in an indoor therapy pool building for bioaerosol mitigation, and their effectiveness was studied over a 2-year period. The HUVAFs reduced concentrations of culturable bacteria by 69 and 80% during monitoring periods executed in respective years. The HUVAFs reduced concentrations of total bacteria by 12 and 76% during the same monitoring period, respectively. Airborne endotoxin concentrations were not affected by the HUVAF operation.