Ambient Vapor Phase Research Articles

Isolated and solvated chiroptical behavior in conformationally flexible butanamines.

The nonresonant optical activity of two highly flexible aliphatic amines, (2R)-3-methyl-2-butanamine (R-MBA) and (2R)-(3,3)-dimethyl-2-butanamine (R-DMBA), has been probed under isolated and solvated conditions to examine the roles of conformational isomerism and to explore the influence of extrinsic perturbations. The optical rotatory dispersion (ORD) measured in six solvents presented uniformly negative rotatory powers over the 320-590 nm region, with the long-wavelength magnitude of chiroptical response growing nearly monotonically as the dielectric constant of the surroundings diminished. The intrinsic specific optical rotation, (in deg dm-1 [g/mL]-1 ), extracted for ambient vapor-phase samples of R-MBA [-11.031(98) and -2.29 (11)] and R-DMBA [-9.434 (72) and -1.350 (48)] at 355 and 633 nm were best reproduced by counterintuitive solvents of high polarity (yet low polarizability) like acetonitrile and methanol. Attempts to interpret observed spectral signatures quantitatively relied on the linear-response frameworks of density-functional theory (B3LYP, cam-B3LYP, and dispersion-corrected analogs) and coupled-cluster theory (CCSD), with variants of the polarizable continuum model (PCM) deployed to account for the effects of implicit solvation. Building on the identification of several low-lying equilibrium geometries (nine for R-MBA and three for R-DMBA), ensemble-averaged ORD profiles were calculated at T = 300K by means of the independent-conformer ansatz, which enabled response properties predicted for the optimized structure of each isomer to be combined through Boltzmann-weighted population fractions derived from corresponding relative internal-energy or free-energy values, the latter of which stemmed from composite CBS-APNO and G4 analyses. Although reasonable accord between theory and experiment was realized for the isolated (vapor-phase) species, the solution-phase results were less satisfactory and tended to degrade progressively as the solvent polarity increased. These trends were attributed to solvent-mediated changes in structural parameters and energy metrics for the transition states that separate and putatively isolate the equilibrium conformations supported by the ground electronic potential-energy surface, with the resulting displacement of barrier locations and/or decrease of barrier heights compromising the underlying premise of the independent-conformer ansatz.

Combined adjuvant effects of ambient vapor-phase organic components and particulate matter potently promote allergic sensitization and Th2-skewing cytokine and chemokine milieux in mice: The importance of mechanistic multi-pollutant research

Although exposure to ambient particulate matter (PM) is linked to asthma, the health effects of co-existing vapor-phase organic pollutants (vapor) and their combined effects with PM on this disease are poorly understood. We used a murine asthma model to test the hypothesis that exposure to vapor would enhance allergic sensitization and this effect would be further strengthened by co-existing PM. We found that vapor and PM each individually exerted adjuvant effects on OVA sensitization. Co-exposure to vapor and PM during sensitization further enhanced allergic lung inflammation and OVA-specific antibody production which was accompanied by pulmonary cytokine/chemokine milieu that favored T-helper 2 immunity (i.e. increased IL-4, downregulation of Il12a and Ifng, and upregulation of Ccl11 and Ccl8). TNFα, IL-6, Ccl12, Cxcl1 and detoxification/antioxidant enzyme responses in the lung were pollutant-dependent. Inhibition of lipopolysaccharide-induced IL-12 secretion from primary antigen-presenting dendritic cells correlated positively with vapor’s oxidant potential. In conclusion, concurrent exposure to vapor and PM led to significantly exaggerated adjuvant effects on allergic lung inflammation which were more potent than that of each pollutant type alone. These findings suggest that the effects of multi-component air pollution on asthma may be significantly underestimated if research only focuses on a single air pollutant (e.g., PM).

Water evaporation from solute-containing aerosol droplets: Effects of internal concentration and diffusivity profiles and onset of crust formation.

The evaporation of droplets is an important process not only in industrial and scientific applications, but also in the airborne transmission of viruses and other infectious agents. We derive analytical and semi-analytical solutions of the coupled heat and mass diffusion equations within a spherical droplet and in the ambient vapor phase that describe the evaporation process of aqueous free droplets containing nonvolatile solutes. Our results demonstrate that the solute-induced water vapor-pressure reduction considerably slows down the evaporation process and dominates the solute-concentration dependence of the droplet evaporation time. The evaporation-induced enhanced solute concentration near the droplet surface, which is accounted for using a two-stage evaporation description, is found to further slow-down the drying process. On the other hand, the presence of solutes is found to produce a lower limit for the droplet size that can be reached by evaporation and, also, to reduce evaporation cooling of the droplet, which tend to decrease the evaporation time. Overall, the first two effects are dominant, meaning that the droplet evaporation time increases in the presence of solutes. Local variation of the water diffusivity inside the droplet near its surface, which is a consequence of the solute-concentration dependence of the diffusion coefficient, does not significantly change the evaporation time. Crust formation on the droplet surface increases the final equilibrium size of the droplet by producing a hollow spherical particle, the outer radius of which is determined as well.

Electrolyte supply and modelling of electrochemical nanofilm processors

The controlled lateral oxidation of nanoscale aluminum layer in nanofilm processors is a new type of electrochemical device providing application for a large variety of smart labels. For this device based on an electrochemical cell the electrolyte function is realized by a thin layer containing a hygroscopic agent harvesting water from the ambient atmosphere necessary for the electrochemical process inside the device. The fundamental experimental principle of supplying a nanofilm processor by water harvesting from the ambient atmosphere in thin electrolyte layer is actually shown in previous paper. In this paper we have a closer view on the volume flows and develop a model describing the occurring volume flows in the electrolyte layer as transfer unit for water from the ambient vapor phase into the nanofilm processor. Based on this model we optimized the electrolyte layer technically to achieve a distinctive improvement of the feeding performance of the nanofilm processor especially under deficit condition concerning the ambient humidity.

Intrinsic Optical Activity and Large-Amplitude Displacement: Conformational Flexibility in (R)-Glycidyl Methyl Ether.

The dispersive optical activity of (R)-(-)-glycidyl methyl ether (R-GME) has been interrogated under ambient vapor-phase and solution-phase conditions, with quantum-chemical analyses built on density functional (B3LYP and CAM-B3LYP) and coupled-cluster (CCSD) implementations of linear-response theory exploited to interpret experimental findings. Inherent flexibility of the heavy atom skeleton leads to nine low-lying structural isomers that possess distinct chiroptical and physicochemical properties, as evinced by marked changes in the magnitude and the sign of rotatory powers observed in various media. These species are interconverted by independent motion along two large-amplitude torsional coordinates and are stabilized differentially by interaction with the surroundings, thereby reapportioning their relative contributions to the collective response evoked from a thermally equilibrated ensemble. The intrinsic behavior exhibited by isolated (vapor-phase) R-GME molecules was calculated through use of both conformer-averaging and restricted vibrational-averaging procedures, the former affording moderately good agreement with measurements of optical rotatory dispersion (ORD) and the latter providing strong evidence for sizable effects arising from vibrational degrees of freedom. A similar conformer-averaging ansatz based on the polarizable-continuum model (PCM) for implicit solvation was deployed to elucidate R-GME specific-rotation parameters acquired for six dilute solutions. This approach gave reasonable predictions for sodium D-line (589.3 nm) experiments performed in the extremes of solvent polarity represented by cyclohexane and acetonitrile but failed to reproduce the overall shape of ORD profiles and suggested more complex processes might be involved in the case of an aromatic medium.

Surface Structure, Adsorption, and Thermal Desorption Behaviors of Methaneselenolate Monolayers on Au(111) from Dimethyl Diselenides

To understand the effect of headgroups (i.e., sulfur and selenium) on surface structure, adsorption states, and thermal desorption behaviors of self-assembled monolayers (SAMs) on Au(111), we examined methanethiolate (CH3–S, MS) and metheneselenolate (CH3–Se, MSe) monolayers formed from dimethyl disulfide (DMDS) and dimethyl diselenide (DMDSe) molecules by ambient vapor-phase deposition. Scanning tunneling microscopy imaging revealed that DMDS molecules on Au(111) after a 1 h deposition form MS monolayers containing a disordered phase and an ordered row phase with an inter-row spacing of 1.51 nm, whereas DMDSe molecules form long-range-ordered MSe monolayers with a (√3 × 3√3)R30° structure. X-ray photoelectron spectroscopy measurements showed that MS or MSe monolayers chemisorbed on Au(111) were formed via S–S bond cleavage of DMDS or Se–Se bond cleavage of DMDSe. On the other hand, we monitored three main desorption fragments for MS and MSe monolayers using TDS monomers (CH3S+, CH3Se+), parent mass speci...

Temperature of critical clusters in nucleation theory: Generalized Gibbs' approach

According to the classical Gibbs' approach to the description of thermodynamically heterogeneous systems, the temperature of the critical clusters in nucleation is the same as the temperature of the ambient phase, i.e., with respect to temperature the conventional macroscopic equilibrium conditions are assumed to be fulfilled. In contrast, the generalized Gibbs' approach [J. W. P. Schmelzer, G. Sh. Boltachev, and V. G. Baidakov, J. Chem. Phys. 119, 6166 (2003); and ibid. 124, 194503 (2006)] predicts that critical clusters (having commonly spatial dimensions in the nanometer range) have, as a rule, a different temperature as compared with the ambient phase. The existence of a curved interface may lead, consequently, to an equilibrium coexistence of different phases with different temperatures similar to differences in pressure as expressed by the well-known Laplace equation. Employing the generalized Gibbs' approach, it is demonstrated that, for the case of formation of droplets in a one-component vapor, the temperature of the critical droplets can be shown to be higher as compared to the vapor. In this way, temperature differences between critically sized droplets and ambient vapor phase, observed in recent molecular dynamics simulations of argon condensation by Wedekind et al. [J. Chem. Phys. 127, 064501 (2007)], can be given a straightforward theoretical interpretation. It is shown as well that - employing the same model assumptions concerning bulk and interfacial properties of the system under consideration - the temperature of critical bubbles in boiling is lower as compared to the bulk liquid.

Isotopic Composition and Fractionation of Mercury in Great Lakes Precipitation and Ambient Air

Atmospheric deposition is a primary pathway by which mercury (Hg) enters terrestrial and aquatic ecosystems; however, the chemical and meteorological processes that Hg undergoes from emission to deposition are not well understood. Hg stable isotope geochemistry is a growing field used to better understand Hg biogeochemical cycling. To examine the atmospheric Hg isotopic composition in the Great Lakes, precipitation and ambient vapor-phase Hg samples were collected in Chicago, IL, Holland, MI, and Dexter, MI, between April 2007 and September 2009. Precipitation samples were characterized by negative mass-dependent fractionation (MDF) (δ(202)Hg = -0.79‰ to 0.18‰), while most vapor-phase samples displayed positive MDF (δ(202)Hg = -0.59‰ to 0.43‰). Positive mass-independent fractionation (MIF) (Δ(199)Hg = 0.04‰ to 0.52‰) was observed in precipitation, whereas MIF was slightly negative in vapor-phase samples (Δ(199)Hg = -0.21‰ to 0.06‰). Significant positive MIF of (200)Hg up to 0.25‰ was also measured in precipitation. Such MIF of an even-mass Hg isotope has not been previously reported in natural samples. These results contrast with recent predictions of the isotopic composition of atmospheric Hg and suggest that, in addition to aqueous photoreduction, other atmospheric redox reactions and source-related processes may contribute to isotopic fractionation of atmospheric Hg.

Two-dimensional ordering of pentafluorobenzenethiol self-assembled monolayers on Au(1 1 1) prepared by ambient-pressure vapor deposition

Formation and surface structures of pentafluorobenzenethiol (PFBT) self-assembled monolayers (SAMs) on Au(1 1 1) prepared by ambient-vapor phase deposition were examined by means of scanning tunneling microscopy (STM) as a function of deposition temperature. PFBT SAMs formed at room temperature have disordered phases with bright aggregated domains, which are very similar to benzenethiol SAMs. As deposition temperature increases to 50 °C, partially ordered domains and large aggregated domains appeared. High-resolution STM clearly revealed that PFBT SAMs formed at 75 °C were composed of long-range, two-dimensional (2D) ordered domains, which can be described as a c(2×√3) structure. The results of this study clearly demonstrate that deposition temperature is a crucial factor for obtaining PFBT SAMs on Au(1 1 1) with a high degree of structural order.

Biochemical and cellular effects of electrophiles present in ambient air samples

Ambient vapor-phase samples collected in Riverside, California had shown that both redox and electrophilic activity were present, with the vapor phase containing higher levels of electrophiles than the particle phase. In this study, the biochemical effects of the vapor-phase electrophiles were examined using the purified thiol proteins, glyceraldehyde-3-phosphate dehydrogenase (GAPDH), protein tyrosine phosphatase 1B (PTP1B) and KELCH-1 like ECH-associated protein 1 (Keap1). The results demonstrated that the thiol proteins were inactivated by the vapor-phase samples through covalent modifications. Next, two cellular responses, epidermal growth factor receptor (EGFR)/mitogen-activated protein (MAP) kinase and NF-E2-related factor 2 (Nrf2), to the ambient vapor-phase samples were assessed in A549 and RAW 264.7 cell lines, respectively. The vapor-phase samples, at non-oxidative concentrations, increased phosphorylation of EGFR, which is negatively regulated by PTP1B, and its downstream MAP kinase, extracellular signal-regulated kinase (ERK)1/2. Activation of Nrf2, which requires Keap1 alkylation, and expression of its downstream proteins were also observed. The electrophilic compounds present in ambient vapor-phase were shown to modify cellular proteins through covalent modification and to activate diverse cellular responses that can lead to inflammatory and adaptive responses.

Atmospheric gaseous mercury concentrations in New York State: relationships with meteorological data and other pollutants

Abstract Ambient vapor-phase mercury concentrations including total gaseous mercury (TGM) and reactive gaseous mercury (RGM) were measured at three locations in rural New York State: Potsdam, Stockton, and Sterling. The RGM concentrations (4.2±6.4, 5.7±9.2, 6.0±10.8 pg m−3 at the Potsdam, Stockton, and Sterling sites, respectively) were about 0.2–3% of the total gaseous phase mercury concentration (TGM: 1.84±1.24, 1.83±1.32, 3.02±2.14 ng m−3, respectively) at the three monitoring sites. Standard deviations of RGM concentrations indicate that their daily variation was larger than that of TGM at all sites. This larger variation is probably because RGM is influenced by local sources to a greater extent than elemental mercury, which makes up to majority of TGM. There was no significant correlation between ozone and mercury concentrations. However, there was a significant positive correlation between water vapor mixing ratio and elemental mercury concentrations, suggesting that reduction of Hg2+ to Hg0 occurred in liquid water contained in clouds and fogs near the three monitoring sites. TGM concentrations had a generally negative correlation with ambient temperature, whereas RGM concentrations had a positive relationship. The negative relationship between TGM and temperature may be due to seasonal differences in emission rates of coal-fired power plants (winter maximum) in the northern hemisphere. This assumption was supported by a positive correlation between TGM and sulfur concentration, one of the major pollutants emitted from coal-fired power plants.

Reaction intermediates on TiO2(110) identified by time-lapse scanning tunneling microscopy

The present account describes first time examples of scanning tunneling microscope (STM) visualization of reaction intermediates on a metal oxide surface. The topographic response of reactant-adsorbed TiO2(110) surfaces to a temperature increment or to a pressure increment was monitored as a sequence of STM images. Acetates thermally decomposing to ketene were resolved in a temperature-jump STM observation. The kinetics of the acetate consumption was determined on the number of acetates resolved in the microscope images and agreed with the macroscopic rate law of ketene production. A pressure-jump study revealed how a chemisorbed carboxylate (RCOO-) is exchanged by another carboxylate (R'COO-) supplied from the ambient vapor phase. An impinging R'COOH was immobilized on the top of a RCOO- and then squeezed itself into the monolayer of the RCOO-. One of the carboxylates in the squeezed state returned to the vapor phase via the immobilized state.

The contribution of nitro- and methylnitronaphthalenes to the vapor-phase mutagenicity of ambient air samples

1- and 2-Nitronaphthalene (NN) and the 14 methylnitronaphthalene (MNN) isomers were identified and quantified in ambient vapor-phase samples collected in Redlands, CA during moderate photochemical air pollution. The mutagenic activities of NN and MNN standards were determined using a microsuspension-preincubation modification of the Ames Salmonella bacterial reversion assay in strain TA98 without microsomal activation. The calculated contributions of the NNs and MNNs to the total vapor-phase ambient mutagenic activity were ∼ 18 and ∼ 32% for daytime and nighttime composite samples, respectively. Enhanced mutagenic activity in the nighttime sample was attributed to NN and MNN formation from nighttime N03 radical-initiated reactions of naphthalene and the methylnaphthalenes.

Wet deposition of mercury and ambient mercury concentrations at a site in the Lake Champlain basin

The “Great Waters” program, established in the 1990 Clean Air Act Amendments, mandated that atmospheric deposition of hazardous air pollutants to Lake Champlain (including Hg) be assessed. An assessment of the magnitude and seasonal variation of atmospheric Hg deposition in the Lake Champlain basin was initiated in December 1992 with one year of event precipitation collection, as well as collection of vapor and particle phase Hg in ambient air. Samples were collected at the Vermont Monitoring Cooperative air monitoring site at the Proctor Maple Research Center in Underhill Center, VT. The average volume-weighted concentration for Hg in precipitation was 8.3 ng/L for the sampling year and the average amount of Hg deposited with each precipitation event was 0.069 μg/m2. The total amount of Hg deposited through precipitation during 1993 was 9.26 μg/m2/yr. A seasonal pattern for Hg in precipitation was evident, with increased concentrations and deposition during spring and summer months. Meteorological analysis indicated the highest levels of Hg in precipitation were associated with regional transport from the south regardless of season, and with transport from the west, southwest and northwest during spring and summer months. Concentrations of ambient vapor phase Hg were typical of rural locations and consistent across seasons. Ambient particulate Hg concentrations averaged 11 pg/m3 with highest concentrations during the winter months.

Alkaline Hydrolysis of Phosphoglycerides on Thin Layer Plates In Situ

Abstract An alkaline hydrolysis method for selective cleavage of the acyl groups in phospholipids is described. The alkaline hydrolysis treatment was achieved with 0.8 N methanolic NaOH by incubation at 37°C in a chamber presaturated with aqueous methanol to saturate the ambient vapor phase and thus maintain the concentration of NaOH. Cleavage of acyl groups was quantitative while cleavage of ether groups was below the level of detection. There was no effect on the alkenyl ether linkages of plasmalogens.

Theory of vapor pressure osmometry when ambient solvent vapor is unsaturated

AbstractThe general theory of the vapor pressure osmometry has been established, as an extension of the KAMIDE and SANADA theory, in the case when ambient vapor phase is unsaturated. The temperature difference (Tn–Tv)s at the steady state between a solution drop and a solvent drop can be expressed in a form of virial expansion of concentration c in the form: with equation image Tn and Tv are the temperatures of the solution and solvent drops, respectively, M1 the molecular weight of the solute, A2,v the second virial coefficient, R the gas constant, Ts the temperature of ambient vapor phase, δH the molar heat of condensation of the solvent, k1n and k2n the coefficients of heat transfer at the interfaces between vapor and the solution drop and between the solution and the thermistor, respectively, A1n the surface area of the solution drop, A2n the surface area of the thermistor in contact with the solution. P0(Ts) saturated vapor pressure of the solvent at the temperature Ts, k′ the saturation coefficient defined by the ratio of the real unsaturated pressure of ambient vapor phase to the saturated pressure at the same temperature, and V0 the molar volume of the solvent.Theoretical examination of k′ showed the difference between Ks and Ks is negligible, i.e., the first equation usually reduces to the corresponding equation derived previously by assuming that the ambient vapor phase is saturated.