Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds

Asymmetric emission profiles of the stereoisomers of plant-derived volatile organic compounds vary with season, geography, plant type, and stress factors. After oxidation of these compounds in the atmosphere, the low-vapor pressure products ultimately contribute strongly to the particle-phase material of the atmosphere. In order to explore the possibility of stereochemical transfer to atmospheric aerosol particles during the oxidation of biogenic volatile organic compounds, second-order coherent vibrational spectra were recorded of the particle-phase organic material produced by the oxidation of different stereoisomeric mixes of alpha-pinene. The spectra show that the stereochemical configurations are not scrambled but instead are transferred from the gas-phase molecular precursors to the particle-phase molecules. The spectra also show that oligomers formed in the particle phase have a handed superstructure that depends strongly and nonlinearly on the initial stereochemical composition of the precursors. Because the stereochemical mix of the precursors for a material can influence the physical and chemical properties of that material, our findings suggest that chirality is also important for such properties of plant-derived aerosol particles. Citation: Ebben, C. J., S. R. Zorn, S.-B. Lee, P. Artaxo, S. T. Martin, and F. M. Geiger (2011), Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds, Geophys. Res. Lett., 38, L16807, doi: 10.1029/2011GL048599.

Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin

Submicron atmospheric particles in the Amazon Basin were characterized by a high-resolution aerosol mass spectrometer during the wet season of 2008. Patterns in the mass spectra closely resembled those of secondary-organic-aerosol (SOA) particles formed in environmental chambers from biogenic precursor gases. In contrast, mass spectral indicators of primary biological aerosol particles (PBAPs) were insignificant, suggesting that PBAPs contributed negligibly to the submicron fraction of particles during the period of study. For 40% of the measurement periods, the mass spectra indicate that in-Basin biogenic SOA production was the dominant source of the submicron mass fraction, contrasted to other periods (30%) during which out-of-Basin organic-carbon sources were significant on top of the baseline in-Basin processes. The in-Basin periods had an average organic-particle loading of 0.6 mu g m(-3) and an average elemental oxygen-to-carbon (O:C) ratio of 0.42, compared to 0.9 mu g m(-3) and 0.49, respectively, during periods of out-of-Basin influence. On the basis of the data, we conclude that most of the organic material composing submicron particles over the Basin derived from biogenic SOA production, a finding that is consistent with microscopy observations made in a concurrent study. This source was augmented during some periods by aged organic material delivered by long-range transport. Citation: Chen, Q., et al. (2009), Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin, Geophys. Res. Lett., 36, L20806, doi: 10.1029/2009GL039880.

Spectral absorption properties of aerosol particles from 350-2500nm

The aerosol spectral absorption efficiency (alpha(a) in m(2)/g) is measured over an extended wavelength range (350-2500 nm) using an improved calibrated and validated reflectance technique and applied to urban aerosol samples from Sao Paulo, Brazil and from a site in Virginia, Eastern US, that experiences transported urban/industrial aerosol. The average alpha(a) values (similar to 3m(2)/g at 550 nm) for Sao Paulo samples are 10 times larger than a a values obtained for aerosols in Virginia. Sao Paulo aerosols also show evidence of enhanced UV absorption in selected samples, probably associated with organic aerosol components. This extra UV absorption can double the absorption efficiency observed from black carbon alone, therefore reducing by up to 50% the surface UV fluxes, with important implications for climate, UV photolysis rates, and remote sensing from space. Citation: Martins, J.V., P. Artaxo, Y.J. Kaufman, A.D. Castanho, and L.A. Remer (2009), Spectral absorption properties of aerosol particles from 350-2500nm, Geophys. Res. Lett., 36, L13810, doi: 10.1029/2009GL037435.

Biomechanical effects of environmental and engineered particles on human airway smooth muscle cells

The past decade has seen significant increases in combustion-generated ambient particles, which contain a nanosized fraction (less than 100 nm), and even greater increases have occurred in engineered nanoparticles (NPs) propelled by the booming nanotechnology industry. Although inhalation of these particulates has become a public health concern, human health effects and mechanisms of action for NPs are not well understood. Focusing on the human airway smooth muscle cell, here we show that the cellular mechanical function is altered by particulate exposure in a manner that is dependent upon particle material, size and dose. We used Alamar Blue assay to measure cell viability and optical magnetic twisting cytometry to measure cell stiffness and agonist-induced contractility. The eight particle species fell into four categories, based on their respective effect on cell viability and on mechanical function. Cell viability was impaired and cell contractility was decreased by (i) zinc oxide (40-100 nm and less than 44 mu m) and copper(II) oxide (less than 50 nm); cell contractility was decreased by (ii) fluorescent polystyrene spheres (40 nm), increased by (iii) welding fumes and unchanged by (iv) diesel exhaust particles, titanium dioxide (25 nm) and copper(II) oxide (less than 5 mu m), although in none of these cases was cell viability impaired. Treatment with hydrogen peroxide up to 500 mu M did not alter viability or cell mechanics, suggesting that the particle effects are unlikely to be mediated by particle-generated reactive oxygen species. Our results highlight the susceptibility of cellular mechanical function to particulate exposures and suggest that direct exposure of the airway smooth muscle cells to particulates may initiate or aggravate respiratory diseases.

On the interaction of the anthraquinone barbaloin with negatively charged DMPG bilayers

Barbaloin is a bioactive glycosilated 1,8-dihydroxyanthraquinone present in several exudates from plants, Such as Aloe vera, which are used for cosmetic or food purposes. It has been shown that barbaloin interacts with DMPG (dimyristoylphosphatidylglycerol) model membranes, altering the bilayer structure (Alves, D. S.; Perez-Fons, L.; Estepa, A.; Micol, V. Biochem. Pharm. 2004, 68, 549). Considering that ESR (electron spin resonance) of spin labels is one of the best techniques to monitor structural properties at the molecular level, the alterations caused by the anthraquinone barbaloin on phospholipid bilayers will be discussed here via the ESR signal of phospholipid spin probes intercalated into the membranes. In DMPG at high ionic strength (10 mM Hepes pH 7.4 + 100 mM NaCl), a system that presents a gel-fluid transition around 23 degrees C, 20 mol % barbaloin turns the gel phase more rigid, does not alter much the fluid phase packing, but makes the lipid thermal transition less sharp. However, in a low-salt DMPG dispersion (10 mM Hepes pH 7.4 + 2 mM NaCl), which presents a rather complex gel-fluid thermal transition (Lamy-Freund, M. T.; Riske, K. A. Chem. Phys. Lipids 2003, 122, 19), barbaloin strongly affects bilayer structural properties, both in the gel and fluid phases, extending the transition region to much higher temperature values. The position of barbaloin in DMPG bilayers will be discussed on the basis of ESR results, in parallel with data from sample viscosity, DSC (differential scanning calorimetry), and SAXS (small-angle X-ray scattering).

Coherent and semiclassical states in a magnetic field in the presence of the Aharonov-Bohm solenoid

A new approach to constructing coherent states (CS) and semiclassical states (SS) in a magnetic-solenoid field is proposed. The main idea is based on the fact that the AB solenoid breaks the translational symmetry in the xy-plane; this has a topological effect such that there appear two types of trajectories which embrace and do not embrace the solenoid. Due to this fact, one has to construct two different kinds of CS/SS which correspond to such trajectories in the semiclassical limit. Following this idea, we construct CS in two steps, first the instantaneous CS (ICS) and then the time-dependent CS/SS as an evolution of the ICS. The construction is realized for nonrelativistic and relativistic spinning particles both in (2 + 1) and (3 + 1) dimensions and gives a non-trivial example of SS/CS for systems with a nonquadratic Hamiltonian. It is stressed that CS depending on their parameters (quantum numbers) describe both pure quantum and semiclassical states. An analysis is represented that classifies parameters of the CS in such respect. Such a classification is used for the semiclassical decompositions of various physical quantities.

Semiclassical and quantum motions on the non-commutative plane

We study the canonical and the coherent state quantizations of a particle moving in a magnetic field on the non-commutative plane. Using a theta-modified action, we perform the canonical quantization and analyze the gauge dependence of the theory. We compare coherent states quantizations obtained through Malkin-Man`ko states and circular squeezed states. The relation between these states and the ""classical"" trajectories is investigated, and we present numerical explorations of some semiclassical quantities. (C) 2009 Elsevier B.V. All rights reserved.

Quantum spin tunneling of magnetization in small ferromagnetic particles

An approach is presented that can also account for the description of small ferromagnetic particle magnetization tunneling. An estimate of the saturation value of an external applied magnetic field along the easy axis is obtained. An analytic expression for the tunneling factor in the absence of an external magnetic field is deduced from the present approach that also allows one to obtain the crossover temperature characterizing the regime where tunneling is dominated by quantum effects. (C) 2009 Published by Elsevier B.V.

Chemical process to separate iron oxides particles in pottery sample for EPR dating

Ancient potteries usually are made of the local clay material, which contains relatively high concentration of iron. The powdered samples are usually quite black, due to magnetite, and, although they can be used for thermoluminescene (TL) dating, it is easiest to obtain better TL reading when clearest natural or pre-treated sample is used. For electron paramagnetic resonance (EPR) measurements, the huge signal due to iron spin-spin interaction, promotes an intense interference overlapping any other signal in this range. Sample dating is obtained by dividing the radiation dose, determined by the concentration of paramagnetic species generated by irradiation, by the natural dose so as a consequence, EPR dating cannot be used, since iron signal do not depend on radiation dose. In some cases, the density separation method using hydrated solution of sodium polytungstate [Na(G)(H(2)W(12)O(40))center dot H(2)O] becomes useful. However, the sodium polytungstate is very expensive in Brazil: hence an alternative method for eliminating this interference is proposed. A chemical process to eliminate about 90% of magnetite was developed. A sample of powdered ancient pottery was treated in a mixture (3:1:1) of HCI, HNO(3) and H(2)O(2) for 4 h. After that, it was washed several times in distilled water to remove all acid matrixes. The original black sample becomes somewhat clearer. The resulting material was analyzed by plasma mass spectrometry (ICP-MS), with the result that the iron content is reduced by a factor of about 9. In EPR measurements a non-treated natural ceramic sample shows a broad spin-spin interaction signal, the chemically treated sample presents a narrow signal in g= 2.00 region, possibly due to a radical of (SiO(3))(3-), mixed with signal of remaining iron [M. lkeya, New Applications of Electron Spin Resonance, World Scientific, Singapore, 1993, p. 285]. This signal increases in intensity under -gamma-irradiation. However, still due to iron influence, the additive method yielded too old age-value. Since annealing at 300 degrees C, Toyoda and Ikeya IS. Toyoda, M. Ikeya, Geochem. J. 25 (1991) 427-445] states that E `(1)-signal with maximum intensity is obtained, while annealing at 400 degrees C E`(1)-signal is completely eliminated, the subtraction of the second one from 300 degrees C heat-treated sample isolate E`(1)-like signal. Since this is radiation dose-dependent, we show that now EPR dating becomes possible. (C) 2008 Elsevier B.V. All rights reserved.

Quasinormal modes of semiclassical electrically charged black holes

We report the results concerning the influence of vacuum polarization due to quantum massive vector, scalar and spinor fields on the scalar sector of quasinormal modes in spherically symmetric charged black holes. The vacuum polarization from quantized fields produces a shift in the values of the quasinormal frequencies, and correspondingly the semiclassical system becomes a better oscillator with respect to the classical Reissner-Nordstrom black hole.

Vesicles with charged domains

This work summarizes results obtained on membranes composed of the ternary mixture dioleoylphosphatidylglycerol (DOPG), egg sphingomyelin (eSM) and cholesterol (Chol). The membrane phase state as a function of composition is characterized from data collected with fluorescence microscopy on giant unilamellar vesicles. The results suggest that the presence of the charged DOPG significantly decreases the composition region of coexistence of liquid ordered and liquid disordered phases as compared to that in the ternary mixture of dioleoylphosphatidycholine, sphingomyelin and cholesterol. The addition of calcium chloride to DOPG:eSM:Chol vesicles, and to a lesser extent the addition of sodium chloride, leads to the stabilization of the two-phase coexistence region, which is expressed in an increase in the miscibility temperature. On the other hand, addition of the chelating agent EDTA has the opposite effect, suggesting that impurities of divalent cations in preparations of giant vesicles contribute to the stabilization of charged domains. We also explore the behavior of these membranes in the presence of extruded unilamellar vesicles made of the positively charged lipid dioleoyltrimethylammoniumpropane (DOTAP). The latter can induce domain formation in DOPG:eSM:Chol vesicles with initial composition in the one-phase region. (C) 2010 Elsevier B.V. All rights reserved.

VACUUM POLARIZATION EFFECTS ON QUASINORMAL MODES IN ELECTRICALLY CHARGED BLACK HOLE SPACE-TIMES

We investigate the influence of vacuum polarization of quantum massive fields on the scalar sector of quasinormal modes in spherically symmetric black holes. We consider the evolution of a massless scalar field on the space-time corresponding to a charged semiclassical black hole, consisting of the quantum-corrected geometry of a Reissner-Nordstrom black hole dressed by a quantum massive scalar field in the large mass limit. Using a sixth order WKB approach we find a shift in the quasinormal mode frequencies due to vacuum polarization.

Multiscale Curvature Analysis of Asphaltic Aggregate Particles

A new method for characterization and analysis of asphaltic mixtures aggregate particles is reported. By relying on multiscale representation of the particles, curvature estimation, and discriminant analysis for optimal separation of the categories of mixtures, a particularly effective and comprehensive methodology is obtained. The potential of the methodology is illustrated with respect to three important types of particles used in asphaltic mixtures, namely basalt, gabbro, and gravel. The obtained results show that gravel particles are markedly distinct from the other two types of particles, with the gabbro category resulting with intermediate geometrical properties. The importance of each considered measurement in the discrimination between the three categories of particles was also quantified in terms of the adopted discriminant analysis.

One-dimensional trapped atoms: critical coupling parameter and critical number of particles

In this paper we consider the case of a Bose gas in low dimension in order to illustrate the applicability of a method that allows us to construct analytical relations, valid for a broad range of coupling parameters, for a function which asymptotic expansions are known. The method is well suitable to investigate the problem of stability of a collection of Bose particles trapped in one- dimensional configuration for the case where the scattering length presents a negative value. The eigenvalues for this interacting quantum one-dimensional many particle system become negative when the interactions overcome the trapping energy and, in this case, the system becomes unstable. Here we calculate the critical coupling parameter and apply for the case of Lithium atoms obtaining the critical number of particles for the limit of stability.

Protein Assembly onto Cationic Supported Bilayers

Cationic supported bilayers on latex are useful to isolate and immobilize oppositely charged proteins as a monomolecular layer over a range of low protein concentrations and particle number densities. Cholera toxin (CT) from Vibrio cholerae, an 87 kDa AB(5) hexameric protein and bovine serum albumin (BSA) self-assembled on dioctadecyldimethylammonium bromide (DODAB) supported bilayers with high affinity yielding highly organized and monodisperse particulates at 5 x 10(9) particles/mL, over a range of low protein concentrations (0-0.025 mg/mL BSA or CT). Protein association onto the bilayer-covered polystyrene sulfate (PSS) was determined from adsorption isotherms, dynamic light scattering for size distributions and zeta-potential analysis revealing a monomolecular, thin and highly organized protein layer surrounding each particle with potential for biospecific recognition such as antigen-antibody, receptor-ligand, hybridization of oligonucleotide sequences, all of them important in immunodiagnosis, selective biomolecular chromatographic separations, microarrays design and others.