Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Hollow capsules formed in a single stage via interfacial hydrogen-bonded complexation of methylcellulose with poly(acrylic acid) and tannic acid

Hollow capsules can be prepared in a single stage by the interfacial complexation of methylcellulose (MC) with poly(acrylic acid) (PAA) or tannic acid (TA) via hydrogen bonding in aqueous solutions. The formation of capsules is observed when viscous solution of methylcellulose is added drop-wise to diluted solutions of polyacids under acidic conditions. The optimal parameters such as polymer concentration and solution pH for the formation of these capsules were established in this work. It was found that tannic acid forms capsules in a broader range of concentrations and pHs compared to poly(acrylic acid). The TA/MC capsules exhibited better stability compared to PAA/MC in response to increase in pH: the dissolution of TA/MC capsules observed at pH > 9.5; whereas PAA/MC capsules dissolved at pH > 3.8. The interfacial complexation can be considered as a potential single stage alternative to the formation of capsules using multistage layer-by-layer deposition method.

Interfacial interactions in concretes with silica fume and SBR latex

This paper deals with the effect of silica fume and styrene-butadiene latex (SBR) on the microstructure of the interfacial transition zone (ITZ) between Portland cement paste and aggregates (basalt). Scanning electron microscope (SEM) equipped with energy dispersive X-ray analysis system (EDX) was used to determine the ITZ thickness. In the plain concrete a marked ITZ around the aggregate particles (55 mu m) was observed, while in concretes with silica fume or latex SBR the ITZ was less pronounced (35-40 mu m). However, better results were observed in concretes with silica fume and latex SBR (20-25 mu m). (C) 2008 Elsevier Ltd. All rights reserved.

Investigation of interfacial processes at tetraruthenated zinc porphyrin films using electrochemical surface plasmon resonance and electrochemical quartz crystal microbalance

In the present work we describe the investigation of interfacial and superficial processes on tetraruthenated zinc porphyrin (ZnTRP) films immobilized on gold electrode surface. In situ and real time measurements employing electrochemical surface plasmon resonance (ESPR)and electrochemical quartz crystal microbalance (EQCM) have given new insights into the electrochemical oxidation of ferrocyanide and phenolic compounds (acetaminophen, dopamine, and catechol) on ZnTRP modified electrodes. The decrease of diode like behavior in the presence of such phenolic species in contrast with ferrocyanide was clearly assigned to the inclusion of those species in the porphyrin film, creating new conduction pathways connecting the gold electrode surface with the film/solution interface. In fact, there are evidences that they can intercalate in the film (catechol > dopamine > acetaminophen), whereas ferrocyanide is completely excluded. Accordingly, the molecular size may play a fundamental role in such a process. (C) 2009 Published by Elsevier Ltd.

Structural and vibrational characterization of polyaniline nanofibers prepared from interfacial polymerization

This work deals with the structural and vibrational characterization of PANI nanofibers prepared through interfacial polymerization using different concentrations of HCl aqueous solution. The results were compared to those obtained by PANI prepared through the conventional route. X-ray diffraction and small-angle X-ray scattering techniques showed that high concentrations of HCl solutions used in the preparation of the PANI nanofibers reduce their crystallinity. The increase of regions with granular morphology was also observed in the scanning electron microscopy images. The changes in the resonance Raman spectra from 200 to 500 cm(-1), FTIR spectra, and the EPR data of the PANI nanofibers reveal an increase in the torsion angles of C-ring-N-C-ring segments owing the formation of bipolarons in the PANI backbone higher than the PANI samples prepared by conventional route.

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Desenvolvimento de microcápsulas contendo as antocianinas presentes no corante do extrato do jambo por polimerização interfacial

The industries of food, medicine and cosmetic apply microencapsulation for many reasons, among them, stabilize the active, control the release of encapsulated and separate incompatible components of the formulation. In this context, microencapsulation techniques have been used in the food industry to provide stable liquid and solid ingredients. Anthocyanins have high antioxidant potential, but they are photodegradable. The challenges are therefore directed to the research for techniques that could make this potential remaining active and bioavailable and could be used as a vehicle for the delivery release of bioactive and micronutrients in appropriate conditions and levels. This work has as main objective to propose a method to encapsulate the anthocyanins in the extract of mountain apple using the interfacial polymerization technique. As well as to define the ideal conditions of temperature and agitation system for this procedure. The microparticles were characterized for size, morphology, active distribution, surface charge, degradation, composition and stability. The results, like particle diameter of 5.94 μm and Zeta potential of 7.03 mV, showed that the technique used to obtain these microparticles was satisfactory and has potential for application in cosmetics and food

Determining the interfacial density of states in metal-insulator-semiconductor devices based on poly(3-hexylthiophene)

Low frequency admittance measurements are used to determine the density of interface states in metal-insulator-semiconductor diodes based on the unintentionally doped, p-type semiconductor poly(3-hexylthiophene). After vacuum annealing at 90 degrees C, interface hole trapping states are shown to be distributed in energy with their density decreasing approximately linearly from similar to 20x10(10) to 5x10(10) cm(-2) eV(-1) over an energy range extending from 0.05 to 0.25 eV above the bulk Fermi level. (c) 2008 American Institute of Physics.

Measurement of Interfacial Porosity at the Acrylic Resin/Denture Tooth Interface

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of dentin conditioning time on nanoleakage

Objectives: To study the nanoleakage pattern in the dentin hybrid layer by using different dentin adhesives. The null hypotheses tested in this study were: 1) dentin conditioning time does not affect nanoleakage within the hybrid layer; 2) the type of dentin adhesive used does not affect nanoleakage. Methods: Standardized Class V cavities were prepared in 30 intact human molars on the buccal and lingual surfaces. The specimens were randomly assigned to 2 total-etch dentin adhesives (OptiBond SOLO Plus [OPS, Kerr] and One-Step [ONS, BISCO Inc]) and 2 self-etch dentin adhesives (Clearfil SE Bond [CSE, Kuraray] and Adper Prompt L-Pop [APL, 3M ESPE]). The specimens were etched or conditioned for 15 seconds, 30 seconds or 60 seconds. Upon restoration of the Class V cavities with the proprietary resin composite, the specimens were isolated with nail polish except for a 2.0-mm rim around the restoration, and they were immersed in 50 wt% ammoniacal silver nitrate solution (pH=9.5) for 24 hours followed by 8 hours of immersion in photo-developing solution to reduce the silver ions to metallic silver. The specimens were fixed, dehydrated and processed for FESEM and TEM. Silver penetration was measured along the cervical wall, and data were analyzed with Kruskal-Wallis non-parametric tests at a significance level of 95%. Results: There were no statistically significant differences among the experimental groups for the factor conditioning time (p>0.926). There were significant differences for the variable dentin adhesive (p<0.0001). The least amount of nanoleakage within the hybrid layer occurred with CSE, while ONS resulted in the greatest penetration of silver ions. The adhesives OPS and APL ranked in the intermediary subset. Under TEM, all adhesives resulted in some degree of nanoleakage within the hybrid layer. Both spotted/reticular and water-tree nanoleakage patterns were observed. Significance: Longer conditioning times did not increase nanoleakage within the hybrid layer. Nanoleakage varied with the type of adhesive used.

Interfacial surface charge and free accessibility to the PLA(2)-active site-like region are essential requirements for the activity of Lys49 PLA(2) homologues

Lys49 phospholipase A(2) homologues are highly myotoxic and cause extensive tissue damage but do not display hydrolytic activity towards natural phospholipids. The binding of heparin, heparin derivatives and polyanionic compounds such as suramin result in partial inhibition (up to 60%) of the myotoxic effects due to a change in the overall charge of the interfacial surface. In vivo experiments demonstrate that polyethylene glycol inhibits more than 90% of the myotoxic effects without exhibiting secondary toxic effects. The crystal structure of bothropstoxin-I complexed with polyethylene glycol reveals that this inhibition is due to steric hindrance of the access to the PLA(2)-active site-like region. These two inhibitory pathways indicate the roles of the overall surface charge and free accessibility to the PLA2-active site-like region in the functioning of Lys49 phospholipases A(2) homologues. Molecular dynamics simulations, small angle X-ray scattering and structural analysis indicate that the oligomeric states both in solution and in the crystalline states of Lys49 phospholipases A2 are principally mediated by hydrophobic contacts formed between the interfacial surfaces. These results provide the framework for the potential application of both clinically approved drugs for the treatment of Viperidae snakebites. (c) 2006 Elsevier Ltd. All rights reserved.

Interfacial concentrations of chloride and bromide in zwitterionic micelles with opposite dipoles: Experimental determination by chemical trapping and a theoretical description

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Interfacial fracture of dentin adhesively bonded to quartz-fiber reinforced composite

The paper presents the results of an experimental study of interfacial failure in a multilayered structure consisting of a dentin/resin cement/quartz-fiber reinforced composite (FRC). Slices of dentin close to the pulp chamber were sandwiched by two half-circle discs made of a quartz-fiber reinforced composite, bonded with bonding agent (All-bond 2, BISCO, Schaumburg) and resin cement (Duo-link. BISCO, Schaumburg) to make Brazil-nut sandwich specimens for interfacial toughness testing. Interfacial fracture toughness (strain energy release rate, G) was measured as a function of mode mixity by changing loading angles from 0 degrees to 15 degrees. The interfacial fracture surfaces were then examined using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX) to determine the failure modes when loading angles changed. A computational model was also developed to calculate the driving forces, stress intensity factors and mode mixities. Interfacial toughness increased from approximate to 1.5 to 3.2 J/m(2) when the loading angle increases from approximate to 0, 0 to 15 degrees. The hybridized dentin/cement interface appeared to be tougher than the resin cement/quartz-fiber reinforced epoxy. The Brazil-nut sandwich specimen was a suitable method to investigate the mechanical integrity of dentin/cement/FRC interfaces. (C) 2011 Elsevier B.V. All rights reserved.

Effect of multiple firing and silica deposition on the zirconia-porcelain interfacial bond strength

Objectives. To test the hypothesis that multiple firing and silica deposition on the zirconia surface influence the bond strength to porcelain.Materials and methods. Specimens were cut from yttria-stabilized zirconia blocks and sintered. Half of the specimens (group S) were silica coated (physical vapor deposition (PVD)) via reactive magnetron sputtering before porcelain veneering. The remaining specimens (group N) had no treatment before veneering. The contact angle before and after silica deposition was measured. Porcelain was applied on all specimens and submitted to two (N2 and S2) or three firing cycles (N3 and S3). The resulting porcelain-zirconia blocks were sectioned to obtain bar-shaped specimens with 1 mm(2) of cross-sectional area. Specimens were attached to a universal testing machine and tested in tension until fracture. Fractured surfaces were examined using optical microscopy. Data were statistically analyzed using two-way ANOVA, Tukey's test (alpha = 0.05) and Weibull analysis.Results. Specimens submitted to three firing cycles (N3 and S3) showed higher mean bond strength values than specimens fired twice (N2 and S2). Mean contact angle was lower for specimens with silica layer, but it had no effect on bond strength. Most fractures initiated at porcelain-zirconia interface and propagated through the porcelain.Significance. The molecular deposition of silica on the zirconia surface had no influence on bond strength to porcelain, while the number of porcelain firing cycles significantly affected the bond strength of the ceramic system, partially accepting the study hypothesis. Yet, the Weibull modulus values of S groups were significantly greater than the m values of N groups. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.