Characterisation of atmospheric deposited particles during a dust storm in urban areas of Eastern Australia.

The characteristics of dust particles deposited during the 2009 dust storm in the Gold Coast and Brisbane regions of Australia are discussed in this paper. The study outcomes provide important knowledge in relation to the potential impacts of dust storm related pollution on ecosystem health in the context that the frequency of dust storms is predicted to increase due to anthropogenic desert surface modifications and climate change impacts. The investigated dust storm contributed a large fraction of fine particles to the environment with an increased amount of total suspended solids, compared to dry deposition under ambient conditions. Although the dust storm passed over forested areas, the organic carbon content in the dust was relatively low. The primary metals present in the dust storm deposition were aluminium, iron and manganese, which are common soil minerals in Australia. The dust storm deposition did not contain significant loads of nickel, cadmium, copper and lead, which are commonly present in the urban environment. Furthermore, the comparison between the ambient and dust storm chromium and zinc loads suggested that these metals were contributed to the dust storm by local anthropogenic sources. The potential ecosystem health impacts of the 2009 dust storm include, increased fine solids deposition on ground surfaces resulting in an enhanced capacity to adsorb toxic pollutants as well as increased aluminium, iron and manganese loads. In contrast, the ecosystem health impacts related to organic carbon and other metals from dust storm atmospheric deposition are not considered to be significant.

Composition and morphology of particle emissions from in-use aircraft during takeoff and landing.

In order to provide realistic data for air pollution inventories and source apportionment at airports, the morphology and composition of ultrafine particles (UFP) in aircraft engine exhaust were measured and characterized. For this purpose, two independent measurement techniques were employed to collect emissions during normal takeoff and landing operations at Brisbane Airport, Australia. PM1 emissions in the airfield were collected on filters and analyzed using the particle-induced X-ray emission (PIXE) technique. Morphological and compositional analyses of individual ultrafine particles in aircraft plumes were performed on silicon nitride membrane grids using transmission electron microscopy (TEM) combined with energy-dispersive X-ray microanalysis (EDX). TEM results showed that the deposited particles were in the range of 5-100 nm in diameter, had semisolid spherical shapes and were dominant in the nucleation mode (18-20 nm). The EDX analysis showed the main elements in the nucleation particles were C, O, S, and Cl. The PIXE analysis of the airfield samples was generally in agreement with the EDX in detecting S, Cl, K, Fe, and Si in the particles. The results of this study provide important scientific information on the toxicity of aircraft exhaust and their impact on local air quality.

Novel alginate gel microspheres produced by impinging aerosols for oral delivery of proteins.

Lysozyme and insulin were encapsulated in alginate gel microspheres using impinging aerosols method. High loadings of around 50% weight/dry microspheres weight were obtained with encapsulation efficiencies of at least 48%. Environmental scanning electron microscopy revealed smooth spherical hydrated microspheres (30-60 µm) in diameter. No lysozyme or insulin release was measured in simulated gastric fluid (HCl, pH 1.2, 37°C). Total insulin release occurred in simulated intestinal fluid (SIF; phosphate buffer saline, pH 7.4, 37°C) in 8 h following 2 h incubation in SGF and was found to retain 75% activity using the ARCHITECT® assay. Lysozyme was released completely in SIF in 10 h following 2 h incubation in SGF and was found to exhibit at least 80% bioactivity using the Micrococcus lysodeikticus assay. The absence of protein release in HCl and the retention of high levels of biological activity demonstrate the potential of alginate gel microspheres, for improving oral delivery of biopharmaceuticals.

A novel impinging aerosols method for production of propranolol hydrochloride-loaded alginate gel microspheres for oral delivery.

Propranolol hydrochloride was directly encapsulated in alginate gel microspheres (40-50 µm in diameter) using a novel method involving impinging aerosols of CaCl(2) cross-linking solution and sodium alginate solution containing the drug. Microspheres formulated using 0.1 M CaCl(2) exhibited the highest drug loading (14%, w/w of dry microspheres) with 66.5% encapsulation efficiency. Less than 4% and 35% propranolol release occurred from hydrated and dried microspheres, respectively, in 2 h in simulated gastric fluid (SGF). The majority of the drug load (90%) was released in 5 and 7 h from hydrated and dried microspheres, respectively, in simulated intestinal fluid (SIF). Prior incubation of hydrated microspheres (cross-linked using 0.5 M CaCl(2)) in SGF prolonged the time of release in SIF to 10 h, which has implications for the design of protocols and correlation with in vivo release behaviour. Restricted propranolol release in SGF and complete extraction in SIF demonstrate the potential of alginate gel microspheres for oral delivery of pharmaceuticals.

Survivability of probiotics encapsulated in alginate gel microbeads using a novel impinging aerosols method.

Encapsulation of probiotic bacteria in cross-linked alginate beads is of major interest for improving the survivability in harsh acid and bile environment and also in food matrices. Alginate micro beads (10-40 µm) containing the probiotics Lactobacillus rhamnosus GG and Lactobacillus acidophilus NCFM were produced by a novel technique based on dual aerosols of alginate solution and CaCl(2) cross linking solution. Extruded macro beads (approximately 2mm diameter) produced by the conventional method and micro beads produced by novel aerosols technique offered comparable protection to L. rhamnosus in high acid and bile environment. Chitosan coating of micro beads resulted in a significant increase in survival time of L. rhamnosus from 40 to 120 min in acid condition and the reduction in cell numbers was confined to 0.94 log over this time. Alginate macro beads are more effective than micro beads in protecting L. acidophilus against high acid and bile. Chitosan coating of micro beads resulted in similar protection to L. acidophilus in macro beads in acid and extended the survival time from 90 to at least 120 min. Viability of this organism in micro beads was 3.5 log after 120 min. The continuous processing capability and scale-up potential of the dual aerosol technique offers potential for an efficient encapsulation of probiotics in very small alginate micro beads below sensorial detection limits while still being able to confer effective protection in acid and bile environment.

Diffusion loading and drug delivery characteristics of alginate gel microparticles produced by a novel impinging aerosols method.

Microencapsulation of a hydrophilic active (gentamicin sulphate (GS)) and a hydrophobic non-steroidal anti-inflammatory drug (ibuprofen) in alginate gel microparticles was accomplished by molecular diffusion of the drug species into microparticles produced by impinging aerosols of alginate solution and CaCl(2) cross-linking solution. A mean particle size in the range of 30-50 µm was measured using laser light scattering and high drug loadings of around 35 and 29% weight/dry microparticle weight were obtained for GS and ibuprofen respectively. GS release was similar in simulated intestinal fluid (phosphate buffer saline (PBS), pH 7.4, 37°C) and simulated gastric fluid (SGF) (HCl, pH 1.2, 37°C) but was accelerated in PBS following incubation of microparticles in HCl. Ibuprofen release was restricted in SGF but occurred freely on transfer of microparticles into PBS with almost 100% efficiency. GS released in PBS over 7 h, following incubation of microparticles in HCl for 2 h was found to retain at least 80% activity against Staphylococcus epidermidis while Ibuprofen retained around 50% activity against Candida albicans. The impinging aerosols technique shows potential for producing alginate gel microparticles of utility for protection and controlled delivery of a range of therapeutic molecules.

Silylation of layered double hydroxides via a calcination-rehydration route.

Silylated layered double hydroxides (LDHs) were synthesized through a surfactant-free method involving an in situ condensation of silane with the surface hydroxyl group of LDHs during its reconstruction in carbonate solution. X-ray diffraction (XRD) patterns showed the silylation reaction occurred on the external surfaces of LDHs layers. The successful silylation was evidenced by (29)Si cross-polarization magic-angle spinning nuclear magnetic resonance ((29)Si CP/MAS NMR) spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and infrared emission spectroscopy (IES). The ribbon shaped crystallites with a "rodlike" aggregation were observed through transmission electron microscopy (TEM) images. The aggregation was explained by the T(2) and T(3) types of linkage between adjacent silane molecules as indicated in the (29)Si NMR spectrum. In addition, the silylated products show high thermal stability by maintained Si related bands even when the temperature was increased to 1000 degrees C as observed in IES spectra.

An investigation into the characteristics and formation mechanisms of particles originating from the operation of laser printers.

While current research has demonstrated that the operation of some laser printers results in emission of high concentrations of ultrafine particles, fundamental gaps in knowledge in relation to the emissions still remain. In particular, there have been no answers provided to questions such as the following: (1) What is the composition of the particles? (2) What are their formation mechanisms? (3) Why are some printers high emitters, while others are low? Considering the widespread use of printers and human exposure to these particles, understanding the process of particle formation is of critical importance. This study, using state-of-the-art instrumental methods, has addressed these three points. We present experimental evidence that indicates that intense bursts of particles are associated with temperature fluctuations and suggest that the difference between high and low emitters lies in the speed and sophistication of the temperature control. We have also shown, for the first time, that the particles are volatile and are of secondary nature, being formed in the air from VOC originating from both the paper and hot toner. Some of the toner is initially deposited on the fuser roller, after which the organic compounds evaporate and then form particles, through one of two main reaction pathways: homogeneous nucleation or secondary particle formation involving ozone.

Encapsulation of a glycosaminoglycan in hydroxyapatite/alginate capsules.

The development of suitable vehicles for the delivery of growth-inducing factors to fracture sites is a challenging area of bone repair. Bone-specific glycosaminoglycan molecules are of particular interest because of their high stability and proven effect on bone growth. Calcium alginate capsules are popular as delivery vehicles because of their low immunogenic response; they offer a versatile route that enables the controlled release of heparin (a member of the glycosaminoglycan family). In this study, hydroxyapatite (HA)/alginate composite capsules are explored as novel drug delivery vehicles for heparin, using both medium- and low-viscosity alginates. The composition, structure, and stability of the capsules are fully characterized and correlated to the release of heparin in vitro. Heparin is found to associate both with the alginate matrix through polymeric flocculation and also with the HA crystals in the composite beads. The mechanism by which heparin is released is dictated by the stability of the capsule in a particular release media and by the composition of the capsule. The use of medium-viscosity alginate is advantageous with respect to both drug loading and prolonging the release. The inclusion of HA increases the encapsulation efficiency, but because of its destabilizing effect to the alginate hydrogel matrix, it also increases the rate of heparin release. The bioactivity of heparin is fully retained throughout the assembly and release processes.

In situ synthesis of surfactant/silane-modified hydrotalcites.

In this study, anionic surfactant and silane-modified hydrotalcites were synthesized through a soft chemical in situ method. The resulting materials were characterized using X-ray diffraction (XRD), high-resolution thermogravimetric analysis (HRTG), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and N2 adsorption-desorption. The Mg-Al hydrotalcite (LDH) and the only surfactant-modified hydrotalcite (LDH-2) display similar XRD patterns while both surfactant and silane-modified hydrotalcite (LDH-3) show two distinct series of reflections, corresponding to hydrotalcite and smectite-like materials, respectively. The smectite-like materials show a series of regular (001) reflections with d 001=12.58 A. Further supporting evidence was obtained from FTIR and TG, for example, the vibration at 1198 cm(-1) corresponds to SiOSi-stretching mode and the mass loss at ca. 861 degrees C to dehydroxylation. In LDH-2, the loaded surfactants are located in both the interlayer space and the interparticle pores with a "house of cards" structure as supported by FTIR, TG, and N2 adsorption-desorption isotherms. Both electron microscopy (SEM and TEM) micrographs and N2 adsorption-desorption isotherms show that in situ modification with surfactant and silane has a significant influence on the morphology and porous parameters of the resulting hydrotalcite materials.

Synthesis, characterization, and surface properties of iron-doped boehmite nanofibers.

Iron-doped boehmite nanofibers with varying iron contents have been prepared at low temperatures using hydrothermal treatment in the presence of poly(ethylene oxide) surfactant. The resulting nanofibers were characterized by transmission electron microscopy (TEM), X-ray diffraction, energy-dispersive X-ray analysis, and N2 adsorption. TEM images showed that the resulting nanostructures are predominantly nanofibers when the doped iron content is less than 5% (mol/mol); in contrast, nanosheets were formed when iron doping was above 4%. Nanotubes instead of nanofibers and iron-rich particles were observed in samples with 20% added iron. A detailed characterization and discussion on the iron-doped nanofibers is presented.

Raman spectroscopic study of the molecular structure of the uranyl mineral zippeite from Jáchymov (Joachimsthal), Czech Republic.

Raman spectra at 298 and 77K and infrared spectra of the uranyl sulfate mineral zippeite from Jáchymov (Joachimsthal), Czech Republic, K(0.6)(H(3)O)0.4[(UO(2))6(SO(4))3(OH)7].8H2O, were studied. Observed bands were tentatively attributed to the (UO(2))2+ and (SO(4))2- stretching and bending vibrations, the OH stretching vibrations of water molecules, hydroxyls and oxonium ions, and H(2)O, oxonium, and delta U-OH bending vibrations. Empirical relations were used for the calculation of U-O bond lengths in uranyl R (A)=f(nu(3) or nu(1)(UO(2))2+). Calculated U-O bond lengths are in agreement with U-O bond lengths from the single crystal structure analysis and those inferred for uranyl anion sheet topology of uranyl pentagonal dipyramidal coordination polyhedra. The number of observed bands supports the conclusion from single crystal structure analysis that at least two symmetrically distinct U6+ (in uranyls) and S6+ (in sulfates), water molecules and hydroxyls may be present in the crystal structure of the zippeite studied. Strong to very weak hydrogen bonds present in the crystal structure of zippeite studied were inferred from the IR spectra.

WITHDRAWN: Interlayer structure and morphology of HDTMA(+)/montmorillonite organoclay.

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Modification of Wyoming montmorillonite surfaces using a cationic surfactant.

Surfaces of Wyoming SWy-2-Na-montmorillonite were modified using ultrasonic and hydrothermal methods through the intercalation and adsorption of the cationic surfactant octadecyltrimethylammonium bromide (ODTMA). Changes in the surfaces and structure were characterized using X-ray diffraction (XRD), thermal analysis (TG), and electron microscopy. The ultrasonic preparation method results in a higher surfactant concentration within the montmorillonite interlayer when compared with that from the hydrothermal method. Three different molecular environments for surfactants within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. Both XRD patterns and TEM images demonstrate that SWy-2-Na-montmorillonite contains superlayers. TEM images of organoclays prepared at high surfactant concentrations show alternate basal spacings between neighboring layers. SEM images show that modification with surfactant reduces the clay particle size and aggregation. Organoclays prepared at low surfactant concentration display curved flakes, whereas they become flat with increasing intercalated surfactant. Novel surfactant-modified montmorillonite results in the formation of new nanophases with the potential for the removal of organic impurities from aqueous media.

Preparation of sub-micrometer silica shells using poly(1-methylpyrrol-2-ylsquaraine).

Poly(1-methylpyrrol-2-ylsquaraine) precipitates from reaction solution as uniformly spherical particles with a diameter of 1.3 microm. Upon heating, the particles reduce in diameter until extinction at approximately 630 degrees C. Treatment of the particles with 9:1 tetraethoxysilane:ethanol solution, and subsequent hydrolysis in dilute acid, results in a polymer core-silica shell structure. Removal of the core, upon heating to 660 degrees C, results in an amorphous silica shell with a diameter half that of the initial template sphere. It has been found that the silica shells produced by this method are able to encapsulate organic dyes upon soaking of the shells in chloroform solutions of the dyes, and further washings with fresh chloroform did not remove the dyes. The production of crystalline titanium dioxide shells was also achieved through the use of the polysquaraine particles as a spherical template.

Calcium phosphate nucleation on surface-modified PTFE membranes.

Highly porous PTFE membranes are currently being used in facial reconstructive surgery. The present study aims at improving this biomaterial through creating a more bioactive surface by introducing ionic groups onto the surface. The unmodified PTFE membrane does not induce inorganic growth after immersion in simulated body fluid (SBF) for up to 4 weeks. Copolymeric grafting with acrylic acid (AAc) by means of gamma irradiation and subsequent in vitro testing in SBF reveals that this copolymer initially acts as an ion-exchange material and subsequently induces growth of a calcium phosphate phase (Ca/P=2.7) when large amounts (15%) of pAAc are introduced onto the membrane surface. This copolymer is not expected to function well from a biomaterials perspective since SEM showed the pores on the surface to be partly blocked. In contrast, the surface of monoacryloxyethyl phosphate (MAEP)-modified samples is altered at a molecular level only. Yet the modified materials are able to induce calcium phosphate nucleation when the external surface coverage is 44% or above. The initial inorganic growth on these membranes in SBF has a (Ca+Mg)/P ratio of 1.1 (presumably Brushite or Monetite). The secondary growth, possibly calcium-deficient apatite or tricalcium phosphate, has a (Ca+Mg)/P ratio of 1.5. This result is a promising indicator of a bioactive biomaterial.