The Role of Thermal Activation and Molecular Structure on the Reaction of Molecular Surfaces.

Though surface modifications of organic thin films dramatically improve optoelectronic device performance, chemistry at organic surfaces presents new challenges that are not seen in conventional inorganic surfaces. This work demonstrates that the subsurface of pentacene remains highly accessible, even to large adsorbates, and that three distinct reaction regimes (surface, subsurface, and bulk) are accessed within the narrow thermal range of 30-75 °C. Progression of this transition is quantitatively measured via polarization modulation infrared reflection absorption spectroscopy, and atomic force microscopy is used to measure the thin-film morphology. Together, they reveal the close relationship between the extent of the reaction and the morphology changes. Finally, the reaction kinetics of the pentacene thin film is measured with a series of adsorbates that have different reactivity and diffusivity in the thin film. The results suggest that reaction kinetics in the thin film is controlled by both the reactivity and the adsorbate diffusivity in the thin-film lattice, which is very different than the traditional solution kinetics that is dominated by the chemical activation barriers. Combined, these experiments guide efforts toward rationally functionalizing the surfaces of organic semiconductors to enable the next generation of flexible devices.

Efficacy of screens in removing long fibers from an aerosol stream--sample preparation technique for toxicology studies.

Fiber dimension (especially length) and biopersistence are thought to be important variables in determining the pathogenicity of asbestos and other elongate mineral particles. In order to prepare samples of fibers for toxicology studies, it is necessary to develop and evaluate methods for separating fibers by length in the micrometer size range. In this study, we have filtered an aerosol of fibers through nylon screens to investigate whether such screens can efficiently remove the long fibers (L >20 µm, a typical macrophage size) from the aerosol stream. Such a sample, deficient in long fibers, could then be used as the control in a toxicology study to investigate the role of length. A well-dispersed aerosol of glass fibers (a surrogate for asbestos) was generated by vortex shaking a Japan Fibrous Material Research Association (JFMRA) glass fiber powder. Fibers were collected on a mixed cellulose ester (MCE) filter, imaged with phase contrast microscopy (PCM) and lengths were measured. Length distributions of the fibers that penetrated through various screens (10, 20 and 60 µm mesh sizes) were analyzed; additional study was made of fibers that penetrated through double screen and centrally blocked screen configurations. Single screens were not particularly efficient in removing the long fibers; however, the alternative configurations, especially the centrally blocked screen configuration, yielded samples substantially free of the long fibers.

Dustiness of fine and nanoscale powders.

Dustiness may be defined as the propensity of a powder to form airborne dust by a prescribed mechanical stimulus; dustiness testing is typically intended to replicate mechanisms of dust generation encountered in workplaces. A novel dustiness testing device, developed for pharmaceutical application, was evaluated in the dustiness investigation of 27 fine and nanoscale powders. The device efficiently dispersed small (mg) quantities of a wide variety of fine and nanoscale powders, into a small sampling chamber. Measurements consisted of gravimetrically determined total and respirable dustiness. The following materials were studied: single and multiwalled carbon nanotubes, carbon nanofibers, and carbon blacks; fumed oxides of titanium, aluminum, silicon, and cerium; metallic nanoparticles (nickel, cobalt, manganese, and silver) silicon carbide, Arizona road dust; nanoclays; and lithium titanate. Both the total and respirable dustiness spanned two orders of magnitude (0.3-37.9% and 0.1-31.8% of the predispersed test powders, respectively). For many powders, a significant respirable dustiness was observed. For most powders studied, the respirable dustiness accounted for approximately one-third of the total dustiness. It is believed that this relationship holds for many fine and nanoscale test powders (i.e. those primarily selected for this study), but may not hold for coarse powders. Neither total nor respirable dustiness was found to be correlated with BET surface area, therefore dustiness is not determined by primary particle size. For a subset of test powders, aerodynamic particle size distributions by number were measured (with an electrical low-pressure impactor and an aerodynamic particle sizer). Particle size modes ranged from approximately 300 nm to several micrometers, but no modes below 100 nm, were observed. It is therefore unlikely that these materials would exhibit a substantial sub-100 nm particle contribution in a workplace.

Comparison of air sampling methods for aerosolized spores of B. anthracis Sterne.

Bacillus anthracis Sterne spores were aerosolized within a chamber at concentrations ranging from 1 x 10³ to 1.7 x 104 spores per cubic meter of air (particles (p)/m³) to compare three different sampling methods: Andersen samplers, gelatin filters, and polytetrafluoroethylene (PTFE) membrane filters. Three samples of each type were collected during each of 19 chamber runs. Chamber concentration was determined by an aerodynamic particle sizer (APS) for the size range of 1.114-1.596 µm. Runs were categorized (low, medium, and high) based on tertiles of the APS estimated air concentrations. Measured air concentrations and recovery efficiency [ratio of the measured (colony forming units (CFU)/m³) to the APS estimated (particles/m³) air concentrations] for the sampling methods were compared using mixed-effects regression models. Limits of detection for each method were estimated based on estimated recovery efficiencies. Mean APS estimated air concentrations were 1600 particles/m³, 4100 particles/m³, and 9100 particles/m³ at the low, medium, and high tertiles, respectively; coefficient of variation (CV) ranged from 25 to 40%. Statistically significant differences were not observed among the three sampling methods. At the high and medium tertiles, estimated correlations of measured air concentration (CFU/m³) among samples collected from the same run of the same type were high (0.73 to 0.93). Among samples collected from the same run but of different types, correlations were moderate to high (0.45 to 0.85); however, correlations were somewhat lower at the low tertile (-0.31 to 0.75). Estimated mean recovery efficiencies ranged from 0.22 to 0.25 CFU/particle with total CVs of approximately 84 to 97%. Estimated detection limits ranged from 35 to 39 particles/m³. These results will enable investigators to conduct environmental sampling, quantify contamination levels, and conduct risk assessments of B. anthracis.

Recovery efficiency and limit of detection of aerosolized Bacillus anthracis Sterne from environmental surface samples.

After the 2001 anthrax incidents, surface sampling techniques for biological agents were found to be inadequately validated, especially at low surface loadings. We aerosolized Bacillus anthracis Sterne spores within a chamber to achieve very low surface loading (ca. 3, 30, and 200 CFU per 100 cm(2)). Steel and carpet coupons seeded in the chamber were sampled with swab (103 cm(2)) or wipe or vacuum (929 cm(2)) surface sampling methods and analyzed at three laboratories. Agar settle plates (60 cm(2)) were the reference for determining recovery efficiency (RE). The minimum estimated surface concentrations to achieve a 95% response rate based on probit regression were 190, 15, and 44 CFU/100 cm(2) for sampling steel surfaces and 40, 9.2, and 28 CFU/100 cm(2) for sampling carpet surfaces with swab, wipe, and vacuum methods, respectively; however, these results should be cautiously interpreted because of high observed variability. Mean REs at the highest surface loading were 5.0%, 18%, and 3.7% on steel and 12%, 23%, and 4.7% on carpet for the swab, wipe, and vacuum methods, respectively. Precision (coefficient of variation) was poor at the lower surface concentrations but improved with increasing surface concentration. The best precision was obtained with wipe samples on carpet, achieving 38% at the highest surface concentration. The wipe sampling method detected B. anthracis at lower estimated surface concentrations and had higher RE and better precision than the other methods. These results may guide investigators to more meaningfully conduct environmental sampling, quantify contamination levels, and conduct risk assessment for humans.

Aerosolization of single-walled carbon nanotubes for an inhalation study.

Single-walled carbon nanotubes (SWCNT) are being produced in increasing quantities because of high interest in applications resulting from their unique properties. Because of potential respiratory exposures during production and handling, inhalation studies are needed to determine potential toxicity. A generation system was designed to produce respirable aerosol at 5 mg/m(3) for a 1-wk animal (mouse) exposure. The starting material used in these experiments was as-produced powder from the high pressure carbon monoxide method that was sieved to number 6 mesh (< 2.3 mm). An acoustic feeder system was developed that handled the SWCNT powder without causing compaction of the material. The feed rate was adjustable, allowing output concentrations as high as 25 mg/m(3). The powder particles were reduced in size using a mill that produced high shear forces, tearing the agglomerates apart. The resulting aerosol was size-separated using a settling chamber and two cyclones to produce a respirable aerosol. The mass output efficiency of the entire system for producing a respirable aerosol from bulk material was estimated to be about 10%.

In vitro cytotoxicity of Manville Code 100 glass fibers: effect of fiber length on human alveolar macrophages.

BACKGROUND: Synthetic vitreous fibers (SVFs) are inorganic noncrystalline materials widely used in residential and industrial settings for insulation, filtration, and reinforcement purposes. SVFs conventionally include three major categories: fibrous glass, rock/slag/stone (mineral) wool, and ceramic fibers. Previous in vitro studies from our laboratory demonstrated length-dependent cytotoxic effects of glass fibers on rat alveolar macrophages which were possibly associated with incomplete phagocytosis of fibers >or= 17 microm in length. The purpose of this study was to examine the influence of fiber length on primary human alveolar macrophages, which are larger in diameter than rat macrophages, using length-classified Manville Code 100 glass fibers (8, 10, 16, and 20 microm). It was hypothesized that complete engulfment of fibers by human alveolar macrophages could decrease fiber cytotoxicity; i.e. shorter fibers that can be completely engulfed might not be as cytotoxic as longer fibers. Human alveolar macrophages, obtained by segmental bronchoalveolar lavage of healthy, non-smoking volunteers, were treated with three different concentrations (determined by fiber number) of the sized fibers in vitro. Cytotoxicity was assessed by monitoring cytosolic lactate dehydrogenase release and loss of function as indicated by a decrease in zymosan-stimulated chemiluminescence. RESULTS: Microscopic analysis indicated that human alveolar macrophages completely engulfed glass fibers of the 20 microm length. All fiber length fractions tested exhibited equal cytotoxicity on a per fiber basis, i.e. increasing lactate dehydrogenase and decreasing chemiluminescence in the same concentration-dependent fashion. CONCLUSION: The data suggest that due to the larger diameter of human alveolar macrophages, compared to rat alveolar macrophages, complete phagocytosis of longer fibers can occur with the human cells. Neither incomplete phagocytosis nor length-dependent toxicity was observed in fiber-exposed human macrophage cultures. In contrast, rat macrophages exhibited both incomplete phagocytosis of long fibers and length-dependent toxicity. The results of the human and rat cell studies suggest that incomplete engulfment may enhance cytotoxicity of fiber glass. However, the possibility should not be ruled out that differences between human versus rat macrophages other than cell diameter could account for differences in fiber effects.