No abstract

A novel active personal nanoparticle sampler (PENS), which enables the collection of both respirable particulate mass (RPM) and nanoparticles (NPs) simultaneously, was developed to meet the critical demand for personal sampling of engineered nanomaterials (ENMs) in workplaces. The PENS consists of a respirable cyclone and a micro-orifice impactor with the cutoff aerodynamic diameter (d(pa50)) of 4 μm and 100 nm, respectively. The micro-orifice impactor has a fixed micro-orifice plate (137 nozzles of 55 μm in the inner diameter) and a rotating, silicone oil-coated Teflon filter substrate at 1 rpm to achieve a uniform particle deposition and avoid solid particle bounce. A final filter is used after the impactor to collect the NPs. Calibration results show that the d(pa50) of the respirable cyclone and the micro-orifice impactor are 3.92 ± 0.22 μm and 101.4 ± 0.1 nm, respectively. The d(pa50) at the loaded micro-Al(2)O(3) mass of 0.36-3.18 mg is shifted to 102.9-101.2 nm, respectively, while it is shifted to 98.9-97.8 nm at the loaded nano-TiO(2) mass of 0.92-1.78 mg, respectively. That is, the shift of d(pa50) due to solid particle loading is small if the PENS is not overloaded. Both NPs and RPM concentrations were found to agree well with those of the IOSH respirable cyclone and MOUDI. By using the present PENS, the collected samples can be further analyzed for chemical species concentrations besides gravimetric analysis to determine the actual exposure concentrations of ENMs in both RPM and NPs fractions in workplaces, which are often influenced by the background or incident pollution sources.

Periodic π-conjugated polymers of the group 16 heterocycles (furan, thiophene, and selenophene) were synthesized with controlled chain lengths and relatively low dispersities using catalyst-transfer polycondensation. The optical gap and redox potentials of these copolymers were fine-tuned by altering the heterocycle sequence, and atomic force microscopy revealed nanofibrillar morphologies for all the materials. Grazing incidence wide-angle X-ray scattering of the thiophene-selenophene copolymers indicated that the π-stacking distance increased with incorporation of the larger heteroatom (from ∼3.7-4.0 Å), while the lamellar spacing decreased (from ∼15.8-15.2 Å). The study also revealed that periodic sequences allow electronic properties to be tuned while retaining nanofibrillar morphologies similar to those observed for poly(3-hexylthiophene).

No abstract

There is intense interest in the rational design of semiconducting materials to improve organic electronics. Furan is a particularly attractive monomer for building biorenewable and biodegradable π-conjugated frameworks. In this report, regioregular head-to-tail and head-to-head poly­(3-hexylfuran) were synthesized using chain-growth polycondensation. The resultant polyfurans have relatively low molecular weights but also low dispersities. The head-to-head polyfuran adopted a nearly identical coplanar backbone conformation as its head-to-tail analog in the solid state, as determined by UV–visible spectroscopy and atomic force microscopy. Extensive aggregation of the furan homopolymer during polymerization led to the investigation of an alternating furan-thiophene copolymer, confirming that furyl-based monomers can polymerize in a chain-growth manner. All of the synthesized polymers are sensitive when exposed to both oxygen and light.