Population variation in biomonitoring data for persistent organic pollutants (POPs) : an examination of multiple population-based datasets for application to Australian pooled biomonitoring data

Background Australian national biomonitoring for persistent organic pollutants (POPs) relies upon age-specific pooled serum samples to characterize central tendencies of concentrations but does not provide estimates of upper bound concentrations. This analysis compares population variation from biomonitoring datasets from the US, Canada, Germany, Spain, and Belgium to identify and test patterns potentially useful for estimating population upper bound reference values for the Australian population. Methods Arithmetic means and the ratio of the 95th percentile to the arithmetic mean (P95:mean) were assessed by survey for defined age subgroups for three polychlorinated biphenyls (PCBs 138, 153, and 180), hexachlorobenzene (HCB), p,p-dichlorodiphenyldichloroethylene (DDE), 2,2′,4,4′ tetrabrominated diphenylether (PBDE 47), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Results Arithmetic mean concentrations of each analyte varied widely across surveys and age groups. However, P95:mean ratios differed to a limited extent, with no systematic variation across ages. The average P95:mean ratios were 2.2 for the three PCBs and HCB; 3.0 for DDE; 2.0 and 2.3 for PFOA and PFOS, respectively. The P95:mean ratio for PBDE 47 was more variable among age groups, ranging from 2.7 to 4.8. The average P95:mean ratios accurately estimated age group-specific P95s in the Flemish Environmental Health Survey II and were used to estimate the P95s for the Australian population by age group from the pooled biomonitoring data. Conclusions Similar population variation patterns for POPs were observed across multiple surveys, even when absolute concentrations differed widely. These patterns can be used to estimate population upper bounds when only pooled sampling data are available.

Design of high mobility DPP-based polymer semiconductors for organic thin film transistors

π-Conjugated polymers are the most promising semiconductor materials to enable printed organic thin film transistors (OTFTs) due to their excellent solution processability and mechanical robustness. However, solution-processed polymer semiconductors have shown poor charge transport properties mainly originated from the disordered polymer chain packing in the solid state as compared to the thermally evaporated small molecular organic semiconductors. The low charge carrier mobility, typically < 0.1 cm2 /V.s, of polymer semiconductors poses a challenge for most intended applications such as displays and radio-frequency identification (RFID) tags. Here we present our recent results on the dike topyrrolopyrrole (DPP)-based polymers and demonstrate that when DPP is combined with appropriate electron donating moieties such as thiophene and thienothiophene, very high charge carrier mobility values of ~1 cm2/V.s could be achieved.

A non-fullerene electron acceptor based on fluorene and diketopyrrolopyrrole building blocks for solution-processable organic solar cells with an impressive open-circuit voltage

A novel solution-processable non-fullerene electron acceptor 6,6′-(5,5′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (DPP1) based on fluorene and diketopyrrolopyrrole conjugated moieties was designed, synthesized and fully characterized. DPP1 exhibited excellent solubility and high thermal stability which are essential for easy processing. Upon using DPP1 as an acceptor with the classical electron donor poly(3-hexylthiophene), solution processable bulk-heterojunction solar cells afforded a power conversion efficiency of 1.2% with a high open-circuit voltage (1.1 V). As per our knowledge, this value of open circuit voltage is one of the highest values reported so far for a bulk-heterojunction device using DPP1 as a non-fullerene acceptor.

Hybrid CuTCNQ/AgTCNQ metal-organic charge transfer complexes via galvanic replacement vs. corrosion recrystallization

This study reports a hybrid of two metal-organic semiconductors that are based on organic charge transfer complexes of 7,7,8,8-tetracyanoquinodimethane (TCNQ). It is shown that the spontaneous reaction between semiconducting microrods of CuTCNQ with Ag+ ions leads to the formation of a CuTCNQ/AgTCNQ hybrid, both in aqueous solution and acetonitrile, albeit with completely different reaction mechanisms. In an aqueous environment, the reaction proceeds by a complex galvanic replacement (GR) mechanism, wherein in addition to AgTCNQ nanowires, Ag0 nanoparticles and Cu(OH)2 crystals decorate the surface of CuTCNQ microrods. Conversely, in acetonitrile, a GR mechanism is found to be thermodynamically unfavorable and instead a corrosion-recrystallization mechanism leads to the decoration of CuTCNQ microrods with AgTCNQ nanoplates, resulting in a pure CuTCNQ/AgTCNQ hybrid metal-organic charge transfer complex. While hybrids of two different inorganic semiconductors are regularly reported, this report pioneers the formation of a hybrid involving two metal-organic semiconductors that will expand the scope of TCNQ-based charge transfer complexes for improved catalysis, sensing, electronics and biological applications.

Evaluation of knowledge management performance: An organic approach

Knowledge management (KM) strategy is the planned or actual coordination of a firm's major goals and learning in time; this coordination continually co-aligns the firm's knowledge-based resources with the environment. Based on the organic perspective of strategy, a KM performance evaluation approach should be able to 1) review the knowledge governance mechanisms and learning routines that underpin the KM strategy, as well as the performance outcomes driven by the strategy, and 2) predict the evolution of performance drivers and outcomes into the future to facilitate strategic planning. This study combined a survey study and a system dynamics (SD) simulation to demonstrate the transformation from a mechanistic to an organic perspective on KM strategy and performance evaluation. The survey study was conducted based on a sample of 143 construction contractors and used structural equation modeling (SEM) techniques to develop a KM performance index for reviewing the key elements that underpin KM strategy. The SD simulation predicted the development of KM strategy configurations and the evolution of KM performance over time. The organic KM performance evaluation approach demonstrated by this study has significant potential to improve the alignment of KM strategy within an increasingly dynamic business environment.

Inorganic-organic composite particle as a staged delivery platform for plasmid DNA-based biopharmaceuticals

Infectious diseases such as SARS, influenza and bird flu may spread exponentially throughout communities. In fact, most infectious diseases remain major health risks due to the lack of vaccine or the lack of facilities to deliver the vaccines. Conventional vaccinations are based on damaged pathogens, live attenuated viruses and viral vectors. If the damage was not complete, the vaccination itself may cause adverse effects. Therefore, researchers have been prompted to prepare viable replacements for the attenuated vaccines that would be more effective and safer to use. DNA vaccines are generally composed of a double stranded plasmid that includes a gene encoding the target antigen under the transcriptional directory and control of a promoter region which is active in cells. Plasmid DNA (pDNA) vaccines allow the foreign genes to be expressed transiently in cells, mimicking intracellular pathogenic infection and inducing both humoral and cellular immune responses. Currently, because of their highly evolved and specialized components, viral systems are the most effective means for DNA delivery, and they achieve high efficiencies (generally >90%), for both DNA delivery and expression. As yet, viral-mediated deliveries have several limitations, including toxicity, limited DNA carrying capacity, restricted target to specific cell types, production and packing problems, and high cost. Thus, nonviral systems, particularly a synthetic DNA delivery system, are highly desirable in both research and clinical applications.

Plasmonic effect of annealed gold islands for improving efficiency of organic solar cells

Embedding metallic nanoparticles in organic solar cells can enhance the photoabsorption through light trapping processes. This paper investigates how gold islands obtained by annealing 1–5 nm thick Au layers affect the photoabsorption. Using finite-difference time-domain simulations, the cell efficiency for various island geometries and thicknesses are analyzed and the properties of the islands for maximal photocurrent are discussed. It is shown that a careful choice of size and concentration of gold islands could contribute to enhance the power conversion efficiencies when compared to standard organic solar cell devices. The conclusions are then compared to experimental data for thermally annealed gold islands in bulk heterojunction solar cells. The results of this paper will contribute to the optimization of plasmonic organic solar cell systems and will pave the way for the development of highly efficient organic solar cell devices.

Optical Characterization of the Hole Polaron in a Series of Diketopyrrolopyrrole Polymers Used for Organic Photovoltaics

Abstract: A strategy that is often used for designing low band gap polymers involves the incorporation of electron-rich (donor) and electron-deficient (acceptor) conjugated segments within the polymer backbone. In this paper we investigate such a series of Diketopyrrolopyrrole (DPP)-based co-polymers. The co-polymers consisted of a DPP unit attached to a phenylene, naphthalene, or anthracene unit. Additionally, polymers utilizing either the thiophene-flanked DPP or the furan-flanked DPP units paired with the naphthalene comonomer were compared. As these polymers have been used as donor materials and subsequent hole transporting materials in organic solar cells, we are specifically interested in characterizing the optical absorption of the hole polaron of these DPP based copolymers. We employ chemical doping, electrochemical doping, and photoinduced absorption (PIA) studies to probe the hole polaron absorption spectra. While some donor-acceptor polymers have shown an appreciable capacity to generate free charge carriers upon photoexcitation, no polaron signal was observed in the PIA spectrum of the polymers in this study. The relations between molecular structure and optical properties are discussed. Keywords: organic solar cell; organic photovoltaic; diketopyrrolopyrrole; chemical doping; spectroelectrochemistry; photoinduced absorption; hole polaron

Time-independent charge carrier mobility in a model polymer:fullerene organic solar cell

The technique of photo-CELIV (charge extraction by linearly increasing voltage) is one of the more straightforward and popular approaches to measure the faster carrier mobility in measurement geometries that are relevant for operational solar cells and other optoelectronic devices. It has been used to demonstrate a time-dependent photocarrier mobility in pristine polymers, attributed to energetic relaxation within the density of states. Conversely, in solar cell blends, the presence or absence of such energetic relaxation on transport timescales remains under debate. We developed a complete numerical model and performed photo-CELIV experiments on the model high efficiency organic solar cell blend poly[3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene] (PDPP-TNT):[6,6]-phenyl-C71-butyric-acid-methyl-ester (PC70BM). In the studied solar cells a constant, time-independent mobility on the scale relevant to charge extraction was observed, where thermalisation of photocarriers occurs on time scales much shorter than the transit time. Therefore, photocarrier relaxation effects are insignificant for charge transport in these efficient photovoltaic devices.

Thiophene–tetrafluorophenyl–thiophene : a promising building block for ambipolar organic field effect transistors

A thiophene–tetrafluorophenyl–thiophene donor–acceptor–donor building block was used in combination with a furan-substituted diketopyrrolopyrrole for synthesizing the polymer semiconductor, PDPPF-TFPT. Due to the balance of tetrafluorophenylene/diketopyrrolopyrrole electron-withdrawing and furan/thiophene electron-donating moieties in the backbone, PDPPF-TFPT exhibits ambipolar behaviour in organic thin-film transistors, with hole and electron mobilities as high as 0.40 cm2 V−1 s−1 and 0.12 cm2 V−1 s−1.

Identification of the sources of primary organic aerosols at urban schools : a molecular marker approach

Children are particularly susceptible to air pollution and schools are examples of urban microenvironments that can account for a large portion of children’s exposure to airborne particles. Thus this paper aimed to determine the sources of primary airborne particles that children are exposed to at school by analyzing selected organic molecular markers at 11 urban schools in Brisbane, Australia. Positive matrix factorization analysis identified four sources at the schools: vehicle emissions, biomass burning, meat cooking and plant wax emissions accounting for 45%, 29%, 16% and 7%, of the organic carbon respectively. Biomass burning peaked in winter due to prescribed burning of bushland around Brisbane. Overall, the results indicated that both local (traffic) and regional (biomass burning) sources of primary organic aerosols influence the levels of ambient particles that children are exposed at the schools. These results have implications for potential control strategies for mitigating exposure at schools.

Analyzing the impact of learning inputs on near-to-far terrain traversability estimation

With the increasing need to adapt to new environments, data-driven approaches have been developed to estimate terrain traversability by learning the rover’s response on the terrain based on experience. Multiple learning inputs are often used to adequately describe the various aspects of terrain traversability. In a complex learning framework, it can be difficult to identify the relevance of each learning input to the resulting estimate. This paper addresses the suitability of each learning input by systematically analyzing the impact of each input on the estimate. Sensitivity Analysis (SA) methods provide a means to measure the contribution of each learning input to the estimate variability. Using a variance-based SA method, we characterize how the prediction changes as one or more of the input changes, and also quantify the prediction uncertainty as attributed from each of the inputs in the framework of dependent inputs. We propose an approach built on Analysis of Variance (ANOVA) decomposition to examine the prediction made in a near-to-far learning framework based on multi-task GP regression. We demonstrate the approach by analyzing the impact of driving speed and terrain geometry on the prediction of the rover’s attitude and chassis configuration in a Marsanalogue terrain using our prototype rover Mawson.

Temporal characteristics of melanopsin inputs to the human pupil light reflex

Rods, cones and melanopsin containing intrinsically photosensitive retinal ganglion cells (ipRGCs) operate in concert to regulate pupil diameter. The temporal properties of intrinsic ipRGC signalling are distinct to those of rods and cones, including longer latencies and sustained signalling after light offset. We examined whether the melanopsin mediated post-illumination pupil response (PIPR) and pupil constriction were dependent upon the inter-stimulus interval (ISI) between successive light pulses and the temporal frequency of sinusoidal light stimuli. Melanopsin excitation was altered by variation of stimulus wavelength (464 nm and 638 nm lights) and irradiance (11.4 and 15.2 log photons cm(-2) s(-1)). We found that 6s PIPR amplitude was independent of ISI and temporal frequency for all melanopsin excitation levels, indicating complete summation. In contrast to the PIPR, the maximum pupil constriction increased with increasing ISI with high and low melanopsin excitation, but time to minimum diameter was slower with high melanopsin excitation only. This melanopsin response to briefly presented pulses (16 and 100 ms) slows the temporal response of the maximum pupil constriction. We also demonstrate that high melanopsin excitation attenuates the phasic peak-trough pupil amplitude compared to conditions with low melanopsin excitation, indicating an interaction between inner and outer retinal inputs to the pupil light reflex. We infer that outer retina summation is important for rapidly controlling pupil diameter in response to short timescale fluctuations in illumination and may occur at two potential sites, one that is presynaptic to extrinsic photoreceptor input to ipRGCs, or another within the pupil control pathway if ipRGCs have differential temporal tuning to extrinsic and intrinsic signalling.

Bisphenol A sorption by organo-montmorillonite: Implications for the removal of organic contaminants from water

Remediation of bisphenol A (BPA) from aqueous solutions by adsorption using organoclays synthesized from montmorillonite (MMT) with different types of organic surfactant molecules was demonstrated. High adsorption capacities of the organoclays for the uptake of BPA were observed and these demonstrated their potential application as strong adsorbents for noxious organic water contaminants. The adsorption of BPA was significantly influenced by pH, with increased adsorption of BPA in acidic pH range. However, the organoclays intercalated with highly loaded surfactants and/or large surfactant molecules were less influenced by the pH of the environment and this was thought to be due to the shielding the negative charge from surfactant molecules and the development of more positive charge on the clay surface, which leads to the attraction of anionic BPA even at alkaline pH. The hydrophobic phase created by loaded surfactant molecules contributed to a partitioning phase, interacting with BPA molecules strongly through hydrophobic interaction. Pseudo-second order kinetic model and Langmuir isotherm provided the best fit for the adsorption of BPA onto the organoclays. In addition, the adsorption process was spontaneous and exothermic with lower temperature facilitating the adsorption of BPA onto the organoclays. The described process provides a potential pathway for the removal of BPA from contaminated waters.