Alternate and new brominated flame retardants detected in U.S. house dust

Due to the voluntary withdrawals and/or bans on the use of two polybrominated diphenyl ether (PBDE) commercial mixtures, an increasing number of alternate flame retardant chemicals are being introduced in commercial applications. To determine if these alternate BFRs are present in indoor environments, we analyzed dust samples collected from 19 homes in the greater Boston, MA area during 2006. Using pure and commercial standards we quantified the following brominated flame retardant chemicals using GC/ECNI-MS methods: hexabromocyclododecane (sigma HBCD), bis(2,4,6,-tribromphenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), and the brominated components found in Firemaster 550 (FM 550): 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB) and (2-ethylhexyl)tetrabromophthalate (TBPH), the latter compound being a brominated analogue of di(2-ethylhexyl)phthalate (DEHP). The concentrations of all compounds were log-normally distributed and the largest range in concentrations was observed for HBCD (sum of all isomers), with concentrations ranging from <4.5 ng/g to a maximum of 130,200 ng/g with a median value of 230 ng/g. BTBPE ranged from 1.6 to 789 ng/g with a median value of 30 ng/g and DBDPE ranged from <10.0 to 11,070 ng/g with a median value of 201 ng/g. Of the FM 550 components, TBB ranged from <6.6 to 15,030 ng/g with a median value of 133 ng/g; whereas TBPH ranged from 1.5 to 10,630 ng/g with a median value of 142 ng/g. Furthermore, the ratio of TBB/TBPH present in the dust samples ranged from 0.05 to 50 (average 4.4), varying considerably from the ratio observed in the FM 550 commercial mixture (4:1 by mass), suggesting different sources with different chemical compositions, and/or differential fate and transport within the home. Analysis of paired dust samples collected from different rooms in the same home suggests HBCD, TBB, and TBPH are higher in dust from the main living area compared to dust collected in bedrooms; however, BTBPE and DBDPE levels were comparable between rooms. This study highlights the fact that numerous types of brominated flame retardants are present in indoor environments, raising questions about exposure to mixtures of these contaminants.     

Environmentally-relevant forms of the prion protein

Scrapie and chronic wasting disease (CWD) are prion diseases of particular environmental concern as they are horizontally transmissible and can remain infectious after years in the environment. Recent evidence suggests that the N-terminus of PrPSC, the infectious conformation of the prion protein, plays an important role in the mechanism of sorption to soil particles. We hypothesize that, in a prion-infected animal carcass, a portion of the N-terminus of PrPSc could be cleaved by proteinases in the brain at ordinary temperatures. Hamster (HY transmissible mink encephalopathy-infected), transgenic mice (CWD-infected), and elk (CWD-infected) brain homogenates were incubated at 22 and 37 degrees C for up to 1 month and then analyzed by Western blot using N-terminal and middle region monoclonal anti-PrP antibodies. For all three systems, there was a very faint or undetectable N-terminal PrP signal after 35 days at both temperatures, which indicates that full-length PrPSc might be rare in the brain matter of animal carcasses. Future studies on prion-soil interactions should therefore consider N-terminal-degraded PrPSc in addition to the full-length form. Both mouse and elk CWD PrPSc demonstrated greater resistance to degradation than HY TME PrPSc. This indicates that the transgenic mouse-CWD model is a good surrogate for natural CWD prions, but that other rodent prion models might not accurately represent CWD prion fate in the environment.     

Use of newborn screening program blood spots for exposure assessment: declining levels of perluorinated compounds in New York State infants

Temporal biomonitoring studies can assess changes in population exposures to contaminants, but collection of biological specimens with adequate representation and sufficient temporal resolution can be resource-intensive. Newborn Screening Programs (NSPs) collect blood as dried spots on filter paper from nearly all infants born in the United States (U.S.). In this study, we investigated the use of NSP blood spots for temporal biomonitoring by analyzing perfluorooctane sulfonate (PFOS), perfluorooctane sulfonamide (PFOSA), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) in 110 New York State (NYS) NSP blood spot composite specimens collected between 1997 and 2007, representing a total of 2640 infants. All analytes were detected in > or =90% of the specimens. Concentrations of PFOS, PFOSA, PFHxS, and PFOA exhibited significant exponential declines after the year 2000, coinciding with the phase-out in PFOS production in the U.S. Calculated disappearance half-lives for PFOS, PFHxS, and PFOA (4.4, 8.2, and 4.1 years, respectively) were similar to biological half-lives reported for retired fluorochemical workers. Our results suggest sharp decreases in perinatal exposure of NYS infants to PFOS, PFOSA, PFHxS, and PFOA and demonstrate, for the first time, the utility of NSP blood spots for assessment of temporal trends in exposure.     

Synthesis and Anticancer Properties of Oxazepines Related to Azaisoerianin and IsoCoQuines

In this article, we report the synthesis and biological properties of a series of novel oxazepines related to isoCA-4 having significant antitumor properties. Among them, three oxazepin-9-ol derivatives display a nanomolar or a sub-nanomolar cytotoxicity level against five human cancer cell lines (HCT116, U87, A549, MCF7, and K562). It was demonstrated that the lead compound in this series inhibits tubulin assembly with an IC₅₀ value of 1 μM and totally arrests the cellular cycle in the G2/M phase at the low concentration of 5 nM in HCT116 and K562 cells. Molecular modeling studies perfectly corroborates these promising results.     

Comparison of two low-hazard organic solvents as individual and cosolvents for the fabrication of polysulfone membranes

Petroleum-derived solvents commonly used in membrane fabrication are often hazardous and toxic, so the investigation of safer alternatives is important. In this study, two low-hazard solvents, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate (Rhodiasolv® PolarClean) and gamma-valerolactone (GVL), were investigated as sole solvents and as cosolvents to cast polysulfone membranes via nonsolvent induced phase inversion. Normalized viscosity was introduced as an indicator of dope solution homogeneity and was used to compare the required time of mixing to achieve full dissolution of the polymer in the different solvents/solvent mixtures. All dope solutions made with low-hazard solvents were found to be more viscous than those made with traditional solvents, which meant additional mixing time was needed, and that fabricated membranes were morphologically different. With respect to operation, membranes cast from dope solutions containing equal amounts of PolarClean and GVL displayed the most similar flux curves and solute rejection to those made using the traditional solvent tested.     

Modelling the propagation of social response during a disease outbreak

Epidemic trajectories and associated social responses vary widely between populations, with severe reactions sometimes observed. When confronted with fatal or novel pathogens, people exhibit a variety of behaviours from anxiety to hoarding of medical supplies, overwhelming medical infrastructure and rioting. We developed a coupled network approach to understanding and predicting social response. We couple the disease spread and panic spread processes and model them through local interactions between agents. The social contagion process depends on the prevalence of the disease, its perceived risk and a global media signal. We verify the model by analysing the spread of disease and social response during the 2009 H1N1 outbreak in Mexico City and 2003 severe acute respiratory syndrome and 2009 H1N1 outbreaks in Hong Kong, accurately predicting population-level behaviour. This kind of empirically validated model is critical to exploring strategies for public health intervention, increasing our ability to anticipate the response to infectious disease outbreaks.     

Fiber Reinforced Layered Dielectric Nanocomposite

Polymer dielectrics find applications in modern electronic and electrical technologies due to their low density, durability, high dielectric breakdown strength, and design flexibility. However, they are not reliable at high temperatures due to their low mechanical integrity and thermal stability. Herein, a self‐assembled dielectric nanocomposite is reported, which integrates 1D polyaramid nanofibers and 2D boron nitride nanosheets through a vacuum‐assisted layer‐by‐layer infiltration process. The resulting nanocomposite exhibits hierarchical stacking between the 2D nanosheets and 1D nanofibers. Specifically, the 2D nanosheets provide a thermally conductive network while the 1D nanofibers provide mechanical flexibility and robustness through entangled nanofiber–nanosheet morphologies. Experiments and density functional theory show that the nanocomposites through thickness heat transfer processes are nearly identical to that of boron nitride due to synergistic stacking of polyaramid units onto boron nitride nanosheets through van der Waals interactions. The nanocomposite sheets outperform conventional dielectric polymers in terms of mechanical properties (about 4–20‐fold increase of stiffness), light weight (density ≈1.01 g cm^?3), dielectric stability over a broad range of temperature (25–200 °C) and frequencies (10³–10⁶ Hz), good dielectric breakdown strength (≈292 MV m^?1), and excellent thermal management capability (about 5–24 times higher thermal conductivity) such as fast heat dissipation.     

Few‐Layer GeAs Field‐Effect Transistors and Infrared Photodetectors

The family of 2D semiconductors (2DSCs) has grown rapidly since the first isolation of graphene. The emergence of each 2DSC material brings considerable excitement for its unique electrical, optical, and mechanical properties, which are often highly distinct from their 3D counterparts. To date, studies of 2DSC are majorly focused on group IV (e.g., graphene, silicene), group V (e.g., phosphorene), or group VIB compounds (transition metal dichalcogenides, TMD), and have inspired considerable effort in searching for novel 2DSCs. Here, the first electrical characterization of group IV–V compounds is presented by investigating few‐layer GeAs field‐effect transistors. With back‐gate device geometry, p‐type behaviors are observed at room temperature. Importantly, the hole carrier mobility is found to approach 100 cm² V^?1 s^?1 with ON–OFF ratio over 10⁵, comparable well with state‐of‐the‐art TMD devices. With the unique crystal structure the few‐layer GeAs show highly anisotropic optical and electronic properties (anisotropic mobility ratio of 4.8). Furthermore, GeAs based transistor shows prominent and rapid photoresponse to 1.6 µm radiation with a photoresponsivity of 6 A W^?1 and a rise and fall time of ≈3 ms. This study of group IV–V 2DSC materials greatly expands the 2D family, and can enable new opportunities in functional electronics and optoelectronics based on 2DSCs.     

Cyclic stretch down-regulates calcium transporter gene expression in neonatal rat ventricular myocytes

Abnormal intracellular Ca2+ handling in hypertrophied and failing hearts is partly due to changes in Ca2+ transporter gene expression, but the mechanisms responsible for these alterations remain largely unknown. We previously showed that intrinsic mechanical load (i.e. spontaneous contractile activity) induced myocyte hypertrophy, and down-regulated SR Ca2+ ATPase (SERCA2) gene expression in cultured neonatal rat ventricular myocytes (NRVM). In the present study, we examined whether extrinsic mechanical load (i.e. cyclic stretch) also induced NRVM hypertrophy, and led to down-regulation of SERCA2 and other Ca2+ transporter genes which have been associated with cardiac hypertrophy and failure in vivo. NRVM were maintained in serum-free culture medium under control conditions, or subjected to cyclic mechanical deformation (1.0 Hz, 20% maximal strain, 48 h). Under these conditions, cyclic stretch induced NRVM hypertrophy, as evidenced by significant increases in total protein/DNA ratio, myosin heavy chain (MHC) content, and atrial natriuretic factor (ANF) secretion. Cyclic stretch also induced the MHC isoenzyme "switch" which is characteristic of hemodynamic overload of the rat heart in vivo. Cyclic stretch significantly down-regulated SERCA2 and ryanodine receptor (RyR) mRNA and protein levels, while simultaneously increasing ANF mRNA. In contrast, Na+-Ca2+ exchanger and phospholamban mRNA levels were unaffected. Load-dependent SERCA2 and RyR down-regulation was independent of Ca2+ influx via voltage-gated, L-type Ca2+ channels, as cyclic stretch down-regulated SERCA2 and RyR mRNA levels in both control and verapamil-treated NRVM. These results indicate that extrinsic mechanical load (in the absence of other exogenous stimuli) induces NRVM hypertrophy and causes down-regulation of Ca2+ transporter gene expression. This in vitro model system should prove useful to dissect the intracellular signaling pathways responsible for transducing this phenotype during cardiac hypertrophy and heart failure in vivo.