Intrinsic carrier multiplication in layered Bi2O2Se avalanche photodiodes with gain bandwidth product exceeding 1 GHz

Emerging layered semiconductors present multiple advantages for optoelectronic technologies including high carrier mobilities, strong light-matter interactions, and tunable optical absorption and emission. Here, metal-semiconductor-metal avalanche photodiodes (APDs) are fabricated from Bi₂O₂Se crystals, which consist of electrostatically bound [Bi₂O₂]²⁺ and [Se]²⁻ layers. The resulting APDs possess an intrinsic carrier multiplication factor up to 400 at 7 K with a responsivity gain exceeding 3,000 A/W and bandwidth of ~ 400 kHz at a visible wavelength of 515.6 nm, ultimately resulting in a gain bandwidth product exceeding 1 GHz. Due to exceptionally low dark currents, Bi₂O₂Se APDs also yield high detectivities up to 4.6 × 10¹⁴ Jones. A systematic analysis of the photocurrent temperature and bias dependence reveals that the carrier multiplication process in Bi₂O₂Se APDs is consistent with a reverse biased Schottky diode model with a barrier height of ~ 44 meV, in contrast to the charge trapping extrinsic gain mechanism that dominates most layered semiconductor phototransistors. In this manner, layered Bi₂O₂Se APDs provide a unique platform that can be exploited in a diverse range of high-performance photodetector applications.

     

HPLC-fluorescence detection and adsorption of bisphenol A, 17beta-estradiol,and 17alpha-ethynyl estradiol on powdered activated carbon

The adsorption of three estrogenic compounds (bisphenol A (BPA), 17beta-estradiol (E2), and 17alpha-ethynyl estradiol (EE2)) on several powdered activated carbons (PAC) was investigated. Without preconcentration, method detection limits (MDL) using high-performance liquid chromatography (HPLC) with fluorescence detection at an excitation wavelength of 280 nm and an emission wavelength of 310 nm were 0.88, 1.15, and 0.96 nM for BPA, E2, and EE2, respectively. Compound recoveries were >90% in raw drinking water matrices. PAC screening studies (six PAC brands) indicated all three compounds were removed by PAC, but the percentage removal ranged from 31% to >99% based upon PAC type/dosage and presence/absence of natural organic matter. The order of removal (E2>EE2>BPA) corresponded with logK(ow) values for the compounds (3.1-4.0, 3.7-3.9, 3.3, respectively). Kinetic and PAC dose-response experiments were conducted with the two best performing PACs. Increasing contact time and PAC dose improved compound removal. Freundlich isotherm parameters were fit to the experimental data. This study confirms that PAC treatment is feasible for >99% removal of three estrogenic compounds from raw drinking waters that may be at risk for containing such compounds, at least at initial concentration of 500 ng/l and higher.     

Evaluation of UV/H2O2 treatment for the oxidation of pharmaceuticals in wastewater

Advanced oxidation treatment using low pressure UV light coupled with hydrogen peroxide (UV/H₂O₂) was evaluated for the oxidation of six pharmaceuticals in three wastewater effluents. The removal of these six pharmaceuticals (meprobamate, carbamazepine, dilantin, atenolol, primidone and trimethoprim) varied between no observed removal and >90%. The role of the water quality (i.e., alkalinity, nitrite, and specifically effluent organic matter (EfOM)) on hydroxyl radical (OH) exposure was evaluated and used to explain the differences in pharmaceutical removal between the three wastewaters. Results indicated that the efficacy of UV/H₂O₂ treatment for the removal of pharmaceuticals from wastewater was a function of not only the concentration of EfOM but also its inherent reactivity towards OH. The removal of pharmaceuticals also correlated with reductions in ultraviolet absorbance at 254 nm (UV₂₅₄), which offers utilities a surrogate to assess pharmaceutical removal efficiency during UV/H₂O₂ treatment.     

Removal of emerging contaminants of concern by alternative adsorbents

The effective removal of emerging contaminants of concern (ECCs) such as endocrine-disrupting chemicals, pharmaceutically active compounds, personal care products, and flame retardants is a desirable water treatment goal. In this study, one activated carbon, one carbonaceous resin, and two high-silica zeolites were studied to evaluate their effectiveness for the removal of an ECC mixture from lake water. Adsorption isotherm experiments were performed with a mixture of 28 ECCs at environmentally relevant concentrations (200–900 ng/L). Among the tested adsorbents, activated carbon was the most effective, and activated carbon doses typically used for taste and odor control in drinking water (<10 mg/L) were sufficient to achieve a 2-log removal for most of the tested ECCs. The carbonaceous resin was less effective than the activated carbon because this adsorbent had a smaller volume of pores in the size range required for the adsorption of many ECCs (6–9 Å). For the removal of ECC mixture constituents, zeolites were less effective than the carbonaceous adsorbents. Because zeolites contain pores of uniform size and shape, a few of the tested ECCs with matching pore size/shape requirements were well removed, but the adsorptive removal of others was negligible, even at zeolite doses of 100 mg/L. The results of this study demonstrate that effective adsorbents for the removal of a broad spectrum of ECCs from water should exhibit heterogeneity in pore size and shape and a large pore volume in the 6–9 Å size range.     

Anti‐HIV Small‐Molecule Binding in the Peptide Subpocket of the CXCR4:CVX15 Crystal Structure

The CXC chemokine receptor 4 (CXCR4) is involved in chemotaxis and serves as a coreceptor for T‐tropic HIV‐1 viral entry, thus making this receptor an attractive drug target. Recently, crystal structures of CXCR4 were reported as complexes with the small molecule IT1t and the CVX15 peptide. Follow‐up efforts to model different antagonists into the small molecule CXCR4:IT1t crystal structure did not generate poses consistent with either the X‐ray crystal structure or site‐directed mutagenesis (SDM). Here, we compare the binding pockets of the two CXCR4 crystal structures, revealing differences in helices IV, V, VI, and VII, with major differences for the His203 residue buried in the binding pocket. The small molecule antagonist AMD11070 was docked into both CXCR4 crystal structures. An AMD11070 pose identified from the CXCR4:CVX15 model presented interactions with Asp171, Glu288, Trp94, and Asp97, consistent with published SDM data, thus suggesting it is the bioactive pose. A CXCR4 receptor model was optimized around this pose of AMD11070, and the resulting model correlated HIV‐1 inhibition with MM‐GBSA docking scores for a congeneric AMD11070‐like series. Subsequent NAMFIS NMR results successfully linked the proposed binding pose to an independent experimental structure. These results strongly suggest that not all small molecules will bind to CXCR4 in a similar manner as IT1t. Instead, the CXCR4:CVX15 crystal structure may provide a binding locus for small organic molecules that is more suitable than the secondary IT1t site. This work is expected to provide modeling insights useful for future CXCR4 antagonist and X4‐tropic HIV‐1 based drug design efforts.     

Oxygen Reduction Reaction Performance of [MTBD][beti]‐Encapsulated Nanoporous NiPt Alloy Nanoparticles

Recent advances in oxygen reduction reaction catalysis for proton exchange membrane fuel cells (PEMFCs) include i) the use of electrochemical dealloying to produce high surface area and sometimes nanoporous catalysts with a Pt‐enriched outer surface, and ii) the observation that oxygen reduction in nanoporous materials can be potentially enhanced by confinement effects, particularly if the chemical environment within the pores can bias the reaction toward completion. Here, these advances are combined by incorporating a hydrophobic, protic ionic liquid, [MTBD][beti], into the pores of high surface‐area NiPt alloy nanoporous nanoparticles (np‐NiPt/C + [MTBD][beti]). The high O₂ solubility of the [MTBD][beti], in conjunction with the confined environment within the pores, biases reactant O₂ toward the catalytic surface, consistent with an increased residence time and enhanced attempt frequencies, resulting in improved reaction kinetics. Half‐cell measurements show the np‐NiPt/C+[MTBD][beti] encapsulated catalyst to be nearly an order of magnitude more active than commercial Pt/C, a result that is directly translated into operational PEMFCs.     

Microstructure and multifunctional properties of liquid + polymer bicomponent structural electrolytes: Epoxy gels and porous monoliths

Multifunctional structural batteries and supercapacitors have the potential to improve performance and efficiency in advanced lightweight systems. A critical requirement is a structural electrolyte with superior multifunctional performance. We present here structural electrolytes prepared by the integration of liquid electrolytes with structural epoxy networks. Two distinct approaches were investigated: direct blending of an epoxy resin with a poly(ethylene‐glycol) (PEG)‐ or propylene carbonate (PC)‐based liquid electrolyte followed by in‐situ cure of the resin; and formation of a porous neat epoxy sample followed by backfill with a PC‐based electrolyte. The results show that in situ cure of the electrolytes within the epoxy network does not lead to good multifunctional performance due to a combination of plasticization of the structural network and limited percolation of the liquid network. In contrast, addition of a liquid electrolyte to a porous monolith results in both good stiffness and high ionic conductivity that approach multifunctional goals. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42681.     

Distribution and Trends in Reference Evapotranspiration in the North China Plain

The distribution and trends in reference evapotranspiration (ETo) are extremely important to water resources planning for agriculture, and it is widely believed that rates of ETo will increase with global warming. This is a big concern in China, where water deficits are common in the North China Plain (NCP). In this study, Penman-Monteith reference evapotranspiration at 26 meteorological stations during 1961–2006 in and around the NCP was calculated. The temporal variations and spatial distribution of ETo were analyzed and the causes for the variations were discussed. The results showed that: (1) the NCP was divided into two climatic regions based on aridity values: a semiarid region that accounts for 69% of the area and subhumid regions that made of the remaining area; (2) over the entire NCP, the highest annual ETo occurred in the central and western areas and the lowest total ETo was observed in the east. Comparing the mean monthly ETo and annual ETo distributions, the high ETo values from May through July mainly determined the annual ETo distribution; (3) for the whole NCP, annual ETo showed a statistically significant decrease of 11.92 mm/decade over the 46 years of data collection in the NCP or approximately a 5% total decrease compared to the ETo values in 1961; (4) to determine which variable has the greatest effect on the decrease in ETo, decadal changes were observed for daily values of maximum air temperature (+0.16°C), minimum air temperature (+0.35°C), net radiation (?0.13?MJ?m?2), and mean wind speed (?0.09?m?s?1). These results indicate that the decreasing net radiation and wind speed had a bigger impact on ETo rates than the increases observed by the maximum and minimum temperatures.