Development of Solid Ceramic Dosimeters for the Time-Integrative Passive Sampling of Volatile Organic Compounds in Waters.

Time-integrative passive sampling of volatile organic compounds (VOCs) in water can now be accomplished using a solid ceramic dosimeter. A nonporous ceramic, which excludes the permeation of water, allowing only gas-phase diffusion of VOCs into the resin inside the dosimeter, effectively captured the VOCs. The mass accumulation of 11 VOCs linearly increased with time over a wide range of aqueous-phase concentrations (16.

Closed Pentaaza[9]helicene and Hexathia[9]/[5]helicene: Oxidative Fusion Reactions of ortho-Phenylene-Bridged Cyclic Hexapyrroles and Hexathiophenes.

Oxidative fusion reactions of ortho-phenylene-bridged cyclic hexapyrroles and hexathiophenes furnished novel closed helicenes in a selective manner. X-Ray diffraction analysis unambiguously revealed the structures to be a closed pentaaza[9]helicene, the longest azahelicene reported so far, and an unexpected double-helical structure of hexathia[9]/[5]helicene, whose formation was assumed to result from multiple oxidative fusion along with a 1,2-aryl shift. The pentaaza[9]helicene exhibited well-defined emission with high fluorescence quantum yield (Φ =0.

Sequential N-Alkylations of Tetrabenzotetraaza[8]circulene as a Tool To Tune Its Optical Properties.

Sequential N-alkylations of tetrabenzotetraaza[8]circulene provided mono-, di-, tri, and tetra-N-alkylated products in a controlled manner. Curiously, only opp isomer was obtained as a di-N-alkylated product. Upon increase of the N-alkyl groups, the absorption and emission spectra exhibit continuous red-shifts, and the excited-state lifetimes become shortened, probably because of increased steric congestion at the nitrogen atoms that causes the central core to deviate from planarity.

Wearable/disposable sweat-based glucose monitoring device with multistage transdermal drug delivery module.

Electrochemical analysis of sweat using soft bioelectronics on human skin provides a new route for noninvasive glucose monitoring without painful blood collection. However, sweat-based glucose sensing still faces many challenges, such as difficulty in sweat collection, activity variation of glucose oxidase due to lactic acid secretion and ambient temperature changes, and delamination of the enzyme when exposed to mechanical friction and skin deformation. Precise point-of-care therapy in response to the measured glucose levels is still very challenging.

Application of diffusive gradients in thin films and core centrifugation methods to determine inorganic mercury and monomethylmercury profiles in sediment porewater.

A diffusive gradient in thin films (DGT) is an in situ sampling technique for the quantitative analysis of contaminant concentrations that is based on the diffusion and adsorption of contaminants on to resin gels. In the present study, a DGT technique was applied to measure total mercury (Hg) and monomethylmercury (MMHg) concentrations in lake and coastal sediment porewaters and compare them with those from ex situ sediment centrifugation. To calculate the total Hg and MMHg concentrations in porewater using the DGT method, the diffusion coefficients of Hg species in a diffusive gel medium was first determined, and then total Hg and MMHg depth profiles were measured using the experimentally determined diffusion coefficients.

Synthesis of a Tetrabenzotetraaza[8]circulene by a "Fold-In" Oxidative Fusion Reaction.

Tetrabenzotetraaza[8]circulene (1) has been synthesized in good yield by a "fold-in" oxidative fusion reaction of a 1,2-phenylene-bridged cyclic tetrapyrrole. X-ray diffraction analysis of 1 has revealed a planar square structure with a central cyclooctatetraene (COT) core that shows little alternation of the bond lengths. Despite these structural features, 1 shows aromatic-like character, such as sharp absorption bands, high fluorescence quantum yields (Φ(F)=0.

Bioaccumulation and biomagnification of mercury and selenium in the Sarasota Bay ecosystem.

The bioaccumulation and biomagnification of Hg and Se were investigated in Sarasota Bay, Florida, USA, to characterize the Hg exposure risks to wild bottlenose dolphins in the bay. Concentrations of total mercury (THg), monomethylmercury (MMHg), and total selenium (TSe) were monitored in the bay, the latter of which might reduce Hg toxicity. The food web structure and dolphins' trophic level-specific consumption rates were evaluated using stable isotope ratios of carbon (δ(13) C) and nitrogen (δ(15) N).

Assessment of mercury and selenium concentrations in captive bottlenose dolphin's (Tursiops truncatus) diet fish, blood, and tissue.

Concentrations of total mercury (Hg) and selenium (Se) were determined in diet fish and whole blood and tissue samples from seven bottlenose dolphins (Tursiops truncatus) housed at the National Aquarium Baltimore (NAB). In addition, concentrations of monomethylmercury (CH(3)Hg(+)) were determined in diet fish and dolphins' tissue samples. The data were compared with the values found in wild populations to better understand how the dietary Hg and Se uptake rates affect the Hg and Se levels in dolphins.

Combination of diffusive gradient in a thin film probe and IC-ICP-MS for the simultaneous determination of CH3Hg+ and Hg2+ in oxic water.

A diffusive gradient in thin film technique (DGT) was combined with ion chromatography and inductively coupled plasma mass spectrometry (IC-ICP-MS) for the in situ simultaneous quantification of CH(3)Hg(+) and Hg(2+) in aquatic environments. After diffusing through an agarose diffusive layer, the Hg species accumulated in a thiol-functionalized resin layer and were extracted using acidic thiourea solution to form stable thiourea-Hg complexes that were separated and detected via ion chromatography and ICP-MS, respectively. The effective diffusion coefficients of CH(3)Hg(+) and Hg(2+) complexes in the agarose diffusion layer with chloride were 5.

Effects of cyclic changes in pH and salinity on metals release from sediments.

The effects of dynamic changes in pH and salinity on metal speciation and release are investigated with sediments posed in a simulated estuarine environment. The release of Zn, Cd, Mn, and Fe was studied using sediment from the Anacostia River (Washington, DC, USA) spiked with freshly precipitated amorphous cadmium sulfide to increase Cd content. The sediment was exposed to salt water (high pH, ionic strength) and freshwater (neutral pH, minimal ionic strength) continuously and alternately (to mimic tidal changes) in small microcosms over 100 d.

Acid volatile sulfides oxidation and metals (Mn, Zn) release upon sediment resuspension: laboratory experiment and model development.

Sediment from the Anacostia River (Washington, DC, USA) was suspended in aerobic artificial river water for 14 d to investigate the dynamics of dissolved metals release and related parameters including pH, acid volatile sulfides (AVS), and dissolved/solid phase Fe(2+). To better understand and predict the underlying processes, a mathematical model is developed considering oxidation of reduced species, dissolution of minerals, pH changes, and pH-dependent metals' sorption to sediment. Oxidation rate constants of elemental sulfur and zinc sulfide, and a dissolution rate constant of carbonate minerals, were adjusted to fit observations.