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 (ΦF =0.31) among the known [9]helicenes. Chiral resolution of the racemic pentaaza[9]helicene and hexathia[9]/[5]helicene were achieved by chiral-phase HPLC and the enantiomers were characterized by circular dichroism spectra and DFT calculations.

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 (16.9 to 1100 µg L-1), and the linearity was dependent upon the Henry's constant (H). The average diffusivity of the VOCs in the solid ceramic was 1.46 × 10-10 m2 s-1 at 25 °C, which was 4 orders of magnitude lower than that in air (8.09 × 10-6 m2 s-1). This value was 60% greater than that in the water-permeable porous ceramic (0.92 × 10-10 m2 s-1), suggesting that its mass accumulation could be more effective than that of porous ceramic dosimeters. The mass accumulation of the VOCs in the solid ceramic dosimeter increased in the presence of salt (≥0.1 M) and with increasing temperature (4 to 40 °C) but varied only slightly with dissolved organic matter concentration. The solid ceramic dosimeter was suitable for the field testing and measurement of time-weighted average concentrations of VOC-contaminated waters.

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. We present a wearable/disposable sweat-based glucose monitoring device integrated with a feedback transdermal drug delivery module. Careful multilayer patch design and miniaturization of sensors increase the efficiency of the sweat collection and sensing process. Multimodal glucose sensing, as well as its real-time correction based on pH, temperature, and humidity measurements, maximizes the accuracy of the sensing. The minimal layout design of the same sensors also enables a strip-type disposable device. Drugs for the feedback transdermal therapy are loaded on two different temperature-responsive phase change nanoparticles. These nanoparticles are embedded in hyaluronic acid hydrogel microneedles, which are additionally coated with phase change materials. This enables multistage, spatially patterned, and precisely controlled drug release in response to the patient's glucose level. The system provides a novel closed-loop solution for the noninvasive sweat-based management of diabetes mellitus.

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. Mixed N-substituted [8]circulenes have been also prepared.

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. Using the diffusion coefficients for artificial lake and estuarine waters containing inorganic salts, rather than those for lake and estuarine waters containing Suwannee River humic acid (∼5 mg C L(-1) ), the DGT method demonstrated similar Hg and MMHg profiles to those using the centrifugation method. Based on the need for fine vertical resolution and high metal concentrations to be collected, DGT is suggested to be a reliable method for determining Hg(II) and MMHg depth profiles in sediment porewater.

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)=0.55 in THF), and a single exponential fluorescence decay with τ(F)=3.8 ns. These observations indicate a dominant contribution of an [8]radialene-like π conjugation and hence aromatic character of the local aromatic segments in 1.

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). Regressions developed for Hg biomagnification in the food chain were log10 CTHg (nanograms per gram) =0.27 × Î´(15) N (‰) - 0.42, R(2) =0.87, for THg and log10 CMMHg =0.33 × Î´(15) N (‰) - 1.0, R(2) =0.93, for MMHg. Unlike Hg, nearly constant TSe concentrations were observed at 248 ± 179 ng g(-1) in the food web, and the TSe-to-THg molar ratio was predicted by log10 (CTSe /CTHg ) = -0.10 × Î´(15) N (‰) +2.8, R(2) =0.60. The THg-uptake rates of Sarasota bottlenose dolphins are estimated to vary between 2.1 and 4.9 µg kg(-1) d(-1) ; however, the estimated TSe-uptake rates (15.1 µg kg(-1) d(-1) ) were higher than those for THg, and the Hg-exposure risks of the Sarasota Bay resident bottlenose dolphins are considered to be low. Approaches employed in the present study can be extended to other environments to characterize Hg contamination in aquatic systems and Hg exposure risks in top predators.

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. The diet fish total Hg concentrations ranged between 14 and 47 ng g(-1) and were markedly lower than for similar fish found in Florida, South Carolina, and other aquaria. CH(3)Hg(+) accounted for 85 to 91% of the total Hg found in diet fish. The diet fish Se concentrations ranged between 270 and 800 ng g(-1), indicating excess molar concentrations of Se over Hg. The Hg concentration range in the blood of NAB dolphins was 27-117 ng g(-1) and the concentrations were about one order of magnitude and several factors lower than the concentrations found in the blood of wild bottlenose dolphins in Florida and in South Carolina, respectively. The total Hg and CH(3)Hg(+) in tissue samples were also significantly lower than the reported values obtained from wild populations of bottlenose dolphins. The differences in the Hg concentrations in the dolphins' blood may be due to the different levels of Hg atmospheric deposition in the area where the dolphins' diet fish were found. The Se concentration range in the blood of NAB dolphins was 221-297 ng g(-1) which was two factors lower than the values found in wild populations. The lower Hg levels, as well as higher Se:Hg molar ratios in the blood of NAB dolphins, suggest that NAB dolphins may be less susceptible to the potential neurotoxicity from the CH(3)Hg(+) in their blood.

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 5.26 (±0.27) × 10(-6) and 4.02 (±0.10) × 10(-6) cm(2) s(-1), respectively. The effective diffusion coefficients of CH(3)Hg(+) and Hg(2+) complexes in the agarose diffusion layer with dissolved organic matter was 3.57 (±0.29) × 10(-6) and 2.16 (±0.19) × 10(-6) cm(2) s(-1), respectively. The practical method detection limits are 0.1 and 0.7 ng L(-1) for CH(3)Hg(+) and Hg(2+) respectively for three weeks deployment. Lower detection limits would be possible by employing a thinner agarose diffusive layer and/or by deploying the probes longer. The method can measure time averaged CH(3)Hg(+) and Hg(2+) concentrations simultaneously in oxic water, making it useful as an in situ monitoring tool.

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. At the conclusion of the experiments, the vertical profiles of acid volatile sulfide (AVS) and simultaneously extracted metals (SEM) as well as porewater metals and anion concentrations were characterized. Acid volatile sulfide oxidation at the sediment surface led to a commensurate increase in dissolved metal species and metal release that was strongly dependent on the changes in the overlying water characteristics. Total Cd release was substantially higher during exposure to salt water, although, as a result of complexation, predicted dissolved Cd(2+) concentration in the overlying water was higher during exposure to freshwater. Total Zn release was little changed during exposure to salt water and freshwater, although the predicted dissolved Zn(2+) concentration was much higher during freshwater exposures. No significant iron was released because of the rapid oxidation of ferrous iron (Fe(2+)) in aerobic surficial sediments and overlying water. The present study suggests that cyclic changes in pH and salinity in the overlying water can dramatically influence metal release from estuarine sediments.

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. The proposed model and parameters were then applied, without further calibration, to literature-reported experimental observations of resuspension in an acid sulfate soil collected in a coastal flood plain. The model provided a good description of the dynamics of AVS, Fe(2+), S(0)((s)), pH, dissolved carbonates concentrations, and the release of Ca((aq)), Mg((aq)), and Zn((aq)) in both sediments. Accurate predictions of Mn((aq)) release required adjustment of sorption partitioning coefficient, presumably due to the presence of Mn scavenging by phases not accounted for in the model. The oxidation of AVS (and the resulting release of sulfide-bound metals) was consistent with a two-step process, a relatively rapid AVS oxidation to elemental sulfur (S(0)((s))) and a slow oxidation of S(0)((s)) to SO(4)(2-)((aq)), with an associated decrease in pH from neutral to acidic conditions. This acidification was the dominant factor for the release of metals into the aqueous phase.