Dibenzoacridines: synthesis by alkyne-carbonyl-metathesis and properties.

Dibenzo[a,j]acridines and regioisomeric dibenzo[c,h]acridines were synthesized from a common starting material, 2,3,5,6-tetrachloropyridine, by combination of site-selective cross-coupling reaction followed by ring-closing alkyne-carbonyl metathesis using simple Brønsted acids. The two regioisomeric series were accessed by change of the order of Sonogashira and Suzuki-Miyaura reactions. The optical properties of the products were studied by steady-state absorption spectroscopy and time-resolved emission measurements. The electronic properties of the products were further elucidated by DFT calculations.

The Ozonolysis of Methylated Selenide Compounds in the Atmosphere: Isotopes, Kinetics, Products, and Mechanisms.

Selenium (Se) is an essential micronutrient with an important atmospheric component in its biogeochemical cycle. In this cycle, phytoplankton form volatile organic Se species, such as dimethyl selenide (CH3SeCH3) and dimethyl diselenide (CH3SeSeCH3), which are emitted into the atmosphere. To predict the atmospheric fate of these methylated Se compounds, we investigated their ozonolysis reaction. We used proton-transfer-reaction time-of-flight mass spectrometry to quantify atmospheric Se and its isotopes, and used this method in kinetic and product studies. The ozonolysis of CH3SeCH3 proceeded with a rate constant of (7.4 ± 2.2) × 10-17 cm3 molec-1 s-1 at 26 ± 1 °C with an activation energy of 50 ± 14 kJ mol-1 forming dimethyl selenoxide (CH3Se(O)CH3). Comparatively, CH3SeSeCH3 reacted with O3 at (2.6 ± 0.9) × 10-17 cm3 molec-1 s-1 at 27 ± 1 °C with an activation energy of 56 ± 5 kJ mol-1 forming methylselinic acid (CH3Se(O)OH). At 20 ppbv of O3, the atmospheric lifetimes of CH3SeCH3 and CH3SeSeCH3 are 7.6 and 22 h, respectively. The Se oxidation products were confirmed by synthesis and can serve as new atmospheric tracers of methylated Se compounds. Overall, we measured Se isotopes in real time and determined the rate constants, activation energies, and oxidation products. These mechanisms can now be used to determine the quantitative atmospheric fate of Se toward O3, and thus its distribution within a changing climate.

Urban-Soil Pedogenesis Drives Contrasting Legacies of Lead from Paint and Gasoline in City Soil.

This study analyzed the impact of urban-soil pedogenesis on soil lead (Pb) contamination from paint and gasoline in the historic core of Durham, North Carolina. Total soil Pb in 1000 samples from streetsides, residential properties, and residual upland and floodplains ranged from 6 to 8825 mg/kg (mean = 211 mg/kg), with 50% of samples between 50 and 200 mg/kg soil Pb. The highest Pb concentrations were within 1 m of pre-1978 residential foundations, with concentrations inversely correlated with house age. Streetside soil Pb concentrations were elevated over the geologic background of <30 mg/kg and correlated with traffic flow. Streetside soil Pb concentrations were lower than Durham streetside soils collected in the 1970s, which was attributed to urban pedogenesis, the complex of natural and human processes that change soils over time. Accelerated erosion redistributes legacy Pb and floodplain sampling indicates sedimentation rates of up to 4 mm/year. Mixing and burial of soil with elevated Pb are also lowering soil Pb concentrations over time. These mechanisms are likely of greater significance on streetsides than near foundation soils. The development of an urban-pedogenesis framework can help guide public health approaches to Pb exposure by incorporating pedogenic processes that reduce and dissipate soil Pb contamination.

Neuronal and metastatic cancer cells: Unlike brothers.

During development neuronal cells traverse substantial distances across the developing tissue. In the mature organism, however, they are bound to the confines of the nervous system. Likewise metastatic cancer cells have the potential to establish auxiliary tumor sites in remote tissues or entirely different organs. The epithelial-mesenchymal transition is the transformation of proliferative cancer cells into a highly invasive state, which facilitates the crossing of tissue boundaries and migration across various environments. This review contributes a first look into the parallels and contrasts between physical aspects of neuronal and metastatic cancer cells.

Surficial gains and subsoil losses of soil carbon and nitrogen during secondary forest development.

Reforestation of formerly cultivated land is widely understood to accumulate above- and belowground detrital organic matter pools, including soil organic matter. However, during 40 years of study of reforestation in the subtropical southeastern USA, repeated observations of above- and belowground carbon documented that significant gains in soil organic matter (SOM) in surface soils (0-7.5 cm) were offset by significant SOM losses in subsoils (35-60 cm). Here, we extended the observation period in this long-term experiment by an additional decade, and used soil fractionation and stable isotopes and radioisotopes to explore changes in soil organic carbon and soil nitrogen that accompanied nearly 50 years of loblolly pine secondary forest development. We observed that accumulations of mineral soil C and N from 0 to 7.5 cm were almost entirely due to accumulations of light-fraction SOM. Meanwhile, losses of soil C and N from mineral soils at 35 to 60 cm were from SOM associated with silt and clay-sized particles. Isotopic signatures showed relatively large accumulations of forest-derived carbon in surface soils, and little to no accumulation of forest-derived carbon in subsoils. We argue that the land use change from old field to secondary forest drove biogeochemical and hydrological changes throughout the soil profile that enhanced microbial activity and SOM decomposition in subsoils. However, when the pine stands aged and began to transition to mixed pines and hardwoods, demands on soil organic matter for nutrients to support aboveground growth eased due to pine mortality, and subsoil organic matter levels stabilized. This study emphasizes the importance of long-term experiments and deep measurements when characterizing soil C and N responses to land use change and the remarkable paucity of such long-term soil data deeper than 30 cm.

Different modes of growth cone collapse in NG 108-15 cells.

In the fundamental process of neuronal path-finding, a growth cone at the tip of every neurite detects and follows multiple guidance cues regulating outgrowth and initiating directional changes. While the main focus of research lies on the cytoskeletal dynamics underlying growth cone advancement, we investigated collapse and retraction mechanisms in NG108-15 growth cones transiently transfected with mCherry-LifeAct and pCS2+/EMTB-3XGFP for filamentous actin and microtubules, respectively. Using fluorescence time lapse microscopy we could identify two distinct modes of growth cone collapse leading either to neurite retraction or to a controlled halt of neurite extension. In the latter case, lateral movement and folding of actin bundles (filopodia) confine microtubule extension and limit microtubule-based expansion processes without the necessity of a constantly engaged actin turnover machinery. We term this previously unreported second type fold collapse and suggest that it marks an intermediate-term mode of growth regulation closing the gap between full retraction and small scale fluctuations.

Development and deployment of a field-portable soil O2 and CO2 gas analyzer and sampler.

Here we present novel method development and instruction in the construction and use of Field Portable Gas Analyzers study of belowground aerobic respiration dynamics of deep soil systems. Our Field-Portable Gas Analysis (FPGA) platform has been developed at the Calhoun Critical Zone Observatory (CCZO) for the measurement and monitoring of soil O2 and CO2 in a variety of ecosystems around the world. The FPGA platform presented here is cost-effective, lightweight, compact, and reliable for monitoring dynamic soil gasses in-situ in the field. The FPGA platform integrates off-the-shelf components for non-dispersive infrared (NDIR) CO2 measurement and electro-chemical O2 measurement via flow-through soil gas analyses. More than 2000 soil gas measurements have been made to date using these devices over 4 years of observations. Measurement accuracy of FPGAs is consistently high as validated via conventional bench-top gas chromatography. Further, time series representations of paired CO2 and O2 measurement under hardwood forests at the CCZO demonstrate the ability to observe and track seasonal and climatic patterns belowground with this FPGA platform. Lastly, the ability to analyze the apparent respiratory quotient, the ratio of apparent CO2 accumulation divided by apparent O2 consumption relative to the aboveground atmosphere, indicates a high degree of nuanced analyses are made possible with tools like FPGAs. In sum, the accuracy and reliability of the FPGA platform for soil gas monitoring allows for low-cost temporally extensive and spatially expansive field studies of deep soil respiration.

Four-decade responses of soil trace elements to an aggrading old-field forest: B, Mn, Zn, Cu, and Fe.

In the ancient and acidic Ultisol soils of the Southern Piedmont, USA, we studied changes in trace element biogeochemistry over four decades, a period during which formerly cultivated cotton fields were planted with pine seedlings that grew into mature forest stands. In 16 permanent plots, we estimated 40-year accumulations of trace elements in forest biomass and O horizons (between 1957 and 1997), and changes in bioavailable soil fractions indexed by extractions of 0.05 mol/L HCl and 0.2 mol/L acid ammonium oxalate (AAO). Element accumulations in 40-year tree biomass plus O horizons totaled 0.9, 2.9, 4.8, 49.6, and 501.3 kg/ha for Cu, B, Zn, Mn, and Fe, respectively. In response to this forest development, samples of the upper 0.6-m of mineral soil archived in 1962 and 1997 followed one of three patterns. (1) Extractable B and Mn were significantly depleted, by -4.1 and -57.7 kg/ha with AAO, depletions comparable to accumulations in biomass plus O horizons, 2.9 and 49.6 kg/ha, respectively. Tree uptake of B and Mn from mineral soil greatly outpaced resupplies from atmospheric deposition, mineral weathering, and deep-root uptake. (2) Extractable Zn and Cu changed little during forest growth, indicating that nutrient resupplies kept pace with accumulations by the aggrading forest. (3) Oxalate-extractable Fe increased substantially during forest growth, by 275.8 kg/ha, about 10-fold more than accumulations in tree biomass (28.7 kg/ha). The large increases in AAO-extractable Fe in surficial 0.35-m mineral soils were accompanied by substantial accretions of Fe in the forest's O horizon, by 473 kg/ha, amounts that dwarfed inputs via litterfall and canopy throughfall, indicating that forest Fe cycling is qualitatively different from that of other macro- and micronutrients. Bioturbation of surficial forest soil layers cannot account for these fractions and transformations of Fe, and we hypothesize that the secondary forest's large inputs of organic additions over four decades has fundamentally altered soil Fe oxides, potentially altering the bioavailability and retention of macro- and micronutrients, contaminants, and organic matter itself. The wide range of responses among the ecosystem's trace elements illustrates the great dynamics of the soil system over time scales of decades.

Estimations of historical atmospheric mercury concentrations from mercury refining and present-day soil concentrations of total mercury in Huancavelica, Peru.

Detailed Spanish records of cinnabar mining and mercury production during the colonial period in Huancavelica, Peru were examined to estimate historical health risks to the community from exposure to elemental mercury (Hg) vapor resulting from cinnabar refining operations. Between 1564 and 1810, nearly 17,000 metric tons of Hg were released to the atmosphere in Huancavelica from Hg production. AERMOD was used with estimated emissions and source characteristics to approximate historic atmospheric concentrations of mercury vapor. Modeled 1-hour and long-term concentrations were compared with present-day inhalation reference values for elemental Hg. Estimated 1-hour maximum concentrations for the entire community exceeded present-day occupational inhalation reference values, while some areas closest to the smelters exceeded present-day emergency response guideline levels. Estimated long-term maximum concentrations for the entire community exceeded the EPA Reference Concentration (RfC) by a factor of 30 to 100, with areas closest to the smelters exceeding the RfC by a factor of 300 to 1000. Based on the estimated historical concentrations of Hg vapor in the community, the study also measured the extent of present-day contamination throughout the community through soil sampling and analysis. Total Hg in soils sampled from 20 locations ranged from 1.75 to 698 mg/kg and three adobe brick samples ranging from 47.4 to 284 mg/kg, consistent with other sites of mercury mining and use. The results of the soil sampling indicate that the present-day population of Huancavelica is exposed to levels of mercury from legacy contamination which is currently among the highest worldwide, consequently placing them at potential risk of adverse health outcomes.