Selector Screening for Enantioseparation of dl‐α‐Methyl Phenylglycine Amide by Liquid–Liquid Extraction

Enantioseparation through liquid extraction technology is an emerging field, e.g., enantioseparations of amino acids (and derivatives thereof), amino alcohols, amines, and carboxylic acids have been reported. Often, when a new selector is developed, the versatility of substrate scope is investigated. From an industrial point of view, the problem is typically approached the other way around, and for a target racemate, a selector needs to be found in order to accomplish the desired enantioseparation. This study presents such a screening approach for the separation of the enantiomers of dl ‐α‐methyl phenylglycine amide (dl ‐α‐MPGA), a model amide racemate with high industrial relevance. Chiral selectors that were reported for other classes of racemates were investigated, i.e., several macrocyclic selectors and Pd‐BINAP complexes. It appeared very challenging to obtain both high extraction yields and good enantioselectivity for most selectors, but Pd‐BINAP‐based selectors performed well, with enantioselectivities up to 7.4 with an extraction yield of the desired enantiomer of 95.8%. These high enantioselectivities were obtained using dichloromethane as solvent. Using less volatile chlorobenzene or 1‐chloropentane, reasonable selectivities of up to 1.7 were measured, making these the best alternative solvents for dichloromethane. Chirality 27:123–130, 2015. © 2014 Wiley Periodicals, Inc.     

Nitrogen availability increases in a tundra ecosystem during five years of experimental permafrost thaw

Perennially frozen soil in high latitude ecosystems (permafrost) currently stores 1330–1580 Pg of carbon (C). As these ecosystems warm, the thaw and decomposition of permafrost is expected to release large amounts of C to the atmosphere. Fortunately, losses from the permafrost C pool will be partially offset by increased plant productivity. The degree to which plants are able to sequester C, however, will be determined by changing nitrogen (N) availability in these thawing soil profiles. N availability currently limits plant productivity in tundra ecosystems but plant access to N is expected improve as decomposition increases in speed and extends to deeper soil horizons. To evaluate the relationship between permafrost thaw and N availability, we monitored N cycling during 5 years of experimentally induced permafrost thaw at the Carbon in Permafrost Experimental Heating Research (CiPEHR) project. Inorganic N availability increased significantly in response to deeper thaw and greater soil moisture induced by Soil warming. This treatment also prompted a 23% increase in aboveground biomass and a 49% increase in foliar N pools. The sedge Eriophorum vaginatum responded most strongly to warming: this species explained 91% of the change in aboveground biomass during the 5 year period. Air warming had little impact when applied alone, but when applied in combination with Soil warming, growing season soil inorganic N availability was significantly reduced. These results demonstrate that there is a strong positive relationship between the depth of permafrost thaw and N availability in tundra ecosystems but that this relationship can be diminished by interactions between increased thaw, warmer air temperatures, and higher levels of soil moisture. Within 5 years of permafrost thaw, plants actively incorporate newly available N into biomass but C storage in live vascular plant biomass is unlikely to be greater than losses from deep soil C pools.     

Plant Community Composition as a Predictor of Regional Soil Carbon Storage in Alaskan Boreal Black Spruce Ecosystems

The boreal forest is the largest terrestrial biome in North America and holds a large portion of the world’s reactive soil carbon. Therefore, understanding soil carbon accumulation on a landscape or regional scale across the boreal forest is useful for predicting future soil carbon storage. Here, we examined the relationship between floristic composition and ecosystem parameters, such as soil carbon pools, the carbon-to-nitrogen (C/N) ratio of live black spruce needles, and normalized basal area increment (NBAI) of trees in black spruce communities, the most widespread forest type in the boreal forest of Alaska. Variability in ecosystem properties among black spruce stands was as large as that which had previously been documented among all forest types in the central interior of Alaska; we found an eightfold range in NBAI and fivefold range in mineral soil carbon and nitrogen pools. Acidic black spruce communities had significantly more carbon in the organic soil horizon than did nonacidic black spruce communities, but did not differ in any other measured ecosystem parameter. We explained 48% of the variation in total soil carbon with a combination of plant community indices and abiotic and biotic factors. Plant community composition was at least as effective as any single environmental factor or stand characteristic in predicting soil C pools in Alaskan black spruce ecosystems. We conclude that among the community properties analyzed, the presence of key groups of species, overall species composition, and diversity of certain functional types, especially Sphagnum moss species, are important predictors of soil carbon sequestration in the black spruce forest type.     

Plants,microorganisms, and soil temperatures contribute to a decrease in methane fluxes on a drained Arctic floodplain

As surface temperatures are expected to rise in the future, ice‐rich permafrost may thaw, altering soil topography and hydrology and creating a mosaic of wet and dry soil surfaces in the Arctic. Arctic wetlands are large sources of CH₄, and investigating effects of soil hydrology on CH₄ fluxes is of great importance for predicting ecosystem feedback in response to climate change. In this study, we investigate how a decade‐long drying manipulation on an Arctic floodplain influences CH₄‐associated microorganisms, soil thermal regimes, and plant communities. Moreover, we examine how these drainage‐induced changes may then modify CH₄ fluxes in the growing and nongrowing seasons. This study shows that drainage substantially lowered the abundance of methanogens along with methanotrophic bacteria, which may have reduced CH₄ cycling. Soil temperatures of the drained areas were lower in deep, anoxic soil layers (below 30 cm), but higher in oxic topsoil layers (0–15 cm) compared to the control wet areas. This pattern of soil temperatures may have reduced the rates of methanogenesis while elevating those of CH₄ oxidation, thereby decreasing net CH₄ fluxes. The abundance of Eriophorum angustifolium, an aerenchymatous plant species, diminished significantly in the drained areas. Due to this decrease, a higher fraction of CH₄ was alternatively emitted to the atmosphere by diffusion, possibly increasing the potential for CH₄ oxidation and leading to a decrease in net CH₄ fluxes compared to a control site. Drainage lowered CH₄ fluxes by a factor of 20 during the growing season, with postdrainage changes in microbial communities, soil temperatures, and plant communities also contributing to this reduction. In contrast, we observed CH₄ emissions increased by 10% in the drained areas during the nongrowing season, although this difference was insignificant given the small magnitudes of fluxes. This study showed that long‐term drainage considerably reduced CH₄ fluxes through modified ecosystem properties.     

Cross‐scale controls on carbon emissions from boreal forest megafires

Climate warming and drying is associated with increased wildfire disturbance and the emergence of megafires in North American boreal forests. Changes to the fire regime are expected to strongly increase combustion emissions of carbon (C) which could alter regional C balance and positively feedback to climate warming. In order to accurately estimate C emissions and thereby better predict future climate feedbacks, there is a need to understand the major sources of heterogeneity that impact C emissions at different scales. Here, we examined 211 field plots in boreal forests dominated by black spruce (Picea mariana) or jack pine (Pinus banksiana) of the Northwest Territories (NWT), Canada after an unprecedentedly large area burned in 2014. We assessed both aboveground and soil organic layer (SOL) combustion, with the goal of determining the major drivers in total C emissions, as well as to develop a high spatial resolution model to scale emissions in a relatively understudied region of the boreal forest. On average, 3.35 kg C m^?2 was combusted and almost 90% of this was from SOL combustion. Our results indicate that black spruce stands located at landscape positions with intermediate drainage contribute the most to C emissions. Indices associated with fire weather and date of burn did not impact emissions, which we attribute to the extreme fire weather over a short period of time. Using these results, we estimated a total of 94.3 Tg C emitted from 2.85 Mha of burned area across the entire 2014 NWT fire complex, which offsets almost 50% of mean annual net ecosystem production in terrestrial ecosystems of Canada. Our study also highlights the need for fine‐scale estimates of burned area that represent small water bodies and regionally specific calibrations of combustion that account for spatial heterogeneity in order to accurately model emissions at the continental scale.     

The effect of nutrient deposition on bacterial communities in Arctic tundra soil

The microbial communities of high‐latitude ecosystems are expected to experience rapid changes over the next century due to climate warming and increased deposition of reactive nitrogen, changes that will likely affect microbial community structure and function. In moist acidic tundra (MAT) soils on the North Slope of the Brooks Range, Alaska, substantial losses of C and N were previously observed after long‐term nutrient additions. To analyse the role of microbial communities in these losses, we utilized 16S rRNA gene tag pyrosequencing coupled with community‐level physiological profiling to describe changes in MAT bacterial communities after short‐ and long‐term nutrient fertilization in four sets of paired control and fertilized MAT soil samples. Bacterial diversity was lower in long‐term fertilized plots. The Acidobacteria were one of the most abundant phyla in all soils and distinct differences were noted in the distributions of Acidobacteria subgroups between mineral and organic soil layers that were also affected by fertilization. In addition, Alpha‐ and Gammaproteobacteria were more abundant in long‐term fertilized samples compared with control soils. The dramatic increase in sequences within the Gammaproteobacteria identified as Dyella spp. (order Xanthomonadales) in the long‐term fertilized samples was confirmed by quantitative PCR (qPCR) in several samples. Long‐term fertilization was also correlated with shifts in the utilization of specific substrates by microbes present in the soils. The combined data indicate that long‐term fertilization resulted in a significant change in microbial community structure and function linked to changes in carbon and nitrogen availability and shifts in above‐ground plant communities.     

Abrupt permafrost thaw drives spatially heterogeneous soil moisture and carbon dioxide fluxes in upland tundra

Permafrost thaw causes the seasonally thawed active layer to deepen, causing the Arctic to shift toward carbon release as soil organic matter becomes susceptible to decomposition. Ground subsidence initiated by ice loss can cause these soils to collapse abruptly, rapidly shifting soil moisture as microtopography changes and also accelerating carbon and nutrient mobilization. The uncertainty of soil moisture trajectories during thaw makes it difficult to predict the role of abrupt thaw in suppressing or exacerbating carbon losses. In this study, we investigated the role of shifting soil moisture conditions on carbon dioxide fluxes during a 13-year permafrost warming experiment that exhibited abrupt thaw. Warming deepened the active layer differentially across treatments, leading to variable rates of subsidence and formation of thermokarst depressions. In turn, differential subsidence caused a gradient of moisture conditions, with some plots becoming consistently inundated with water within thermokarst depressions and others exhibiting generally dry, but more variable soil moisture conditions outside of thermokarst depressions. Experimentally induced permafrost thaw initially drove increasing rates of growing season gross primary productivity (GPP), ecosystem respiration (R_eco), and net ecosystem exchange (NEE) (higher carbon uptake), but the formation of thermokarst depressions began to reverse this trend with a high level of spatial heterogeneity. Plots that subsided at the slowest rate stayed relatively dry and supported higher CO₂ fluxes throughout the 13-year experiment, while plots that subsided very rapidly into the center of a thermokarst feature became consistently wet and experienced a rapid decline in growing season GPP, R_eco, and NEE (lower carbon uptake or carbon release). These findings indicate that Earth system models, which do not simulate subsidence and often predict drier active layer conditions, likely overestimate net growing season carbon uptake in abruptly thawing landscapes.     

Degradation of benzene compounds by yeasts in acidic soils

Attemps were made to demonstrate the role of yeasts in the degradation of benzene compounds under natural soil conditions. Yeasts were isolated from acidic sandy soil supplied with benzene compounds. For this purpose the slant culture method was used. Growth on the benzene compounds took place on solid growth media at 10°C. Several yeast species were isolated: Leucosporidium scottii, Rhodotorula aurantiaca, Rhodotorula mucilaginosa, Trichosporon dulcitum, Trichosporon moniliiforme and Schizoblastosporion starkeyi-henricii. Cryptococcus humicolus and Cryptococcus laurentii were isolated from liquid enrichment cultures. All these strains assimilated several benzene compounds in pure culture.Cresol removal from contaminated soil was speeded up by inoculation with Rhodotorula aurantiaca G36. It was demonstrated that this yeast utilized this compound in competition with the soil microflora.     

Comparing Visually Assessed BI-RADS Breast Density and Automated Volumetric Breast Density Software: A Cross-Sectional Study in a Breast Cancer Screening Setting

Introduction

The objective of this study is to compare different methods for measuring breast density, both visual assessments and automated volumetric density, in a breast cancer screening setting. These measures could potentially be implemented in future screening programmes, in the context of personalised screening or screening evaluation.

Materials and Methods

Digital mammographic exams (N = 992) of women participating in the Dutch breast cancer screening programme (age 50–75y) in 2013 were included. Breast density was measured in three different ways: BI-RADS density (5^th edition) and with two commercially available automated software programs (Quantra and Volpara volumetric density). BI-RADS density (ordinal scale) was assessed by three radiologists. Quantra (v1.3) and Volpara (v1.5.0) provide continuous estimates. Different comparison methods were used, including Bland-Altman plots and correlation coefficients (e.g., intraclass correlation coefficient [ICC]).

Results

Based on the BI-RADS classification, 40.8% of the women had ‘heterogeneously or extremely dense’ breasts. The median volumetric percent density was 12.1% (IQR: 9.6–16.5) for Quantra, which was higher than the Volpara estimate (median 6.6%, IQR: 4.4–10.9). The mean difference between Quantra and Volpara was 5.19% (95% CI: 5.04–5.34) (ICC: 0.64). There was a clear increase in volumetric percent dense volume as BI-RADS density increased. The highest accuracy for predicting the presence of BI-RADS c+d (heterogeneously or extremely dense) was observed with a cut-off value of 8.0% for Volpara and 13.8% for Quantra.

Conclusion

Although there was no perfect agreement, there appeared to be a strong association between all three measures. Both volumetric density measures seem to be usable in breast cancer screening programmes, provided that the required data flow can be realized.