Photocontrolled Degradation of Stimuli-Responsive Poly(ethyl glyoxylate): Differentiating Features and Traceless Ambient Depolymerization

The depolymerization of coatings prepared from a 6-nitroveratryl carbonate end-capped poly(ethyl glyoxylate) (PEtG) self-immolative polymer was studied. This polymer undergoes end-to-end depolymerization following cleavage of the end-cap by UV light. Several important fundamental diff erences between this class of polymers and conventional degradable polymers were revealed. For example, polymer backbone cleavage and depolymerization exhibited different dependencies on pH, emphasizing the decoupling of these processes. Probing of the coating erosion mechanism illustrated an interesting combination of features from surface erosion and bulk degradation mechanisms that arise from the end-to-end depolymerization mechanism and further differentiate these polymers from convention degradable polymers. It was also demonstrated that, unlike backbone cleavage, PEtG depolymerization did not exhibit a dependence on water and that PEtG could depolymerize back to the volatile monomer ethyl glyoxylate at ambient temperature and pressure. This unusual feature was utilized to perform facile polymer reprogramming/recycling via an irradiation− trapping− repolymerization sequence as well as polymer patterning by a simple irradiation− evaporation sequence

High-affinity and selective detection of pyrophosphate in water by a resorcinarene salt receptor

Pyrophosphate (PPi) is a byproduct of DNA and RNA synthesis, and abnormal levels are indicative of disease. We report the high-affinity binding of PPi in water by N-alkyl ammonium resorcinarene chloride receptors. Experimental analysis using 1H and 31P NMR, isothermal titration calorimetry, mass spectrometry, and UV-vis spectroscopy all support exceptional selectivity of these systems for PPi in water. The measured affinity of K1 = 1.60 × 107 M-1 for PPi is three orders of magnitude larger than that observed for binding to another phosphate, ATP. This exceptional anion-binding affinity in water is explored through a detailed density functional theory computational study. These systems provide a promising avenue for the development of future innovative medical diagnostic tools

Tree spatial pattern within the forest–tundra ecotone: a comparison of sites across Canada

Accepted VersionAlthough many studies have focused on factors influencing treeline advance with climate change, less consideration has been given to potential changes in tree spatial pattern across the forest–tundra ecotone. We investigated trends in spatial pattern across the forest–tundra ecotone and geographical variation in the Yukon, Manitoba, and Labrador, Canada. Tree cover was measured in contiguous quadrats along transects up to 100 m long located in Forest, Ecotone, and Tundra sections across the forest–tundra transition. Spatial patterns were analyzed using new local variance to estimate patch size and wavelet analysis to determine the scale and amount of aggregation. Compared with the Forest, tree cover in the Ecotone was less aggregated at most sites, with fewer smaller patches of trees. We found evidence that shorter trees may be clumped at some sites, perhaps due to shelter from the wind, and we found little support for regular spacing that would indicate competition. With climate change, trees in the Ecotone will likely become more aggregated as patches enlarge and new patches establish. However, results were site-specific, varying with aspect and the presence of krummholz (stunted trees); therefore, strategies for adaptation of communities to climate change in Canada’s subarctic forest would need to reflect these differences

Reproduction as a bottleneck to treeline advance across the circumarctic forest tundra ecotone

Published versionThe fundamental niche of many species is shifting with climate change, especially in sub-arctic ecosystems with pronounced recent warming. Ongoing warming in sub-arctic regions should lessen environmental constraints on tree growth and reproduction, leading to increased success of trees colonizing tundra. Nevertheless, variable responses of treeline ecotones have been documented in association with warming temperatures. One explanation for time lags between increasingly favourable environmental conditions and treeline ecotone movement is reproductive limitations caused by low seed availability. Our objective was to assess the reproductive constraints of the dominant tree species at the treeline ecotone in the circumpolar north. We sampled reproductive structures of trees (cones and catkins) and stand attributes across circumarctic treeline ecotones. We used generalized linear mixed models to estimate the sensitivity of seed production and the availability of viable seed to regional climate, stand structure, and species-specific characteristics. Both seed production and viability of available seed were strongly driven by specific, sequential seasonal climatic conditions, but in different ways. Seed production was greatest when growing seasons with more growing degree days coincided with years with high precipitation. Two consecutive years with more growing degree days and low precipitation resulted in low seed production. Seasonal climate effects on the viability of available seed depended on the physical characteristics of the reproductive structures. Large-coned and -seeded species take more time to develop mature embryos and were therefore more sensitive to increases in growing degree days in the year of flowering and embryo development. Our findings suggest that both moisture stress and abbreviated growing seasons can have a notable negative influence on the production and viability of available seed at treeline. Our synthesis revealed that constraints on pre-dispersal reproduction within the treeline ecotone might create a considerable time lag for range expansion of tree populations into tundra ecosystems

Climate sensitivity of shrub growth across the tundra biome

The tundra biome is experiencing rapid temperature increases that have been linked to a shift in tundra vegetation composition towards greater shrub dominance. Shrub expansion can amplify warming by altering the surface albedo, energy and water balance, and permafrost temperatures. To account for these feedbacks, global climate models must include realistic projections of vegetation dynamics, and in particular tundra shrub expansion, yet the mechanisms driving shrub expansion remain poorly understood. Dendroecological data consisting of multi-decadal time series of annual growth of shrub species provide a previously untapped resource to explore climate-growth relationships across the tundra biome. We analysed a dataset of approximately 42,000 annual growth records from 1821 individuals, comprising 25 species from eight genera, from 37 arctic and alpine sites. Our analyses demonstrate that the sensitivity of shrub growth to climate was (1) heterogeneous across the tundra biome, (2) greater at sites with higher soil moisture and (3) strongest for taller shrub species growing at the northern or upper elevational edge of their range. Across latitudinal gradients in the Arctic, climate sensitivity of growth was greatest at the boundary between low- and high-arctic vegetation zones, where permafrost conditions are changing and the majority of the global permafrost soil carbon pool is stored. Thus, in order to more accurately estimate feedbacks among shrub change, albedo, permafrost thaw, carbon storage and climate, the observed variation in climate-growth relationships of shrub species across the tundra biome will need to be incorporated into earth system models.JRC.H.3-Forest Resources and Climat

Identification and developmental expression of the full complement of Cytochrome P450 genes in Zebrafish

© The Authors, 2010. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in BMC Genomics 11 (2010): 643, doi:10.1186/1471-2164-11-643.Increasing use of zebrafish in drug discovery and mechanistic toxicology demands knowledge of cytochrome P450 (CYP) gene regulation and function. CYP enzymes catalyze oxidative transformation leading to activation or inactivation of many endogenous and exogenous chemicals, with consequences for normal physiology and disease processes. Many CYPs potentially have roles in developmental specification, and many chemicals that cause developmental abnormalities are substrates for CYPs. Here we identify and annotate the full suite of CYP genes in zebrafish, compare these to the human CYP gene complement, and determine the expression of CYP genes during normal development. Zebrafish have a total of 94 CYP genes, distributed among 18 gene families found also in mammals. There are 32 genes in CYP families 5 to 51, most of which are direct orthologs of human CYPs that are involved in endogenous functions including synthesis or inactivation of regulatory molecules. The high degree of sequence similarity suggests conservation of enzyme activities for these CYPs, confirmed in reports for some steroidogenic enzymes (e.g. CYP19, aromatase; CYP11A, P450scc; CYP17, steroid 17a-hydroxylase), and the CYP26 retinoic acid hydroxylases. Complexity is much greater in gene families 1, 2, and 3, which include CYPs prominent in metabolism of drugs and pollutants, as well as of endogenous substrates. There are orthologous relationships for some CYP1 s and some CYP3 s between zebrafish and human. In contrast, zebrafish have 47 CYP2 genes, compared to 16 in human, with only two (CYP2R1 and CYP2U1) recognized as orthologous based on sequence. Analysis of shared synteny identified CYP2 gene clusters evolutionarily related to mammalian CYP2 s, as well as unique clusters. Transcript profiling by microarray and quantitative PCR revealed that the majority of zebrafish CYP genes are expressed in embryos, with waves of expression of different sets of genes over the course of development. Transcripts of some CYP occur also in oocytes. The results provide a foundation for the use of zebrafish as a model in toxicological, pharmacological and chemical disease research.This work was supported by NIH grants R01ES015912 and P42ES007381 (Superfund Basic Research Program at Boston University) (to JJS). MEJ was a Guest Investigator at the Woods Hole Oceanographic Institution (WHOI) and was supported by grants from the Swedish research council Formas and Carl Trygger's foundation. AK was a Post-doctoral Fellow at WHOI, and was supported by a fellowship from the Japanese Society for Promotion of Science (JSPS). JZ and TP were Guest Students at the WHOI and were supported by a CAPES Ph.D. Fellowship and CNPq Ph.D. Sandwich Fellowship (JZ), and by a CNPq Ph.D. Fellowship (TP), from Brazil

Persistence at the Tree Line: Old Trees as Opportunists

While old trees have long been of interest, their significant role in responding to climate change at northern tree lines has been overlooked. Long-lived black spruces at the tree line in Labrador show a radial growth response that is synchronous with recent climate warming. The ability of individuals to persist with suppressed radial growth rates during adverse growing conditions may have significant implications for the rate at which these trees are able to respond when conditions become favourable

Changing treelines : how variability in scale and approach improve our understanding

With treeline position expected to expand northward, and upward, with climate change, there is increased attention towards understanding the mechanisms that control these patterns. Using a regional and broad scale approach, treeline dynamics, disturbance and response to recent climate warming were explored along an altitudinal gradient in the Mealy Mountains, Labrador (Canada), and across the circumpolar subarctic. To complement the western science approach to understanding climate change, a critique of modules taught to the Innu Guardians will be presented. At a regional scale in the Mealy Mountains, treeline dynamics over the past few centuries showed species-specific differences in when treeline was established and the relative rates of subsequent infilling and mortality. All tree species showed increased variability in recruitment correlations to climate across the treeline ecotone with black spruce (Picea mariana) showing consistently positive correlations, while larch (Larix laricina) shifted from strongly positive to negative and white spruce (Picea glauca) showing consistently negative correlations. Long-lived black spruce krummholz also showed significant recent increases in radial growth. Disturbance at treeline resulted in characteristic gap dynamics with low-levels of tree mortality attributed to porcupine (Erethizon dorsatum) herbivory and small-scale outbreaks of spruce budworm (Choristoneura fumiferana) and larch sawfly (Pristiphora erichsonii). These outbreaks occurred at lower magnitudes than observed in other parts of the boreal forest due to decreased tree density, supporting the Resource Concentration Hypothesis. Canopy gaps associated with windthrow did not have significantly different canopy structures but seedling densities of larch and black spruce, were significantly higher in exposed soil associated with windthrow disturbance. At broader spatial scales across circumpolar treeline, growth form and advancement were not significantly related to the extent of site warming but rather treeline advancement was predicted by diffuse, or 'gradual' treelines and closeness to the ocean. At the regional scale, it was expected that larch and black spruce would capitalize on warming temperatures, since these species are already exhibiting early signs of response. The frequency and magnitude of insect outbreaks is expected to increase with climate change and these data suggest that larch, and to a lesser extent, black spruce, will have enhanced regeneration dynamics. At broad spatial scales, ecological factors will continue to be significant drivers of treeline change until temperatures warm past a point where regeneration limitations, such as seed viability and establishment, are removed. Teaching and communicating climate change science illustrated the best results when taught in field conditions, while some difficulties were encountered in differentiating between short-term versus long-term change. Working with the Innu Environmental Guardians to develop a framework for detecting change in northern forests, helped to contextualize the western science approach to treeline research

Roads Impact Tree and Shrub Productivity in Adjacent Boreal Peatlands

Peatlands in the western boreal plains of Canada are important ecosystems as they store over two percent of global terrestrial carbon. However, in recent decades, many of these peatlands have been fragmented by access roads constructed for resource extraction and transportation, challenging their carbon storage potential. To investigate how roads have been impacting tree and shrub growth and productivity in these peatlands, this study was conducted in a forested bog and woody fen in Carmon Creek, Alberta, Canada. In 2017, vegetation surveys were conducted along 20 m transects that extended on both sides of the road with 4 m2 circular plots at 2, 6 and 20 m distance from the road and were followed by disc or core collection from woody stems. Within 20 m of the road at the bog site, we observed a shift towards significantly larger radial growth of trees in the downstream areas (t = 3.23, p = 0.006) where water table position was deeper, while at the fen site, radial growth of tall shrubs had little response to the road. Combining the effects of direct tree clearing and hydrology induced shifts in growth, aboveground net primary productivity (NPPag) post-road construction was reduced significantly in areas where vegetation was cleared during the road construction (i.e., upstream areas of the bog: t = 5.21, p < 0.0001 and downstream areas of the fen: t = 2.64, p = 0.07). Substantially lower NPPag around the road construction areas compared to reference areas shows tremendous loss of carbon sink potential of trees and shrubs after road construction through peatlands. Altogether, roads constructed through peatlands perpendicular to the water flow may shift long-term carbon sinks into sources of carbon, at least for the initial few years following road construction