Amine-substituted α-N(standard)- and δ-N(remote)-pyridylidene complexes: Synthesis and bonding

Reaction of ortho-amino-para-chloro- and ortho-chloro-para-amino-pyridinium triflate with tetrakis(triphenylphosphine) complexes of Ni or Pd afforded by oxidative substitution compounds that can be represented as cationic carbene complexes. NMR as well as X-ray structural studies revealed the role played by the NMe₂ and M(PPh)₂Cl (M = Ni or Pd) substituents in stabilizing the complexes by π-retro-donation and, consequently, in governing the relative importance of certain mesomeric representations describing their structures.     

Development of remote sensing indicators for mapping episodic die-off of an invasive annual grass (Bromus tectorum) from the Landsat archive

The exotic annual grass Bromus tectorum (cheatgrass) dominates vast acreages of rangeland in the western USA, leading to increased fire frequency and ecosystem degradation that is often irreversible. Episodic regeneration failure (“die-off”) has been observed in cheatgrass monocultures and can have negative ecosystem consequences, but can also provide an opportunity for restoration of native species and ecological function within the imperiled sagebrush steppe ecosystem. Proximate causes of cheatgrass die-off are uncertain, although several taxa of fungal soil pathogens have been implicated. Die-off occurrence is stochastic and can occur in remote areas. Thus, developing remote sensing indicators that are repeatable over long time periods, across extensive regions, and at relatively fine spatial resolution would be beneficial for accurately pinpointing events.We developed a remote sensing approach for mapping historical die-off from the Landsat archive (1985–2015), and used this to quantify spatial and temporal patterns of die-off occurrence annually at 30-m resolution. A Random Forests classification of image-derived spectral endmembers, trained on 2014 data, predicted die-off with 93% accuracy (κ = 0.845) when applied to independent validation data from 2009. Die-off extent varied greatly across years, though some areas experienced die-off multiple times during the observation period. We found a strong correspondence between die-off occurrence and winter drought conditions, with strongest negative associations with current-year winter precipitation and previous years’ lagged winter and annual precipitation. Die-off duration was heavily skewed towards single-year die-off (81.5% of events), even in localized areas of more frequent occurrence (‘die-off hotspots’).Our retrospective classification of the Landsat archive suggests that cheatgrass die-off occurrence is predictable as the intersection of particular site environmental conditions with annual weather conditions, possibly because they are favorable for disease expression. Associations with previous year conditions suggest that die-off may also depend upon feedbacks between cheatgrass dominance and litter production, suitable sites for seedling establishment, and abundance and persistence of pathogen inoculum. Remote sensing indicators such as those developed in this study are needed to develop hypotheses about die-off causal factors, as well as support improved management of cheatgrass, mitigation for negative consequences associated with die-off (e.g. wind erosion), and successful restoration of native plant communities on die-off areas.     

A Conserved Mechanism of GABA Binding and Antagonism Is Revealed by Structure-Function Analysis of the Periplasmic Binding Protein Atu2422 in Agrobacterium tumefaciens

Bacterial periplasmic binding proteins (PBPs) and eukaryotic PBP-like domains (also called as Venus flytrap modules) of G-protein-coupled receptors are involved in extracellular GABA perception. We investigated the structural and functional basis of ligand specificity of the PBP Atu2422, which is implicated in virulence and transport of GABA in the plant pathogen Agrobacterium tumefaciens. Five high-resolution x-ray structures of Atu2422 liganded to GABA, Pro, Ala, and Val and of point mutant Atu2422-F77A liganded to Leu were determined. Structural analysis of the ligand-binding site revealed two essential residues, Phe⁷⁷ and Tyr²⁷⁵, the implication of which in GABA signaling and virulence was confirmed using A. tumefaciens cells expressing corresponding Atu2422 mutants. Phe⁷⁷ restricts ligand specificity to α-amino acids with a short lateral chain, which act as antagonists of GABA signaling in A. tumefaciens. Tyr²⁷⁵ specifically interacts with the GABA γ-amino group. Conservation of these two key residues in proteins phylogenetically related to Atu2422 brought to light a subfamily of PBPs in which all members could bind GABA and short α-amino acids. This work led to the identification of a fingerprint sequence and structural features for defining PBPs that bind GABA and its competitors and revealed their occurrence among host-interacting proteobacteria.     

Gini coefficient predictions from airborne lidar remote sensing display the effect of management intensity on forest structure

In this study, two forest sites located in Finland were compared by means of predictions of Gini coefficient (GC) obtained from airborne laser scanning (ALS). We discuss the potential of the proposed method for identifying differences in structural complexity in relation with the management history of forests. The first study site (2200 ha), the Koli National Park (NP), includes areas where human intervention was restricted after 1907, in addition to forests which were protected only after the 1990s. The second study site in the municipality of Kiihtelysvaara (800 ha) has been under intensive management. These are commercial forests which include areas with different types of ownership: a large estate owned by an industrial company together with smaller private properties. We observed that GC predictions may be used to evaluate the effects of management practice on forest structure. Conservation and commercial forests showed significant differences, with the old-protected area of Koli having the highest, and the most intensively managed area in Kiihtelysvaara the lowest GC values. The effect of management history was revealed, as the 1990s’ extensions of Koli NP were more similar to unprotected areas than to forests contained within the original borders of the 1907s’ state property. Yet, their conservation status for almost two decades has been sufficient for developing significant differences against the outside of the NP. In Kiihtelysvaara, we found significant differences in GC according to the type of ownership. Moreover, the ALS predictions of GC also detected differences near lakeshores, which are driven by limitations on logging governed by Finnish law. Estimating this indicator with ALS remote sensing allowed to observe its spatial distribution and to detect peculiarities which would otherwise be unavailable from field plot sampling. Consequently, the method presented appears to be well suited for monitoring the effects of management practice, as well as verifying its compliance with legal restrictions.     

Combining stratification and up-scaling method-block cokriging with remote sensing imagery for sampling and mapping an erosion cover factor

When a ground and vegetation cover factor related to soil erosion is mapped with the aid of remotely sensed data, a cost-efficient sample design to collect ground data and to obtain an accurate map is required. However, the supports used to collect ground data are often smaller than the desirable pixels used for mapping, which leads to complexity in developing procedures for sample design and mapping. For these purposes, a sampling and mapping method was developed by integrating stratification and an up-scaling method in geostatistics — block cokriging with Landsat Thematic Mapper imagery. This method is based on spatial correlation and stratified sampling. It scales up not only the ground sample data but also the uncertainties associated with the data aggregation from smaller supports to larger pixels or blocks. This method uses the advantages of both stratification and block cokriging variance-based sample design, which leads to sample designs with variable grid spacing, and thus significantly increases the unit cost-efficiency of sample data in sampling and mapping. This outcome was verified by the results of this study.     

Characterization of diverse plant communities in Aspen Parkland rangeland using LiDAR data

Question: How effective is high-resolution airborne LiDAR technology for quantifying biophysical characteristics of multiple community types within diverse rangeland environments? Location: Native Aspen Parkland vegetation in central Alberta, Canada. Methods: Vegetation within 117 reference plots stratified across eight types, including forest, shrubland, upland grassland and lowland meadow communities, were assessed in 2001 for the height, cover and density of vegetation within various strata (herb, shrub and tree layers). Actual ground data were subsequently compared against modelled values for each community type and strata derived from the analysis of airborne LiDAR data obtained in 2000. Results: LiDAR data were effective for quantifying vegetation height, cover and density of the overstory within closed- and open Populus forest communities. However, LiDAR measurements typically underestimated the height and cover of shrublands, as well as most of the herbaceous communities. Analysis of LiDAR intensity data indicated reflectance generally decreased as LiDAR sampling points moved upwards from the ground to the vegetation canopy. Conclusions: While LiDAR technology is useful for characterizing deciduous forest properties, the quantification of understory vegetation characteristics, as well as those of individual shrublands and grasslands, was more limiting. Further refinements in analysis methods are necessary to increase the reliability of characterizing these communities.     

Remote magnetic navigation vs. manual navigation for ablation of ventricular tachycardia: a meta-analysis

Background

The purpose of this study was to prospectively evaluate the efficacy and safety of remote magnetic navigation (RMN) in comparison with manual catheter navigation (MCN) in performing ventricular tachycardia ablation.

Methods

An electronic search was performed using PubMed (1948–2013) and EMBASE (1974–2013) studies comparing RMN with MCN which were published prior to 31 December 2013. Outcomes of interest were as follows: acute success, recurrence rate, complications, total procedure and fluoroscopic times. Standard mean difference (SMD) and its 95 % confidence interval (CI) were used for continuous outcomes; odds ratios (OR) were reported for dichotomous variables.

Results

Four non-randomised studies, including a total of 328 patients, were identified. RMN was deployed in 191 patients. Acute success and long-term freedom from arrhythmias were not significantly different between the RMN and control groups (OR 1.845, 95 % CI 0.731–4.659, p = 0.195 and OR 0.676, 95 % CI 0.383–1.194, p = 0.177, respectively). RMN was associated with less peri-procedural complications (OR 0.279, 95 % CI 0.092–0.843, p = 0.024). Shorter procedural and fluoroscopy times were achieved (95 % CI -0.487 to -0.035, p = 0.024 and 95 % CI -1.467 to -0.984, p<0.001, respectively).

Conclusion

The acute and long-term success rates for VT ablation are equal between RMN and MCN, whereas the RMN-guided procedure can be performed with a lower complication rate and less procedural and fluoroscopic times. More prospective randomised trials will be needed to better evaluate the superior role of RMN for catheter ablation of ventricular tachycardia.