Tryptophan to Tryptophan Hole Hopping in an Azurin Construct.

Electron transfer (ET) between neutral and cationic tryptophan residues in the azurin construct [ReI(H126)(CO)3(dmp)](W124)(W122)CuI (dmp = 4,7-Me2-1,10-phenanthroline) was investigated by Born-Oppenheimer quantum-mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) simulations. We focused on W124•+ ← W122 ET, which is the middle step of the photochemical hole-hopping process *ReII(CO)3(dmp•-) ← W124 ← W122 ← CuI, where sequential hopping amounts to nearly 10,000-fold acceleration over single-step tunneling (ACS Cent. Sci. 2019, 5, 192-200). In accordance with experiments, UKS-DFT QM/MM/MD simulations identified forward and reverse steps of W124•+ ↔ W122 ET equilibrium, as well as back ET ReI(CO)3(dmp•-) → W124•+ that restores *ReII(CO)3(dmp•-). Strong electronic coupling between the two indoles (≥40 meV in the crossing region) makes the productive W124•+ ← W122 ET adiabatic. Energies of the two redox states are driven to degeneracy by fluctuations of the electrostatic potential at the two indoles, mainly caused by water solvation, with contributions from the protein dynamics in the W122 vicinity. ET probability depends on the orientation of Re(CO)3(dmp) relative to W124 and its rotation diminishes the hopping yield. Comparison with hole hopping in natural systems reveals structural and dynamics factors that are important for designing efficient hole-hopping processes

A global view of aspen : Conservation science for widespread keystone systems

Across the northern hemisphere, six species of aspen (Populus spp.) play a disproportionately important role in promoting biodiversity, sequestering carbon, limiting forest disturbances, and providing other ecosystem services. These species are illustrative of efforts to move beyond single-species conservation because they facilitate hundreds of plants and animals worldwide. This review is intended to place aspen in a global conservation context by focusing on the many scientific advances taking place in such biologically diverse systems. In this manner, aspen may serve as a model for other widespread keystone systems where science-based practice may have world implications for biodiversity conservation. In many regions, aspen can maintain canopy dominance for decades to centuries as the sole major broadleaf trees in forested landscapes otherwise dominated by conifers. Aspen ecosystems are valued for many reasons, but here we highlight their potential as key contributors to regional and global biodiversity. We present global trends in research priorities, strengths, and weaknesses based on, 1) a qualitative survey, 2) a systematic literature analysis, and 3) regional syntheses of leading research topics. These regional syntheses explore important aspen uses, threats, and research priorities with the ultimate intent of research sharing focused on sound conservation practice. In all regions, we found that aspen enhance biodiversity, facilitate rapid (re)colonization in natural and damaged settings (e.g., abandoned mines), and provide adaptability in changing environments. Common threats to aspen ecosystems in many, but not all, regions include effects of herbivory, land clearing, logging practices favoring conifer species, and projected climate warming. We also highlight regional research gaps that emerged from the three survey approaches above. We believe multi-scale research is needed that examines disturbance processes in the context of dynamic climates where ecological, physiological, and genetic variability will ultimately determine widespread aspen sustainability. Based on this global review of aspen research, we argue for the advancement of the “mega-conservation” strategy, centered on the idea of sustaining a set of common keystone communities (aspen) that support wide arrays of obligate species. This approach contrasts with conventional preservation which focuses limited resources on individual species residing in narrow niches.Peer reviewe

<scp>ReSurveyEurope</scp>: A database of resurveyed vegetation plots in Europe

AbstractAimsWe introduce ReSurveyEurope — a new data source of resurveyed vegetation plots in Europe, compiled by a collaborative network of vegetation scientists. We describe the scope of this initiative, provide an overview of currently available data, governance, data contribution rules, and accessibility. In addition, we outline further steps, including potential research questions.ResultsReSurveyEurope includes resurveyed vegetation plots from all habitats. Version 1.0 of ReSurveyEurope contains 283,135 observations (i.e., individual surveys of each plot) from 79,190 plots sampled in 449 independent resurvey projects. Of these, 62,139 (78%) are permanent plots, that is, marked in situ, or located with GPS, which allow for high spatial accuracy in resurvey. The remaining 17,051 (22%) plots are from studies in which plots from the initial survey could not be exactly relocated. Four data sets, which together account for 28,470 (36%) plots, provide only presence/absence information on plant species, while the remaining 50,720 (64%) plots contain abundance information (e.g., percentage cover or cover–abundance classes such as variants of the Braun‐Blanquet scale). The oldest plots were sampled in 1911 in the Swiss Alps, while most plots were sampled between 1950 and 2020.ConclusionsReSurveyEurope is a new resource to address a wide range of research questions on fine‐scale changes in European vegetation. The initiative is devoted to an inclusive and transparent governance and data usage approach, based on slightly adapted rules of the well‐established European Vegetation Archive (EVA). ReSurveyEurope data are ready for use, and proposals for analyses of the data set can be submitted at any time to the coordinators. Still, further data contributions are highly welcome.</jats:sec

Magnetism in TmCo₂

Recently a new wave of interest in physics of RCo₂ compounds has been boosted by reports on unusual magnetic short range order configurations in the heavy rare-earth RCo₂ ferrimagnets in paramagnetic state. The newly observed phenomenon called parimagnetism consists in a short-range antiferromagnetic coupling between small ferromagnetic Co clusters and the nearest rare-earth moments. This paper is devoted to results of our experimental investigation of carefully prepared and characterized samples of TmCo₂, a compound on which controversial results can be found in literature. Detailed magnetization, AC susceptibility, specific heat and electrical resistivity measurements revealed two magnetic phase transitions at 4.6 and 3.6 K, respectively. The anomalies connected with the transitions are strongly dependent on magnetic field and hydrostatic pressure. The AC susceptibility anomaly connected with the onset of parimagnetism has been found at $T_{f}$=35 K. Contrary to other heavy rare-earth RCo₂ counterparts $T_{f}$ of TmCo₂ is entirely pressure independent