Resonant Tip-Enhanced Raman Spectroscopy of a Single-Molecule Kondo System.

Tip-enhanced Raman spectroscopy (TERS) under ultrahigh vacuum and cryogenic conditions enables exploration of the relations between the adsorption geometry, electronic state, and vibrational fingerprints of individual molecules. TERS capability of reflecting spin states in open-shell molecular configurations is yet unexplored. Here, we use the tip of a scanning probe microscope to lift a perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecule from a metal surface to bring it into an open-shell spin one-half anionic state. We reveal a correlation between the appearance of a Kondo resonance in differential conductance spectroscopy and concurrent characteristic changes captured by the TERS measurements. Through a detailed investigation of various adsorbed and tip-contacted PTCDA scenarios, we infer that the Raman scattering on suspended PTCDA is resonant with a higher excited state. Theoretical simulation of the vibrational spectra enables a precise assignment of the individual TERS peaks to high-symmetry Ag modes, including the fingerprints of the observed spin state. These findings highlight the potential of TERS in capturing complex interactions between charge, spin, and photophysical properties in nanoscale molecular systems and suggest a pathway for designing single-molecule spin-optical devices.

Revealing legacy effects of extreme droughts on tree growth of oaks across the Northern Hemisphere.

Forests are undergoing increasing risks of drought-induced tree mortality. Species replacement patterns following mortality may have a significant impact on the global carbon cycle. Among major hardwoods, deciduous oaks (Quercus spp.) are increasingly reported as replacing dying conifers across the Northern Hemisphere. Yet, our knowledge on the growth responses of these oaks to drought is incomplete, especially regarding post-drought legacy effects. The objectives of this study were to determine the occurrence, duration, and magnitude of legacy effects of extreme droughts and how that vary across species, sites, and drought characteristics. The legacy effects were quantified by the deviation of observed from expected radial growth indices in the period 1940-2016. We used stand-level chronologies from 458 sites and 21 oak species primarily from Europe, north-eastern America, and eastern Asia. We found that legacy effects of droughts could last from 1 to 5 years after the drought and were more prolonged in dry sites. Negative legacy effects (i.e., lower growth than expected) were more prevalent after repetitive droughts in dry sites. The effect of repetitive drought was stronger in Mediterranean oaks especially in Quercus faginea. Species-specific analyses revealed that Q. petraea and Q. macrocarpa from dry sites were more negatively affected by the droughts while growth of several oak species from mesic sites increased during post-drought years. Sites showing positive correlations to winter temperature showed little to no growth depression after drought, whereas sites with a positive correlation to previous summer water balance showed decreased growth. This may indicate that although winter warming favors tree growth during droughts, previous-year summer precipitation may predispose oak trees to current-year extreme droughts. Our results revealed a massive role of repetitive droughts in determining legacy effects and highlighted how growth sensitivity to climate, drought seasonality and species-specific traits drive the legacy effects in deciduous oak species.

Variations in Wood Anatomy in Afrotropical Trees with a special emphasis on radial and axial parenchyma.

BACKGROUND AND AIMS: Understanding anatomical variations across plant phylogenies and environmental gradients is vital for comprehending plant evolution and adaptation. Prior studies on tropical woody plants have paid limited attention to quantitative differences in major xylem tissues, which serve specific roles in mechanical support (fibers), carbohydrate storage and radial conduction (radial parenchyma, rays), wood capacitance (axial parenchyma), and water transport (vessels). To address this gap, we investigate xylem fractions in 173 tropical tree species spanning 134 genera and 53 families along a 2200 m elevational gradient on Mount Cameroon, West Africa. METHODS: We determined how elevation, stem height, and wood density affect interspecific differences in vessel, fiber, and specific axial (AP) and radial (RP) parenchyma fractions. We focus on quantifying distinct subcategories of homogenous or heterogeneous rays and apotracheal, paratracheal, and banded axial parenchyma. KEY RESULTS: Elevation-related cooling correlated with reduced AP fractions and vessel diameters, while fiber fractions increased. Lower elevations exhibited elevated AP fractions due to abundant paratracheal and wide-banded parenchyma in tall trees from coastal and lowland forests. Vasicentric and aliform AP were predominantly associated with greater tree height and wider vessels, which might help cope with high evaporative demands via elastic wood capacitance. In contrast, montane trees featured a higher fiber proportion, scarce axial parenchyma, smaller vessel diameters, and higher vessel densities. The lack of AP in montane trees was often compensated by extended uniseriate ray sections with upright or squared ray cells or the presence of living fibers. CONCLUSIONS: Elevation gradient influenced specific xylem fractions, with lower elevations showing elevated AP due to abundant paratracheal and wide-banded parenchyma, securing greater vessel-to-parenchyma connectivity and lower embolism risk. Montane trees featured a higher fiber proportion and smaller vessel diameters, which may aid survival under greater environmental seasonality and fire risk.

Cumulative nitrogen enrichment alters the drivers of grassland overyielding.

Effects of plant diversity on grassland productivity, or overyielding, are found to be robust to nutrient enrichment. However, the impact of cumulative nitrogen (N) addition (total N added over time) on overyielding and its drivers are underexplored. Synthesizing data from 15 multi-year grassland biodiversity experiments with N addition, we found that N addition decreases complementarity effects and increases selection effects proportionately, resulting in no overall change in overyielding regardless of N addition rate. However, we observed a convex relationship between overyielding and cumulative N addition, driven by a shift from complementarity to selection effects. This shift suggests diminishing positive interactions and an increasing contribution of a few dominant species with increasing N accumulation. Recognizing the importance of cumulative N addition is vital for understanding its impacts on grassland overyielding, contributing essential insights for biodiversity conservation and ecosystem resilience in the face of increasing N deposition.

Effects of plant diversity on productivity strengthen over time due to trait-dependent shifts in species overyielding.

Plant diversity effects on community productivity often increase over time. Whether the strengthening of diversity effects is caused by temporal shifts in species-level overyielding (i.e., higher species-level productivity in diverse communities compared with monocultures) remains unclear. Here, using data from 65 grassland and forest biodiversity experiments, we show that the temporal strength of diversity effects at the community scale is underpinned by temporal changes in the species that yield. These temporal trends of species-level overyielding are shaped by plant ecological strategies, which can be quantitatively delimited by functional traits. In grasslands, the temporal strengthening of biodiversity effects on community productivity was associated with increasing biomass overyielding of resource-conservative species increasing over time, and with overyielding of species characterized by fast resource acquisition either decreasing or increasing. In forests, temporal trends in species overyielding differ when considering above- versus belowground resource acquisition strategies. Overyielding in stem growth decreased for species with high light capture capacity but increased for those with high soil resource acquisition capacity. Our results imply that a diversity of species with different, and potentially complementary, ecological strategies is beneficial for maintaining community productivity over time in both grassland and forest ecosystems.

Contrasting biomass allocations explain adaptations to cold and drought in the world's highest-growing angiosperms.

BACKGROUND AND AIMS: Understanding biomass allocation among plant organs is crucial for comprehending plant growth optimization, survival and responses to global change drivers. Yet, mechanisms governing mass allocation in vascular plants from extreme elevations exposed to cold and drought stresses remain poorly understood. METHODOLOGY: We analyzed organ mass weights and fractions in 258 Himalayan herbaceous species across diverse habitats (wetland, steppe, alpine), growth forms (annual, perennial taprooted, rhizomatous, cushiony), and climatic gradients (3500-6150 m elevation) to explore whether biomass distribution adhered to fixed allometric or optimal partitioning rules, and how variation in size, phylogeny, and ecological preferences influence their strategies for resource allocation. KEY FINDINGS: Following the optimal partitioning theory, Himalayan plants distribute more biomass to key organs vital for acquiring and preserving limited resources necessary for their growth and survival. Allocation strategies are mainly influenced by plant growth forms and habitat conditions, notably temperature, water availability, and evaporative demands. Alpine plants primarily invest in belowground stem bases for storage and regeneration, reducing aboveground stems while increasing leaf mass fraction to maximize carbon assimilation in their short growing season. Conversely, arid steppe plants prioritize deep roots over leaves to secure water and minimize transpiration. Wetland plants allocate resources to aboveground stems and belowground rhizomes, enabling them to resist competition and grazing in fertile environments. CONCLUSIONS: Himalayan plants from extreme elevations optimize their allocation strategies to acquire scarce resources under specific conditions, efficiently investing carbon from supportive to acquisitive and protective functions with increasing cold and drought. Intraspecific variation and shared ancestry did not significantly alter Himalayan plants' biomass allocation strategies. Despite diverse evolutionary histories, plants from similar habitats have developed comparable phenotypic structures to adapt to their specific environments. This study offers new insights into plant adaptations in diverse Himalayan environments and underscores the importance of efficient resource allocation for survival and growth in challenging conditions.

Single-Molecule Time-Resolved Spectroscopy in a Tunable STM Nanocavity.

Spontaneous fluorescence rates of single-molecule emitters are typically on the order of nanoseconds. However, coupling them with plasmonic nanostructures can substantially increase their fluorescence yields. The confinement between a tip and sample in a scanning tunneling microscope creates a tunable nanocavity, an ideal platform for exploring the yields and excitation decay rates of single-molecule emitters, depending on their coupling strength to the nanocavity. With such a setup, we determine the excitation lifetimes from the direct time-resolved measurements of phthalocyanine fluorescence decays, decoupled from the metal substrates by ultrathin NaCl layers. We find that when the tip is approached to single molecules, their lifetimes are reduced to the picosecond range due to the effect of coupling with the tip-sample nanocavity. On the other hand, ensembles of the adsorbed molecules measured without the nanocavity manifest nanosecond-range lifetimes. This approach overcomes the drawbacks associated with the estimation of lifetimes for single molecules from their respective emission line widths.

Major tree species of Central European forests differ in their proportion of positive, negative, and nonstationary growth trends.

Temperate forests are undergoing significant transformations due to the influence of climate change, including varying responses of different tree species to increasing temperature and drought severity. To comprehensively understand the full range of growth responses, representative datasets spanning extensive site and climatic gradients are essential. This study utilizes tree-ring data from 550 sites from the temperate forests of Czechia to assess growth trends of six dominant Central European tree species (European beech, Norway spruce, Scots pine, silver fir, sessile and pedunculate oak) over 1990-2014. By modeling mean growth series for each species and site, and employing principal component analysis, we identified the predominant growth trends. Over the study period, linear growth trends were evident across most sites (56% increasing, 32% decreasing, and 10% neutral). The proportion of sites with stationary positive trends increased from low toward high elevations, whereas the opposite was true for the stationary negative trends. Notably, within the middle range of their distribution (between 500 and 700 m a.s.l.), Norway spruce and European beech exhibited a mix of positive and negative growth trends. While Scots pine growth trends showed no clear elevation-based pattern, silver fir and oaks displayed consistent positive growth trends regardless of site elevation, indicating resilience to the ongoing warming. We demonstrate divergent growth trajectories across space and among species. These findings are particularly important as recent warming has triggered a gradual shift in the elevation range of optimal growth conditions for most tree species and has also led to a decoupling of growth trends between lowlands and mountain areas. As a result, further future shifts in the elevation range and changes in species diversity of European temperate forests can be expected.

Patterns of tropical forest understory temperatures.

Temperature is a fundamental driver of species distribution and ecosystem functioning. Yet, our knowledge of the microclimatic conditions experienced by organisms inside tropical forests remains limited. This is because ecological studies often rely on coarse-gridded temperature estimates representing the conditions at 2 m height in an open-air environment (i.e., macroclimate). In this study, we present a high-resolution pantropical estimate of near-ground (15 cm above the surface) temperatures inside forests. We quantify diurnal and seasonal variability, thus revealing both spatial and temporal microclimate patterns. We find that on average, understory near-ground temperatures are 1.6 °C cooler than the open-air temperatures. The diurnal temperature range is on average 1.7 °C lower inside the forests, in comparison to open-air conditions. More importantly, we demonstrate a substantial spatial variability in the microclimate characteristics of tropical forests. This variability is regulated by a combination of large-scale climate conditions, vegetation structure and topography, and hence could not be captured by existing macroclimate grids. Our results thus contribute to quantifying the actual thermal ranges experienced by organisms inside tropical forests and provide new insights into how these limits may be affected by climate change and ecosystem disturbances.

Global warming alters Himalayan alpine shrub growth dynamics and climate sensitivity.

Global climate change is having significant effects on plant growth patterns and mountain plants can be particularly vulnerable to accelerated warming. Rising temperatures are releasing plants from cold limitation, such as at high elevations and latitudes, but can also induce drought limitation, as documented for trees from lower elevations and latitudes. Here we test these predictions using a unique natural experiment with Himalayan alpine shrub Rhododendron anthopogon and its growth responses to changing climate over a large portion of its latitudinal and elevational ranges, including steep precipitation and temperature gradients. We determined growth dynamics during the last three decades, representing period of accelerated warming, using annual radial growth increments for nine populations growing on both wet and warm southern localities and drier and cold northern localities in the Himalayas along elevation gradients encompassing the lower and upper species range limits. A significant growth increase over past decades was observed after controlling for confounding effect of shrub age and microsites. However, the magnitude of increase varied among populations. Particularly, populations situated in the lower elevation of the northernmost (cold and dry) locality exhibited most substantial growth enhancement. The relationship between growth variability and climate varied among populations, with the populations from the coldest location displaying the strongest responsiveness to increasing minimum temperatures during July. Minimum temperatures of April and August were the most important factor limiting the growth across most populations. Potential warming-induced drought limitation had no significant impact on growth variation in any part of the species geographic range. Overall, our findings indicate that plant growth is continuously increasing in recent decades and growth-climate relationships are not consistent across populations, with populations from the coldest and wettest localities showing stronger responses. The observed patterns suggest that dwarf-shrubs benefit from ongoing warming, leading to increased shrubification of high elevation alpine ecosystems.

Rooting depth and xylem vulnerability are independent woody plant traits jointly selected by aridity, seasonality, and water table depth.

Evolutionary radiations of woody taxa within arid environments were made possible by multiple trait innovations including deep roots and embolism-resistant xylem, but little is known about how these traits have coevolved across the phylogeny of woody plants or how they jointly influence the distribution of species. We synthesized global trait and vegetation plot datasets to examine how rooting depth and xylem vulnerability across 188 woody plant species interact with aridity, precipitation seasonality, and water table depth to influence species occurrence probabilities across all biomes. Xylem resistance to embolism and rooting depth are independent woody plant traits that do not exhibit an interspecific trade-off. Resistant xylem and deep roots increase occurrence probabilities in arid, seasonal climates over deep water tables. Resistant xylem and shallow roots increase occurrence probabilities in arid, nonseasonal climates over deep water tables. Vulnerable xylem and deep roots increase occurrence probabilities in arid, nonseasonal climates over shallow water tables. Lastly, vulnerable xylem and shallow roots increase occurrence probabilities in humid climates. Each combination of trait values optimizes occurrence probabilities in unique environmental conditions. Responses of deeply rooted vegetation may be buffered if evaporative demand changes faster than water table depth under climate change.

Plant-symbiotic fungal diversity tracks variation in vegetation and the abiotic environment along an extended elevational gradient in the Himalayas.

Arbuscular mycorrhizal (AM) fungi can benefit plants under environmental stress, and influence plant adaptation to warmer climates. However, very little is known about the ecology of these fungi in alpine environments. We sampled plant roots along a large fraction (1941-6150 m asl (above sea level)) of the longest terrestrial elevational gradient on Earth and used DNA metabarcoding to identify AM fungi. We hypothesized that AM fungal alpha and beta diversity decreases with increasing elevation, and that different vegetation types comprise dissimilar communities, with cultured (putatively ruderal) taxa increasingly represented at high elevations. We found that the alpha diversity of AM fungal communities declined linearly with elevation, whereas within-site taxon turnover (beta diversity) was unimodally related to elevation. The composition of AM fungal communities differed between vegetation types and was influenced by elevation, mean annual temperature, and precipitation. In general, Glomeraceae taxa dominated at all elevations and vegetation types; however, higher elevations were associated with increased presence of Acaulosporaceae, Ambisporaceae, and Claroideoglomeraceae. Contrary to our expectation, the proportion of cultured AM fungal taxa in communities decreased with elevation. These results suggest that, in this system, climate-induced shifts in habitat conditions may facilitate more diverse AM fungal communities at higher elevations but could also favour ruderal taxa.

Poleward migration of tropical cyclones induced severe disturbance of boreal forest above 50°.

With global warming, tropical cyclones (TCs) are moving to northern latitudes with devastating effects on boreal forests and significant ecological and socioeconomic consequences in the northern hemisphere. Recently, TCs disturbances have been documented in the northern temperate and even the southern boreal forest zone. Here we report and quantify the impact of TC Lingling (2019), which damaged the boreal forests >50° latitude in a remote area of Sakhalin Island, Northeast Asia. A multi-step algorithm was used to identify disturbed forested areas together with Sentinel-2 imagery to recognize windthrow patches caused by TCs and evaluate tree species composition. We found extensive damage to boreal forests caused by TC Lingling, with forested area losses of >80 km2. The affected areas mainly belonged to zonal dark coniferous forests, which account for 54 km2 of windthrows. In contrast, a lower impact was recorded in deciduous broadleaf and larch forests. TC Lingling caused a high proportion (>50 %) of large gaps (>10 ha), however, gaps of such extent have not been previously recorded in these dark coniferous forests. Hence, our study highlights the potential of TCs as the new disturbance agent responsible for extensive disturbances of boreal forests at more northern latitudes than previously thought. This implies the significant role of TCs in disturbance regimes and boreal forest dynamics. We suggest that continued poleward migration of TCs may lead to an unprecedentedly large area of disturbed boreal forests resulting in complex changes in diversity and ecosystem functioning. Our findings are crucial for identifying potential shifts in boreal forest structure and dynamics under ongoing global climate change and altered forest disturbance regimes.

Metabarcoding of soil environmental DNA to estimate plant diversity globally.

Introduction: Traditional approaches to collecting large-scale biodiversity data pose huge logistical and technical challenges. We aimed to assess how a comparatively simple method based on sequencing environmental DNA (eDNA) characterises global variation in plant diversity and community composition compared with data derived from traditional plant inventory methods. Methods: We sequenced a short fragment (P6 loop) of the chloroplast trnL intron from from 325 globally distributed soil samples and compared estimates of diversity and composition with those derived from traditional sources based on empirical (GBIF) or extrapolated plant distribution and diversity data. Results: Large-scale plant diversity and community composition patterns revealed by sequencing eDNA were broadly in accordance with those derived from traditional sources. The success of the eDNA taxonomy assignment, and the overlap of taxon lists between eDNA and GBIF, was greatest at moderate to high latitudes of the northern hemisphere. On average, around half (mean: 51.5% SD 17.6) of local GBIF records were represented in eDNA databases at the species level, depending on the geographic region. Discussion: eDNA trnL gene sequencing data accurately represent global patterns in plant diversity and composition and thus can provide a basis for large-scale vegetation studies. Important experimental considerations for plant eDNA studies include using a sampling volume and design to maximise the number of taxa detected and optimising the sequencing depth. However, increasing the coverage of reference sequence databases would yield the most significant improvements in the accuracy of taxonomic assignments made using the P6 loop of the trnL region.

Surface-Mediated Spin Locking and Thermal Unlocking in a 2D Molecular Array.

Molecule-based functional devices may take advantage of surface-mediated spin state bistability. Whereas different spin states in conventional spin crossover complexes are only accessible at temperatures well below room temperature, and the lifetimes of the high-spin state are relatively short, a different behavior exhibited by prototypical nickel phthalocyanine is shown here. Direct interaction of the organometallic complex with a copper metal electrode mediates the coexistence of a high spin and a low spin state within the 2D molecular array. The spin state bistability is extremely non-volatile, since no external stimuli are required to preserve it. It originates from the surface-induced axial displacement of the functional nickel cores, which generates two stable local minima. Spin state unlocking and the full conversion to the low spin state are only possible by a high temperature stimulus. This spin state transition is accompanied by distinct changes in the molecular electronic structure that might facilitate the state readout at room temperature, as evidenced by valence spectroscopy. The non-volatility of the high spin state up to elevated temperatures and the controllable spin bistability render the system extremely intriguing for applications in molecule-based information storage devices.

Long-term tropical cyclones activity shapes forest structure and reduces tree species diversity of U.S. temperate forests.

Increasing tropical cyclone (TC) pressure on temperate forests is inevitable under the recent global increase of the intensity and poleward migration of TCs. However, the long-term effects of TCs on large-scale structure and diversity of temperate forests remain unclear. Here, we aim to ascertain the legacy of TCs on forest structure and tree species richness by using structural equation models that consider several environmental gradients and use an extensive dataset containing >140,000 plots with >3 million trees from natural temperate forests across eastern United States impacted by TCs. We found that high TC activity (a combination of TC frequency and intensity) leads to a decrease in maximum tree sizes (height and diameter), an increase in tree density and basal area, and a decline in the number of tree species and recruits. We identified TC activity as the strongest predictor of forest structure and species richness in xeric (dry) forests, while it had a weaker impact on hydric (wet) forests. We highlight the sensitivity of forest structure and tree species richness to impacts of likely further increase of TC activity in interaction with climate extremes, especially drought. Our results show that increased TC activity leads to the homogenization of forest structure and reduced tree species richness in U.S. temperate forests. These findings suggest that further declines in tree species richness may be expected because of the projected increase of future levels of TC activity.