Fast Turnover Research Articles

PGM-Free Oer Catalyst for Water Splitting – an Interrogation on the Structural Dynamics of Catalyst during Reaction

Green hydrogen production through proton exchange membrane water electrolyzer (PEMWE) offers the advantages of high current density and high H2 purity with low footprint. At present, the platinum group metal (PGM) such as Ir are the catalysts of choice for the oxygen evolution reaction (OER) at PEMWE anode. The high cost and limited reserve of Ir add a significant cost to broad implementation of PEM electrolyzer.Replacing Ir with earth-abundant transition metals could help to reduce the electrolyzer system cost. For PEMWE application, a PGM-free anodic catalyst must be highly active to match the performance of Ir. Furthermore, it must be stable against oxidative acid corrosion. At Argonne, we recently developed a nanofibrous cobalt spinel OER catalyst prepared from cobalt zeolitic methyl-imidazolate framework (Co-ZIF) doped with manganese and lanthanum. [1] A PEMWE containing this catalyst with the anodic loading of ~2.0 mg/cm2 demonstrated a current density of 2A/cm2 at 2.47 volts or 4A/cm2 at 3.00 volts. The catalyst also showed a promising stability under accelerated-stress-test (AST) through voltage cycling as well as galvanostatic tests at different current densities.To better understand the structure-function relationship, we conducted extensive structural characterizations and computational modeling. For example, our high-resolution electron microscopy study showed a catalyst morphology mimicking that of ZIF precursor but composed of cobalt spinel crystallites with an average size of 3.5 nm. The oxygen atoms on the top layer of the spinel surface are in the relaxed mode. X-ray absorption spectroscopy showed strong oxygen deficiencies around cobalt compared to standard spinel reference. Such deficiency became more predominant at higher cell voltage. Contrary to general perception, the cobalt oxidation state actually decreased instead of increasing at the escalating OER potential and fast turnover rate. Accompanying the change of oxidation state, reduction of oxygen coordination number surrounding Co and growth of Debby-Weller factor of Co-O shell were observed, indicating rapid exchange of the lattice oxygen in spinel during OER. On the other hand, no such changes were observed for the atomically dispersed Mn ion in the spinel as the dopant.In this presentation, we will discuss in our detailed findings and offer our perspective on the future research direction for PGM-free OER catalyst for PEM water electrolyzer application. Acknowledgement: This work is supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewal Energy, Hydrogen and Fuel Cell Technologies Office, and by Laboratory Directed Research and Development funding of Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DEAC02-06CH11357. Work performed at the Center for Nanoscale Materials and Advanced Photon Source, both U.S. Department of Energy Office of Science User Facilities, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.[1] “La- and Mn-doped cobalt spinel oxygen evolution catalyst for proton exchange membrane electrolysis” Lina Chong, Guoping Gao, Jianguo Wen, Haixia Li, Haiping Xu, Zach Green, Joshua D. Sugar, A. Jeremy Kropf, Wenqian Xu, Xiao-Min Lin, Hui Xu, Lin-Wang Wang, Di-Jia Liu, Science 380, 609–616 (2023)

Carbon translocation within land snails affects the carbon isotopic fractionation

Stable carbon isotope composition (δ13C) of land snail materials is widely used as a proxy for reconstructing past vegetation and environmental changes. Interpretation δ13C data is challenging due to the complexities of snail physiology. This study cultured Lissachatina fulica (Bowdich, 1822) snails to investigate δ13C of their soft tissues and excrement under various plant types and dietary carbonate content. Our results show that snails primarily assimilate organic matter (OM), with limited use of dietary carbonates. δ13C of organic matter in excrement correlates positively with that in the diet, but exhibits deviations due to variable carbon isotopic fractionation during assimilation. Tissue δ13C (δ13Ctissue) is positively related to the δ13C of OM (δ13COM) in the diet, varying by turnover rates, with faster turnover rate, such as the digestive gland, exhibiting more negative δ13Ctissue values. Moreover, carbon isotopic fractionation between tissues and diet (Δ13Ctissue-OM) differs based on plant type. Snails fed with C3 plants show positive Δ13Ctissue-OM values, whereas those fed with C4 plants exhibit negative values. These Δ13Ctissue-OM values are far from equilibrium (Δ13Ctissue-OM = 0) with conditions of rapid snail growth. Our findings indicate that the snails fed with C3 and C4 plants result in distinct carbon isotopic fractionation, leading to the deviation in δ13C between plants and land snail materials (e.g., excrement, tissues, shells and shell-bound organic matter). A comprehensive model of carbon metabolism and isotopic fractionation in snails is proposed including the assimilation process from diet to soft tissues and excretion. This study highlights the importance of physiological factors such as growth rates and turnover rates when interpreting δ13C of land snail materials for paleoenvironmental reconstructions.

Highly Specific and Rapid Multiplex Identification of Candida Species Using Digital Microfluidics Integrated with a Semi-Nested Genoarray.

Candida species are the most common cause of fungal infections around the world, associated with superficial and even deep-seated infections. In clinical practice, there is great significance in identifying different Candida species because of their respective characteristics. However, current technologies have difficulty in onsite species identification due to long turnover time, high cost of reagents and instruments, or limited detection performance. We developed a semi-nested recombinase polymerase amplification (RPA) genoarray as well as an integrated system for highly specific identification of four Candida species with a simple design of primers, high detection sensitivity, fast turnover time, and good cost-effectiveness. The system constructed to perform the assay consists of a rapid sample processing module for nucleic acid release from fungal samples in 15 min and a digital microfluidic platform for precise and efficient detection reactions in 35 min. Therefore, our system could automatically identify specific Candida species, with a reagent consumption of only 2.5 μL of the RPA reaction mixture per target and no cross-reaction. Its detection sensitivity for four Candida species achieved 101-102 CFU/mL, which was 10-fold better than conventional RPA and even comparable to a common polymerase chain reaction. Evaluated by using cultured samples and 24 clinical samples, our system shows great applicability to onsite multiplex nucleic acid analysis.

Quantifying protein kinetics in vivo: Influence of precursor dynamics on product labeling.

Protein kinetics can be quantified by coupling stable isotope tracer methods with mass spectrometry readouts; however, inter-connected decision points in the experimental design affect the complexity of the workflow and impact data interpretations. For example, choosing between a single bolus (pulse-chase) or a continuous exposure protocol influences subsequent decisions regarding when to measure and how to model the temporal labeling of a target protein. Herein, we examine the merits of in vivo tracer protocols, we direct attention towards stable isotope tracer experiments that rely on administering a single bolus since these are generally more practical to use as compared to continuous administration protocols. We demonstrate how the interplay between precursor and product kinetics impacts downstream analytics and calculations by contrasting fast vs slow turnover precursors (e.g. 13C-leucine vs 2H-water, respectively). Although the data collected here underscore certain advantages of using longer lived precursors (e.g. 2H- or 18O-water) the results also highlight the influence of tracer recycling on measures of protein turnover. We discuss the impact of tracer recycling and consider how the sampling interval is critical for interpreting studies. Finally, we demonstrate that tracer recycling does not limit the ability to perform back-to-back studies of protein kinetics. It is possible to run experiments in which subjects are used as their own controls even though the precursor and product remain labeled following an initial tracer dosing.

Computational Modeling and Analysis of the TGF-β-induced ERK and SMAD Pathways.

TGF-β, an important cytokine that plays a key role in many diseases regulates a wide array of cellular and physiologic processes via several TGF-β-driven signaling cascades, including the SMAD and non-SMAD-driven pathways. However, the detailed mechanisms by which TGF-β induces such diverse responses remain poorly understood. In particular, compared to the SMAD-dependent pathway, SMAD-independent pathways such as the ERK/MAPK pathway, which is critical in cancer progression, are less characterized. Here, we develop an integrated mechanistic model of the TGF-β-triggered ERK activation pathway and its crosstalk with the SMAD pathway, an analysis of which demonstrates how SMAD dynamics can be significantly modulated and regulated by the ERK pathway. In particular, SMAD-mediated transcription can be altered and delayed due to expedited phosphorylation of the linker of SMAD by TGF-β-activated ERK; and enhanced ERK activity, but attenuated SMAD activity, can be achieved simultaneously by fast turnover of TGF-β receptors via lipid-rafts. Also, in silico mutations of the TGF-β pathways reveal that the dynamic characteristics of both SMAD and ERK signaling may change significantly during cancer development. Specifically, normal cells may exhibit enhanced and sustained SMAD signaling with transient ERK activation, whereas cancerous cells may produce elevated and prolonged ERK signaling with enervated SMAD activation. These distinctive differences between normal and cancerous signaling behavior provide clues concerning, and potential explanations for, the seemingly contradictory roles played by TGF-β during cancer progression. We demonstrate how crosstalk among various branch pathways of TGF-β can influence overall cellular behavior. Based on model analysis, we hypothesize that aberrant molecular alterations drive changes in the intensity and duration of SMAD and ERK signaling during cancer progression and ultimately lead to an imbalance between the SMAD and ERK pathways in favor of tumor promotion. Thus, to treat cancer patients with a genetic signature of oncogenic Ras effectively may require at least a combination therapy to restore both the expression of TGF-β receptors and the GTPase activity of Ras.

Glucoproteins in particulate and mineral-associated organic matter pools during grassland restoration

Glomalin related soil proteins (GRSP) produced by arbuscular mycorrhizal fungi are important stabilizing components of soil aggregates, and consequently helping to entrap organic matter and encapsulate it from microbial decomposition. Grasslands provide excellent opportunity to study GRSP effects because arbuscular mycorrhiza responsible for GRSP production is well development on roots of grasses. Fast GRSP production will accelerate soil organic carbon (SOC) accumulation, but the contribution of GRSP to particulate organic C (POC) and mineral-associated organic C (MAOC) pool remain unclear. We investigated GRSP content and thermal stability of POC and MAOC in topsoil (0–10 cm) as dependent on grassland restoration. SOC content had a nonlinear rise tendency with grassland restoration, and SOC changes were largely dependent on MAOC (>64 %). The POC content decreased by 58 %, while the MAOC content increased by 34 % after 40 years of restoration, microbial transformation of POC plays important role for MAOC formation. The GRSP content contributed 1.7 times more to MAOC (15 %) content than to POC (9 %), but the potential accumulation of GRSP in POC was higher than that in MAOC. The GRSP in the POC pool (less protected) is more sensitive to grassland restoration than in the MAOC pool (more protected). Thermally easily decomposable and refractory organic matter was quantified in POC and MAOC. Thermal stability of MAOC was higher than POC, and GRSP contribute to increase in SOC thermal stability. The GRSP content and thermal stability of POC pool gradually decreased with grassland restoration, reflecting production of more organic matter available for microorganisms and with fast turnover. In conclusion, we must account for the role of GRSP in maintaining SOC thermal stability, and the potential for GRSP sequestration during grassland restoration.

Variation in Successional Dynamics Shape Biodiversity Patterns over a Tropical-Temperate Latitudinal Gradient.

AbstractSuccessional dynamics can vary because of a range of ecological and environmental factors, but our understanding of biogeographic variation in succession, and the processes contributing to community development across ecosystems, is limited. The pattern and rate of recruitment of dispersive propagules likely differs over large spatial scales and can be an important predictor of successional trajectory. Over a 20° tropical-temperate latitudinal gradient, we measured sessile invertebrates over 12 months of community development and successive 3-month recruitment windows to understand succession and how it is influenced by recruitment. Succession and recruitment patterns varied over latitude. In the tropics, fast temporal turnover, fluctuating abundances, and lack of successional progression suggest that the contribution of stochastic processes was high. As latitude increased, successional progression became more apparent, characterized by increasing species richness and community cover and a shift to more competitive taxa over time. At temperate locations, species identities were similar between older communities and recruiting assemblages; however, community composition became more variable across space over time. Such divergence suggests an important role of early colonizers and species interactions on community structure. These findings demonstrate differences in the processes contributing to community development and biodiversity patterns over latitude. Understanding such biogeographic variation in community dynamics and identifying the prevalence of different processes can provide insights into how communities assemble and persist in response to environmental variability.

A continental-wide decline of occupancy and diversity in five Neotropical carnivores

The Neotropics are a global biodiversity hotspot that has undergone dramatic land use changes over the last decades. However, a temporal perspective on the continental-wide distributions of species in this region is still missing. To unveil it, we model the entire area of occupancy of five Neotropical carnivore species at two time periods (2000–2013 and 2014–2021) using integrated species distribution models (ISDMs) in a Bayesian framework. The carnivores are the jaguarundi (Herpailurus yagouaroundi), margay (Leopardus wiedii), maned wolf (Chrysocyon brachyurus), tayra (Eira barbara), and giant otter (Pteronura brasiliensis). We mapped the temporal change, the areas where gains and losses accumulated for all species (hotspots of change) and calculated the temporal species turnover and change in spatial turnover. We show that (1) most carnivore species have declined their area of occupancy (i.e., range size) in the last two decades, (2) their diversity has decreased over time, mostly in the Chaco region, and (3) that hotspots of fast species composition turnover are in Chaco, the Caatinga region, and northwest of Mexico. We discuss how these newly identified hotspots of change overlap with regions of well-known and pronounced land use transformation. These estimated patterns of overall decline are alarming, more so given that four out of the five species had been classified as not threatened by IUCN. The official global threat status of these species may need to be re-evaluated. All this would be invisible if standard forecasts, local expert knowledge, or static threat criteria, such as range size, were used. We thus provide a new approach to evaluate past species range dynamics based on multiple lines of evidence, which can be employed over more species in the future, particularly in under-sampled regions.

AAMP and MTSS1 Are Novel Negative Regulators of Endothelial Barrier Function Identified in a Proteomics Screen.

Cell-cell adhesion in endothelial monolayers is tightly controlled and crucial for vascular integrity. Recently, we reported on the importance of fast protein turnover for maintenance of endothelial barrier function. Specifically, continuous ubiquitination and degradation of the Rho GTPase RhoB is crucial to preserve quiescent endothelial integrity. Here, we sought to identify other barrier regulators, which are characterized by a short half-life, using a proteomics approach. Following short-term inhibition of ubiquitination with E1 ligase inhibitor MLN7243 or Cullin E3 ligase inhibitor MLN4924 in primary human endothelial cells, we identified sixty significantly differentially expressed proteins. Intriguingly, our data showed that AAMP and MTSS1 are novel negative regulators of endothelial barrier function and that their turnover is tightly controlled by ubiquitination. Mechanistically, AAMP regulates the stability and activity of RhoA and RhoB, and colocalizes with F-actin and cortactin at membrane ruffles, possibly regulating F-actin dynamics. Taken together, these findings demonstrate the critical role of protein turnover of specific proteins in the regulation of endothelial barrier function, contributing to our options to target dysregulation of vascular permeability.

How Does Escherichia coli Allocate Proteome?

Microorganisms are shown to actively partition their intracellular resources, such as proteins, for growth optimization. Recent experiments have begun to reveal molecular components unpinning the partition; however, quantitatively, it remains unclear how individual parts orchestrate to yield precise resource allocation that is both robust and dynamic. Here, we developed a coarse-grained mathematical framework that centers on guanosine pentaphosphate (ppGpp)-mediated regulation and used it to systematically uncover the design principles of proteome allocation in Escherichia coli. Our results showed that the cellular ability of resource partition lies in an ultrasensitive, negative feedback-controlling topology with the ultrasensitivity arising from zero-order amino acid kinetics and the negative feedback from ppGpp-controlled ribosome synthesis. In addition, together with the time-scale separation between slow ribosome kinetics and fast turnovers of ppGpp and amino acids, the network topology confers the organism an optimization mechanism that mimics sliding mode control, a nonlinear optimization strategy that is widely used in man-made systems. We further showed that such a controlling mechanism is robust against parameter variations and molecular fluctuations and is also efficient for biomass production over time. This work elucidates the fundamental controlling mechanism of E. coli proteome allocation, thereby providing insights into quantitative microbial physiology as well as the design of synthetic gene networks.

Pengaruh Perputaran Modal Kerja Terhadap Profitabilitas Pada Usaha Mikro Sembako Mitra Indo Grosir Di Karawang

The objectives of this study are (1) To know, analyze and explain how the turnover of working capital and profitability in micro businesses of Indo Grosir partners in Karawang. (2) To find out, analyze and explain how the effect of working capital turnover on profitability in micro grocery businesses of Indo Grosir partners in Karawang. Through descriptive verifiability, simple regression analysis as the method with the use of quantitative research as the type of research where a total of 61 micro business partners, basic necessities, and wholesale partners in Karawang are the population of this study. 30 samples of micro food businesses were obtained by the purposive sampling method used for sampling. The results of the Descriptive Test in this study show that the working capital turnover rate in micro grocery enterprises of Indo Wholesale partners in Karawang has a fast period with the highest working capital turnover rate of 1.12. Meanwhile, the highest profitability level in micro grocery businesses of Indo Wholesale partners in Karawang is 16.93%. This is due to the low profits obtained in running the business, which affects the turnover of working capital and profitability. Partially, the results show that the profitability of micro grocery enterprises of Indo Wholesale partners in Karawang is not affected by the turnover of working capital, where the results are based on the output of verifiable tests that have been carried out on problems that have been formulated with simple linear regression analysis. The absence of influence is due to the low profits of micro-food businesses with fast working capital turnover.

Butyrylcholinesterase with altered catalytic triad, acting as a promising bioscavenger against organophosphorus agents

Cholinesterases (ChEs) are irreversibly inhibited by organophosphorus compounds (OP) through phosphylation of their active site serine. OPs can be regarded as pseudo-substrates of ChEs in which water-mediated dephosphylation is very slow or impossible. Then, it has been attempted by genetic engineering to convert ChEs into OP hydrolases by speeding up dephosphylation rates. The knowledge of ChEs crystal structure and implementation of potent in silico methods allow rational computer design of new mutants. Such ChE mutants could be used as catalytic bioscavengers in medical counter-measures of OP poisoning. In the present work, using QM/MM MD, we designed a new mutant of human butyrylcholinesterase (BChE). This double mutant, Glu325Gly/Asn322Glu, alters the functioning of the catalytic triad (Ser198.His438.Glu325 in wild-type enzyme), making a new one Ser198.His438.Glu322. Calculations with echothiophate as a model OP showed that the new catalytic triad is stable and capable of hydrolysing the phosphorylated serine. Thus, self-reactivation of the mutated enzyme is possible. Although the calculated dephosphylation rate constant is low, it is expected that the introduction of a third mutation will lead to a much faster turnover.

Screening Cover Crops for Utilization in Irrigated Vineyards: A Greenhouse Study on Species' Nitrogen Uptake and Carbon Sequestration Potential.

This study examines the potential of 23 plant species, comprising 10 legumes, 9 grasses, and 4 forbs, as cover crops to enhance carbon (C) sequestration and soil nitrogen (N) in vineyards. After a 120-day evaluation period, cover crop biomass was incorporated into the soil, and grapevine seedlings were planted in its place. Among the established cover crops, the C input potential ranged from 0.267 to 1.69 Mg ha-1, and the N input potential ranged from 12.3 to 114 kg ha-1. Legume species exhibited up to threefold greater shoot dry weight (SDW) compared to grass species. Ladino white clover, Dutch white clover, and Clover blend were superior in SDW, total dry weight (TDW), total C content, and total N content. Legumes exhibited slightly higher root dry weight (RDW) than grasses, with the exception of Fall rye leading at 15 g pot-1, followed by Ladino white clover and Dutch white clover at an average of 12 g pot-1. Legumes, particularly clover blend and Alsike clover, displayed high shoot N concentration at an average of 2.95%. Root N concentration in Legumes (Fabaceae) were significantly higher at 1.82% compared to other plant families at 0.89%, while their root C/N ratio was lower at 18.3, contrasting with others at 27.7, resulting in a faster turnover. Biomass production exhibited a negative relationship (R2 = 0.51) with soil residual NO3-. Fall rye, Winfred brassica, and buckwheat had the highest N utilization efficiency (NUtE) values (ava. 121 g g-1). Alsike clover, Ladino white clover, and clover blend showed the highest N uptake efficiency (NUpE) values (ava. 75%). The Readily Available N (RAN) Reliance Index (RANRI) is introduced as a novel indicator for quantifying the extent to which a plant relies on RAN for its total N requirement. The RANRI value represents the percentage of the plant's total N sourced from RAN, ranging from 11% for legumes to 86% for grasses. This implies a substantial influx of nitrogen through a pathway independent of RAN in legumes. Grape shoot N concentration positively correlated with soil NO3- (R2 = 0.31) and cover crop C/N ratio (R2 = 0.17) but negatively correlated with cover crop TDW (R2 = 0.31). This study highlights legume plants as more effective in C and N assimilation during establishment but cautions about potential soil mineral N depletion before reaching their full biological N fixation capacity.

The success, satisfaction and experiences of international students in an immersive block model

Despite growing interest in immersive block models in higher education, very little is known about the experiences of international students in these non-traditional forms of learning. To enable an initial view of how international students perceive and perform in an immersive block model, we used an exploratory mixed methods approach to examine the academic success, satisfaction, and experiences of international students in a 6-week immersive block model at a regional public Australian university. Inferential statistical tests were used to explore the success rates and unit and teaching satisfaction of onshore and offshore international students in the immersive block model and in the traditional trimester model. Overall, the immersive block model made a significant positive difference to the academic success of international students, both onshore and offshore. However, a decline in satisfaction was observed among science and engineering students, contrasting with an increase in satisfaction among business and arts students. Data collected through semi-guided interviews with 10 students from this latter group indicate several key benefits and challenges associated with immersive block learning. Students reported heightened focus and motivation, supportive teaching, and a healthy study-work-life balance. Challenges included not knowing what to expect, forming social connections with classmates, and the fast turnover between assessments. These findings indicate that it is important for institutions to prepare international students well for the pace and time management demands of studying in an immersive block model and to encourage the formation of social connections. Assessment timing, volume, and scaffolding should also be key considerations in immersive block model curriculum design.

Decoupled shifts of dominant and rarer fish species as a response to warming and extreme events in a large estuary

AbstractDisentangling community responses to multiple stressors in a warming context is one of the most challenging tasks ecologists face. Taking advantage of a long‐term (1989–2017) and intensive fish monitoring survey (N = ~900K from 804 seines‐day), we present a comprehensive analysis on the dynamics of coastal fish communities in Jamaica Bay, New York, by addressing multiple dimensions of community change that although closely related are rarely considered in a single work. Specifically, we tested hypotheses about changes in composition, composition variability and community functional attributes, and the role of environmental drivers acting at different temporal scales. Our analyses suggest two decoupled community dynamics triggered by two different extreme events. First, the 1999 Atlantic Multidecadal Oscillation phase switch caused an abrupt shift from a single‐species dominance to intermittent co‐dominance, with species preferring higher temperatures, a shift that has persisted in time but that may be cyclical at a multidecadal scale. Second, the 2012 heat wave promoted an abrupt collapse of rare and cold‐water species, and the sudden arrival of warmer‐water species in a portion of the community that was already increasingly variable due to long‐term warming. Functionally, the entire community subtly shifted toward species with faster turnover and lower trophic levels. Our work sheds light on the complex responses of biological communities to warming in terms of the impacts on composition, its temporal variability, and its functional dimension, by disentangling the interplay of long‐term environmental trends such as warming, multidecadal cycles, and extreme events on different portions (i.e., dominant and rare thermal species) of the community.

Dynamics of tree stems and biomass in old‐growth and secondary forests along gradients in liana dominance, elevation and soil

Abstract Lianas, or woody vines, are key components of many tropical forests and can have substantial impacts on the dynamics and functioning of these important ecosystems. Their competition with trees for resources, in particular light, can hamper the recovery of forests from disturbances. Yet, it is unclear how forest disturbance interacts with liana–tree ratio (LTR), topography and soil properties to shape tree dynamics and the trajectories of forest succession. Using temporal data from the Kilombero Valley and the Udzungwa Mountains of Tanzania, we demonstrate how the dynamics of tree stems and biomass vary between secondary and old‐growth forests with changes in the dominance of lianas and environmental gradients. Greater tree recruitment and mortality in secondary forests compared with old‐growth forests suggested rapid regeneration processes and faster turnover. However, no significant differences were found in the net annual changes in the number or biomass of trees between secondary and old‐growth forests. Our findings also showed that higher LTRs were positively associated with stem mortality but also with tree biomass growth, indicating a nuanced ecological role of lianas in forest ecosystems, which warrants further investigation to fully understand the causal factors at play. Net changes in tree stem numbers decreased significantly with elevation, implying climatic constraints on forest regeneration at higher elevations. Soil cation exchange capacity and organic carbon were found to significantly influence tree stem recruitment and net change in abundance, although their effects on biomass remained unclear. Synthesis: Our findings indicate that the recovery of tropical forests from disturbance in terms of the number and biomass of tree stems may be predictable along environmental gradients. These insights have the potential to broaden our capacity to develop more nuanced strategies that identify when and where tropical forests may require restoration interventions, with a focus on structural recovery.

Environmental warming increases the importance of high-turnover energy channels in stream food webs.

Warming temperatures are altering communities and trophic networks across Earth's ecosystems. While the overall influence of warming on food webs is often context-dependent, increasing temperatures are predicted to change communities in two fundamental ways: (1) by reducing average body size and (2) by increasing individual metabolic rates. These warming-induced changes have the potential to influence the distribution of food web fluxes, food web stability, and the relative importance of deterministic and stochastic ecological processes shaping community assembly. Here, we quantified patterns and the relative distribution of organic matter fluxes through stream food webs spanning a broad natural temperature gradient (5-27°C). We then related these patterns to species and community trait distributions of mean body size and population biomass turnover (P:B) within and across streams. We predicted that (1) communities in warmer streams would exhibit smaller body size and higher P:B and (2) organic matter fluxes within warmer communities would increasingly skew toward smaller, higher P:B populations. Across the temperature gradient, warmer communities were characterized by smaller body size (~9% per °C) and higher P:B (~7% faster turnover per °C) populations on average. Additionally, organic matter fluxes within warmer streams were increasingly skewed toward higher P:B populations, demonstrating that warming can restructure organic matter fluxes in both an absolute and relative sense. With warming, the relative distribution of organic matter fluxes was decreasingly likely to arise through the random sorting of species, suggesting stronger selection for traits driving high turnover with increasing temperature. Our study suggests that a warming world will favor energy fluxes through "smaller and faster" populations, and that these changes may be more predictable than previously thought.

2D electron gas formation on InAs wurtzite nanosheet surfaces

The two-dimensional electron gas (2DEG) that forms on a semiconductor surface can be used to explore a variety of phenomena in quantum physics and plays an important role in nanoscale electronics, such as transistors. Controlling its formation is, thus, relevant. Using angle-resolved photoemission spectroscopy (ARPES) and accumulating the signal over many nanocrystals, we find that on clean InAs nanosheets with non-polar surfaces and wurtzite (WZ) crystal structures, a 2DEG can be observed at the Γ-point. We suggest that the step morphology on the WZ InAs specimens facilitates the appearance of the electron gas, since previous studies on InAs nanowire surfaces with the same crystal facet and a similar defect density did not exhibit a 2DEG. Subsequently, bismuth deposition leads to the disappearance of the 2DEG as well as a shift of the valence band. This is in contrast to previous observations on InAs surfaces, in which metal deposition would lead to the formation of a 2DEG. The control of the 2DEG with the addition of Bi atoms is relevant for applications of InAs nanosheets in quantum technologies. This study also illustrates that ARPES accumulated over several 2D materials oriented randomly around their normal axis can provide valuable information on their band structure with a fast turnover and low irradiation.

Cx31.1 can selectively intermix with co-expressed connexins to facilitate its assembly into gap junctions.

Connexins are channel-forming proteins that function to facilitate gap junctional intercellular communication. Here, we use dual cell voltage clamp and dye transfer studies to corroborate past findings showing that Cx31.1 (encoded by GJB5) is defective in gap junction channel formation, illustrating that Cx31.1 alone does not form functional gap junction channels in connexin-deficient mammalian cells. Rather Cx31.1 transiently localizes to the secretory pathway with a subpopulation reaching the cell surface, which is rarely seen in puncta reminiscent of gap junctions. Intracellular retained Cx31.1 was subject to degradation as Cx31.1 accumulated in the presence of proteasomal inhibition, had a faster turnover when Cx43 was present and ultimately reached lysosomes. Although intracellularly retained Cx31.1 was found to interact with Cx43, this interaction did not rescue its delivery to the cell surface. Conversely, the co-expression of Cx31 dramatically rescued the assembly of Cx31.1 into gap junctions where gap junction-mediated dye transfer was enhanced. Collectively, our results indicate that the localization and functional status of Cx31.1 is altered through selective interplay with co-expressed connexins, perhaps suggesting Cx31.1 is a key regulator of intercellular signaling in keratinocytes.

Ligand Field Sensitive Spin Acceleration in the Iron-Catalyzed [2 + 2] Cycloaddition of Unactivated Alkenes and Dienes.

Redox-active pyridine(diimine) (PDI) iron catalysts promote the reversible [2 + 2] cycloaddition of alkenes and dienes to cyclobutane derivatives that have applications ranging from fuels to chemically recyclable polymers. Metallacycles were identified as key intermediates, and spin crossover from the singlet to the triplet surface was calculated to facilitate the reductive coupling step responsible for the formation of the four-membered ring. In this work, a series of sterically and electronically differentiated PDI ligands was studied for the [2 + 2] cycloaddition of ethylene and butadiene to vinylcyclobutane. Kinetic studies revealed that the fastest and slowest turnover were observed with equally electron-deficient supporting ligands that either feature phenyl-substituted imine carbon atoms (MeBPDI) or a pyrazine core (MePZDI). While the oxidative cyclization was comparatively slow for both catalysts, the rate of reductive coupling─determined by stoichiometric 13C2H4 labeling studies─correlated with the turnover frequencies. Two-state density functional theory studies and the distinct electronic structures of related (iPrBPDI) and (iPrPZDI) iron methyl complexes revealed significantly different ligand field strengths due to either diminished ligand σ-donation (MeBPDI) or promoted metal π-backbonding (MePZDI). Spin acceleration, leading to fast reductive coupling and catalytic turnover, was promoted in the case of the weaker ligand field and depends on both the nature and position of the electron-withdrawing group. This study provides strong evidence for the role of two-state reactivity in C(sp3)-C(sp3) bond formation and insights on how ligand design either promotes or inhibits spin acceleration in earth-abundant metal catalysis.