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X-ray spectroscopy is a valuable technique for the study of many materials systems. Characterizing reactions in situ and operando can reveal complex reaction kinetics, which is crucial to understanding active site composition and reaction mechanisms. In this project, the design, fabrication and testing of an open-source and easy-to-fabricate electrochemical cell for in situ electrochemistry compatible with X-ray absorption spectroscopy in both transmission and fluorescence modes are accomplished via windows with large opening angles on both the upstream and downstream sides of the cell. Using a hobbyist computer numerical control machine and free 3D CAD software, anyone can make a reliable electrochemical cell using this design. Onion-like carbon nanoparticles, with a 1:3 iron-to-cobalt ratio, were drop-coated onto carbon paper for testing in situ X-ray absorption spectroscopy. Cyclic voltammetry of the carbon paper showed the expected behavior, with no increased ohmic drop, even in sandwiched cells. Chronoamperometry was used to apply 0.4 V versus reversible hydrogen electrode, with and without 15 min of oxygen purging to ensure that the electrochemical cell does not provide any artefacts due to gas purging. The XANES and EXAFS spectra showed no differences with and without oxygen, as expected at 0.4 V, without any artefacts due to gas purging. The development of this open-source electrochemical cell design allows for improved collection of in situ X-ray absorption spectroscopy data and enables researchers to perform both transmission and fluorescence simultaneously. It additionally addresses key practical considerations including gas purging, reduced ionic resistance and leak prevention. [ABSTRACT FROM AUTHOR]

Overcoming slow kinetics and high overpotential in electrocatalytic oxygen evolution reaction (OER) requires innovative catalysts and approaches that transcend the scaling relationship between binding energies for intermediates and catalyst surfaces. Inorganic complexes provide unique, customizable geometries, which can help enhance their efficiencies. However, they are unstable and susceptible to chemical reaction under extreme pH conditions. Immobilizing complexes on substrates creates single‐molecule catalysts (SMCs) with functional similarities to single‐atom catalysts (SACs). Here, an efficient SMC, composed of dichloro(1,3‐bis(diphenylphosphino)propane) nickel [NiCl2dppp] anchored to a graphene acid (GA), is presented. This SMC surpasses ruthenium‐based OER benchmarks, exhibiting an ultra‐low onset and overpotential at 10 mAcm−2 when exposed to a static magnetic field. Comprehensive experimental and theoretical analyses imply that an interfacial charge transfer from the Ni center in NiCl2dppp to GA enhances the OER activity. Spectroscopic investigations reveal an in situ geometrical transformation of the complex and the formation of a paramagnetic Ni center, which under a magnetic field, enables spin‐selective electron transfer, resulting in enhanced OER performance. The results highlight the significance of in situ geometric transformations in SMCs and underline the potential of an external magnetic field to enhance OER performance at a single‐molecule level. [ABSTRACT FROM AUTHOR]

Carbon dioxide electroreduction facilitates the sustainable synthesis of fuels and chemicals1. Although Cu enables CO2-to-multicarbon product (C2+) conversion, the nature of the active sites under operating conditions remains elusive2. Importantly, identifying active sites of high-performance Cu nanocatalysts necessitates nanoscale, time-resolved operando techniques3–5. Here, we present a comprehensive investigation of the structural dynamics during the life cycle of Cu nanocatalysts. A 7 nm Cu nanoparticle ensemble evolves into metallic Cu nanograins during electrolysis before complete oxidation to single-crystal Cu2O nanocubes following post-electrolysis air exposure. Operando analytical and four-dimensional electrochemical liquid-cell scanning transmission electron microscopy shows the presence of metallic Cu nanograins under CO2 reduction conditions. Correlated high-energy-resolution time-resolved X-ray spectroscopy suggests that metallic Cu, rich in nanograin boundaries, supports undercoordinated active sites for C–C coupling. Quantitative structure–activity correlation shows that a higher fraction of metallic Cu nanograins leads to higher C2+ selectivity. A 7 nm Cu nanoparticle ensemble, with a unity fraction of active Cu nanograins, exhibits sixfold higher C2+ selectivity than the 18 nm counterpart with one-third of active Cu nanograins. The correlation of multimodal operando techniques serves as a powerful platform to advance our fundamental understanding of the complex structural evolution of nanocatalysts under electrochemical conditions.By investigation of structural dynamics during the life cycle of Cu nanocatalysts, correlation of multimodal operando techniques was found to serve as a powerful platform to advance understanding of their complex structural evolution. [ABSTRACT FROM AUTHOR]

This document is a correction to a research article titled "Nickel-Based Single-Molecule Catalysts with Synergistic Geometric Transition and Magnetic Field-Assisted Spin Selection Outperform RuO2 for Oxygen Evolution" published in the journal Advanced Energy Materials. The correction addresses an error in Figure S5d of the supporting information, specifically related to the O1s raw spectrum of NiGA. The corrected data is provided in a revised figure. Additionally, the document includes revised sentences in the "Computation Details" section to provide greater clarity about the methodology used in the research. The authors apologize for the error. [Extracted from the article]

Platinum is used extensively as a catalyst for a wide variety of chemical reactions, though its scarcity and price present limitations to expansions of its use. To understand the origin of platinum's versatility—with the goals of both improving the efficiency of existing catalysts and mimicking its reactivity with more abundant metals—the mechanisms of platinum-catalyzed chemical reactions must be understood via structural and spectroscopic characterization of these catalysts under operando conditions. Such data, typically consisting of complex mixtures of species, often prove challenging to interpret, inviting the aid of chemical theory. DFT calculations in particular have proven successful at predicting structural and spectroscopic parameters of transition metal species, though a thorough investigation of how these methods perform for platinum-based complexes has yet to be undertaken. Herein, we evaluated the performance of geometry optimization for five commonly used functionals (BP86, PBE, B3LYP, PBE0, and TPSSh) in combination with various ligand basis sets, relativistic approximations, and solvation and dispersion models. We applied these DFT methods to a training set of 14 platinum-containing complexes with varying sizes, oxidation states, and number and type of ligands and determined that the best-performing method was the PBE0 functional together with the def2-TZVP basis set for the ligand atoms, the ZORA relativistic approximation, and solvation and dispersion corrections. The ability of this DFT methodology to accurately predict metrical parameters was confirmed using two case studies, most notably by comparing the DFT optimized geometry of a previously uncharacterized complex to newly collected EXAFS data, which showed excellent agreement. [ABSTRACT FROM AUTHOR]

Urbanisation is a globally occurring phenomenon and is predicted to continue increasing rapidly. Urban ecosystems present novel environments and challenges which species must acclimate or adapt to. These novel challenges alter existing or create new selection pressures on behaviours which provide an opportunity to investigate eco-evolutionary responses to contemporary environmental change. We used 7 years of breeding data from urban and forest populations of blue and great tits to understand whether selection for timing of breeding or clutch size differed between the two habitats and species. We found that urban great tits laid eggs earlier than their forest counterparts, but there was no evidence of a difference in selection for earlier breeding. Blue tits, however, did not differ in timing of egg laying between the two habitats, but selection for earlier laying was weaker in the urban environment. Both species laid smaller clutches in the urban site and had positive selection for larger clutch sizes which did not differ in strength for the great tits but did for blue tits, with weaker selection in the urban population. Our results suggest that food availability for nestlings may be constraining urban birds, and that the temporal cues females use to time breeding correctly, such as tree budburst and food availability, may be absent or reduced in urban areas due to lower caterpillar availability. These results have implications for our understanding of the adaptation of wild animals to city life. Significance statement: Urbanisation is expanding rapidly and changing the environment many species live in. A key challenge is to understand how species adapt to the urban environment, why some species can adapt, why others cannot and what we can do to ensure that cities are ecologically sustainable and biodiversity rich. Here we show that the strength of natural selection for early breeding and larger clutch size is weaker in urban than non-urban blue tits, likely due to reduced and irregular availability of natural insect food in urban areas. This effect was not found in great tits. Thus, urbanisation can alter the selection pressures wild animals are exposed to, but this effect may differ between species, even when closely related. This has implications for our understanding of how species adapt to urban life. [ABSTRACT FROM AUTHOR]

To robustly predict the effects of disturbance and ecosystem changes on species, it is necessary to produce structurally realistic models with high predictive power and flexibility. To ensure that these models reflect the natural conditions necessary for reliable prediction, models must be informed and tested using relevant empirical observations. Pattern‐oriented modelling (POM) offers a systematic framework for employing empirical patterns throughout the modelling process and has been coupled with complex systems modelling, such as in agent‐based models (ABMs). However, while the production of ABMs has been rising rapidly, the explicit use of POM has not increased. Challenges with identifying patterns and an absence of specific guidelines on how to implement empirical observations may limit the accessibility of POM and lead to the production of models which lack a systematic consideration of reality. This review serves to provide guidance on how to identify and apply patterns following a POM approach in ABMs (POM‐ABMs), specifically addressing: where in the ecological hierarchy can we find patterns; what kinds of patterns are useful; how should simulations and observations be compared; and when in the modelling cycle are patterns used? The guidance and examples provided herein are intended to encourage the application of POM and inspire efficient identification and implementation of patterns for both new and experienced modellers alike. Additionally, by generalising patterns found especially useful for POM‐ABM development, these guidelines provide practical help for the identification of data gaps and guide the collection of observations useful for the development and verification of predictive models. Improving the accessibility and explicitness of POM could facilitate the production of robust and structurally realistic models in the ecological community, contributing to the advancement of predictive ecology at large. [ABSTRACT FROM AUTHOR]

Recent reviews on sexual dichromatism in frogs included Mannophryne trinitatis as the only example they could find of dynamic dichromatism (males turn black when calling) within the family Aromobatidae and found no example of ontogenetic dichromatism in this group. We demonstrate ontogenetic dichromatism in M. trinitatis by rearing post-metamorphic froglets to near maturity: the throats of all individuals started as grey coloured; at around seven weeks, the throat became pale yellow in some, and more strongly yellow as development proceeded; the throats of adults are grey in males and variably bright yellow in females, backed by a dark collar. We demonstrated the degree of throat colour variability by analysing a large sample of females. The red: green (R:G) ratio ranged from ~1.1 to 1.4, reflecting variation from yellow to yellow/orange, and there was also variation in the tone and width of the dark collar, and in the extent to which the yellow colouration occurred posterior to the collar. Female M. trinitatis are known to be territorial in behaviour. We show a positive relationship between throat colour (R:G ratio) and escape performance, as a proxy for quality. Our field observations on Tobago's M. olmonae showed variability in female throat colour and confirmed that males in this species also turn black when calling. Our literature review of the 20 Mannophryne species so far named showed that all females have yellow throats with dark collars, and that male colour change to black when calling has been reported in eight species; in the remaining 12 species, descriptions of males calling are usually lacking so far. We predict that both dynamic and ontogenetic sexual dichromatism are universal in this genus and provide discussion of the ecological role of dichromatism in this genus of predominantly diurnal, non-toxic frogs, with strong paternal care of offspring. [ABSTRACT FROM AUTHOR]

In an article published in Advanced Energy Materials, Sreeprasad T. Sreenivasan and his team discuss the use of in-situ geometric changes in single molecule catalysts to enhance electrocatalytic activity under a magnetic field. This innovative approach to spin-polarized oxygen evolution reaction surpasses established benchmarks and opens up new possibilities for magnetically activated single-molecule catalysts. The authors provide a comprehensive analysis of their findings, highlighting the potential applications of this research in the field of energy materials. [Extracted from the article]

Abstract: Proton transfer reactions are of central importance to a wide variety of biochemical processes, though determining proton location and monitoring proton transfers in biological systems is often extremely challenging. Herein, we use two‐color valence‐to‐core X‐ray emission spectroscopy (VtC XES) to identify protonation events across three oxidation states of the O2‐activating, radical‐initiating manganese–iron heterodinuclear cofactor in a class I‐c ribonucleotide reductase. This is the first application of VtC XES to an enzyme intermediate and the first simultaneous measurement of two‐color VtC spectra. In contrast to more conventional methods of assessing protonation state, VtC XES is a more direct probe applicable to a wide range of metalloenzyme systems. These data, coupled to insight provided by DFT calculations, allow the inorganic cores of the MnIVFeIV and MnIVFeIII states of the enzyme to be assigned as MnIV(μ‐O)2FeIV and MnIV(μ‐O)(μ‐OH)FeIII, respectively. [ABSTRACT FROM AUTHOR]

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The bioinorganic chemistry community has had a long history of utilizing a diverse range of spectroscopic techniques to obtain detailed geometric and electronic structural insights into metalloprotein active sites. In recent years, the development of beamlines optimized for high-resolution X-ray spectroscopy has provided novel tools for the elucidation of biological active site structures. These methods include both non-resonant and resonant X-ray emission spectroscopy. Herein, we briefly introduce both X-ray absorption and X-ray emission spectroscopy, and the added information that can be obtained through high-resolution measurements. The information content of each spectroscopic approach, as well as the required instrumentation, is discussed. Applications of these methods in bioinorganic chemistry are highlighted. [ABSTRACT FROM AUTHOR]

The Cerrado biome covers a large area of central Brazil, containing a mosaic of physiognomies determined by soil fertility, seasonal rainfall, and fire. The ground layer vegetation presents a high eudicot diversity and a high proportion of belowground phytomass, represented mainly by a diversity of underground organs storing carbohydrates. Fructans and other soluble carbohydrates are claimed to be more than reserves, conferring protection against abiotic stresses due to osmoregulation properties and rapid turnover. Inulin- and levan-type fructans are prominent and found respectively in the underground organs of Asteraceae and Amaranthaceae, abundant families in the herbaceous Cerrado flora. Poaceae, mainly Panicoideae, is also abundant and accumulates glucose, sucrose, and malto-oligosaccharides, but not fructans, in contrast with temperate grasses. Here, we review evidence that fructans in the herbaceous flora of the Cerrado play a significant role in tolerance to drought and fire, promoting the rapid recovery of the ground-layer vegetation after environmental disturbances. [ABSTRACT FROM AUTHOR]

Pressure-probe measurements and single-cell sampling and analysis techniques were used to determine the effect of photosynthetic production and accumulation of sugars on osmotic and turgor pressures of individual cells of barley (Hordeum vulgare L.) source leaves. In control plants, the changes in osmotic pressure in individual cells during the photoperiod were different for mesophyll (increase of 276 mOsmol/kg), parenchymatous bundle sheath (PBS; increase of 100 mOsmol/kg) and epidermis (remains constant). There was also an increase in osmotic pressure at the tissue level. Cooling of roots and the shoot apical meristem restricted the export of sugars from leaves, and the resulting changes in osmotic and turgor pressure were monitored. In contrast to the control leaves, mesophyll, PBS, and epidermal cells showed a similar increase in osmotic pressure (up to 500 mOsmol/kg). Cooling also increased the turgor pressure in epidermal and (to a greater extent) PBS cells. The difference in turgor pressure between epidermal and PBS cells is consistent with the presence of a water potential gradient within the leaf, from the vascular bundles towards the leaf surface. [ABSTRACT FROM AUTHOR]

Leaf sucrose, starch, hexose and maximum extractable soluble acid invertase activity were compared throughout the day in source leaves of 13 plant species chosen for their putative phloem-loading type (apoplastic or symplastic). Four species which represent the different phloem-loading types (tomato, barley, maize and Fuchsia) were studied in detail. Using this information we wished to determine whether a positive correlation between foliar carbohydrates and acid invertase activity exists in leaves from different species and, furthermore, whether this relationship is determined by phloem-loading type. Acid invertase activity was relatively constant throughout the day in all species. The extent of sucrose, hexose and starch accumulation and the sucrose: starch ratio measured at a given time were species-dependent. No correlations were found between foliar soluble acid invertase activity and the hexose, sucrose or starch content of the leaves in any of the species, regardless of phloem-loading type. The species examined could be divided into three distinct groups: (1) high sucrose, low invertase; (2) low sucrose, low invertase; and (3) low sucrose, high invertase. The absence of an inverse relationship between leaf sucrose, hexose or starch contents and endogenous soluble acid invertase suggests that this enzyme is not directly involved in carbon partitioning in leaves but serves an auxiliary function. [ABSTRACT FROM AUTHOR]

In this paper, the response to temperature of three physiological processes has been examined in detail in seedlings of sorghum and pearl millet. These have been compared with their field performance under high temperature conditions with the aim of developing laboratory-based screening techniques for seedling thermotolerance. Membrane thermostability, as assessed by electrolyte leakage, seedling re-growth and protein synthetic ability were measured in seedlings exposed to a range of temperatures using a thermal gradient bar, The effect of genotype, seedling age and pre-treatment was examined. Differences between genotypes were only apparent after seedlings had been given a brief high temperature pre-treatment (2 h at 43 °C). Similar results were found with all three methods used and their suitability for use in the screening of large numbers of entries is discussed. Significant correlation was found between the ability of membrane thermostability to acclimate and seedling survival in the field. [ABSTRACT FROM AUTHOR]

Photoassimilate produced by mature leaves is usually loaded into the phloem as sucrose. Transport of sucrose from the mesophyll cells to the phloem might involve an apoplastic step or be entirely symplastic, depending on species. Acid invertase occurs as both soluble and cell-wall-bound forms and has been detected in mature leaves. However, the ability of this enzyme to act as a regulator of carbon export and storage depends on whether it occurs either in the sucrose transport path (which could decrease export), or is located within the mesophyll cells (potentially resulting in intracellular futile cycling between sucrose synthesis in the cytoplasm and hydrolysis in the vacuole). Tissue-level localization of acid invertase was investigated by tissue printing, which establishes protein distribution within a leaf. Antiserum was raised against a synthetic peptide corresponding to a region close to the active site of acid invertase. Tissue prints from Pisum sativum L. and Hordeum vulgare L. showed invertase to be located in the vascular regions, which was not observed in Fuchsia hybrida L. This corresponds to differences in the presence of oligosaccharides in leaf extracts and in the pattern of plasmodesmatal connections between mesophyll cells and the vasculature. We hypothesize that the location of acid invertase activity is implicated in species-specific differences in sucrose and oligosacchande metabolism. [ABSTRACT FROM AUTHOR]

A soluble acid invertase was extracted by mechanical disruption of mycelium of the psychrophile Monographella nivalis grown on sucrose in submerged culture. The crude preparation was stable to incubation at pH 6.2 for 1 h at temperatures up to 47 °C and was stable to handling at room temperature. Half of the initial activity was lost after 1 h at 52 °C and all activity was lost after 1 h at 57 °C. A single isoform with activity against sucrose was detected on both native PAGE and IEF activity gels, exhibiting an isoelectric point of pH 3.6. The activity bound tightly to Concanavalin A-sepharose and was not displaced by 500 mM α-methyl mannopyranosidase indicating the enzyme to be a mannose-containing glycoprotein. By gel filtration, the apparent Mr was determined at 195 kDa. The invertase was purified 106-fold by salt precipitation. The partially purified enzyme exhibited maximal activity at pH 4.2 and apparent Michaelis constants for sucrose of 1.2, 2.0 and 2.6 mM at 3, 9 and 15 °C. The activity increased exponentially with temperature in the range 7-55 °C. Q10 fell with increased temperature giving values of 1.96 between 5 and 15 °C and 1.60 between 40 and 50°C. Maximal activity was recorded at 55 °C. Arrhenius analysis of temperature data in the range 7-52 °C produced a continuous linear relationship. The activation energy for sucrose hydrolysis was 38.8 kJ mol-1. The thermal stability and thermal kinetic properties of the invertase were similar to those of invertases from mesophilic organisms. The invertase catalysed fructosyl transfer at 13% of the molar activity against sucrose when assayed under conditions analogous to those in culture. The major fructan products were neokestose, isokestose, kestose and an unidentified tetrasaccharide. Traces of larger fructans were also detected. The transient accumulation of fructan in cultures of M. nivalis can be explained as a side reaction of invertase activity. The enzymological and physiological data do not suggest a cryoprotective function for fructan during the growth of the fungus. [ABSTRACT FROM AUTHOR]

An asporogenous strain of the pink snow mould fungus, Monographella nivalis (Schaffnit) E. Müller, anamorph Gerlachia nivalis Ces. ex Sac.) W. Gams & E. Müller (Syn. Fusarium nivale Ces. ex Sacc.), grew at 5 °C on a defined salts medium plus vitamins and utilized a variety of simple and polymeric carbohydrates as the sole carbon and energy source. Mycelium was grown at temperatures between 3 and 15 °C in aerated submerged fermentation culture in chemically defined mediam plus sucrose. Optimum growth rates of 0.035-0.033 h-1 occurred between 9 and 12 °C. Growth in a simple medium showed that all biochemical and physiological processes necessary for growth were functional at 3 °C. The growth performance of the organism at low temperatures was no better than would be expected from extrapolation of mesophilic growth responses to temperature. The optimum growth temperature of 9-12 °C showed that some biochemical or physiological process was impaired above 12 °C. Uptake and incorporation of 35S-methionine by mycelium at different temperatures showed that general protein synthesis increased up to 25 °C, and hence was not responsible per se for the sensitivity to temperatures above 12 °C. Heat shock proteins were synthesized at the relatively low temperature of 25 °C, consistent with the low temperature optimum for growth. When grown with sucrose as the sole carbon source, the mycelium catalyzed the extracellular hydrolysis of sucrose, releasing glucose and fructose together with a small amount of fructan trisaccharides and a trace of tetra- and penta-saccharides. Fructan accumulation was transient, corresponding with maximal rates of sucrose hydrolysis. Most biomass formation occurred in the absence of fructan in the culture, hence fructan was not necessary for growth at low temperature and did not appear to function as a cryoprotectant. Invertase activity was mostly (60-70%) bound to mycelium; the remainder was free in the culture supernatant. The regulation of invertase expression appeared to be by sucrose-induction, rather than by end-product repression. Rates of sucrose hydrolysis in culture were temperature-sensitive and were markedly depressed above 12c, indicating inhibition of invertase formation. [ABSTRACT FROM AUTHOR]

Vegetative plants of Lolium temulentum L, grown at 20°C with an 8 h photoperiod were transferred to either 5 or 2°C (8 h photoperiod) at 4th leaf maturity. Measurement of dry weight gain indicated a marked decline in relative growth rate below 5°C, with growth being reduced as much between 5 and 2°C as between 20 and 5°C. This reduction was not associated with increased mortality and was reversible if plants were returned to 20°C. Tissue explants from cold‐treated plants retained the ability to extend if returned to 20°C Rates of extension in explants were less temperature sensitive than the relative growth rates observed in intact plants. Measurements of photosynthetic capacity, and of the patterns of accumulation of reserve carbohydrate in plants exposed to different temperatures, suggested that the inhibition of growth caused by chilling is not caused by an inability of the plants to fix sufficient carbon. [ABSTRACT FROM AUTHOR]

Discusses the distribution and activity of invertase in mature leaves of Lolium temulentum in relation to the anabolic and catabolic processes that occur in such tissues. Metabolism of sucrose in heterotophic epidermis and vasculature tissues; Changes in assimilate abundance; Patterns of gene expression; Metabolism of oligosaccharides based on sucrose.