Distinct Valence States of the [4Fe4S] Cluster Revealed in the Hydrogenase CrHydA1.

Iron-sulfur clusters play a crucial role in electron transfer for many essential enzymes, including [FeFe]-hydrogenases. This study focuses on the [4Fe4S] cluster ([4Fe]H) of the minimal [FeFe]-hydrogenase from Chlamydomonas reinhardtii (CrHydA1) and employs advanced spectroscopy, site-directed mutagenesis, molecular dynamics simulations, and QM/MM calculations. We provide insights into the complex electronic structure of [4Fe]H and its role in the catalytic reaction of CrHydA1, serving as paradigm for understanding [FeFe]-hydrogenases.

The Effect of Protein Supplementation and Playing Time on Recovery Kinetics During a Congested Basketball Schedule.

Background/objectives: Despite being widely promoted, protein supplementation's overall effectiveness during demanding basketball schedules remains unclear. This study investigated whether increased protein intake can accelerate recovery of muscle function during a 6-day congested basketball microcycle consisting of three consecutive games while accounting for the impact of playing time.

Methods: In a randomized, two-trial, cross-over, double-blind repeated measures design, eighteen male basketball players were assigned to a high (High PT) or a moderate (Mod PT) playing time group and participated in two trials, receiving daily either milk protein (PRO trial) or an isoenergetic amount of carbohydrates.

The Effect of Intraset Rest Periods on External and Internal Load During Small-Sided Games in Soccer.

The purpose of this study was to compare the internal and external load in continuous and intermittent small-sided games (SSG) formats. Eight semi-professional soccer players participated in the study, and they completed three protocols: (a) I-intermittent SSG protocol (Int-I, 4 sets of 4 min with a 3 min recovery); (b) Continuous SSG protocol (Con, 2 sets of 8 min with a 3 min recovery); (c) II-SSG protocol (Int-II, 4 sets of 4 min, where each set includes 1 min of exercise with varying recovery periods (10, 20, 30 s), with a 3 min recovery period between sets). A one-way analysis of variance (ANOVA) was used to analyze the dependent variables, with significance determined at < 0.

Identifying Key Factors for Predicting the Age at Peak Height Velocity in Preadolescent Team Sports Athletes Using Explainable Machine Learning.

Maturation is a key factor in sports participation and often determines the young athletes' characterization as a talent. However, there is no evidence of practical models for understanding the factors that discriminate children according to maturity. Hence, this study aims to deepen the understanding of the factors that affect maturity in 11-year-old Team Sports Athletes by utilizing explainable artificial intelligence (XAI) models.

Meta-Dimethylation of Arenes via Catellani Reaction from Aryl Thianthrenium Salts.

Here we report the reaction of aryl thianthrenium salts that allows selective functionalization of the meta position of arenes. The combination of a site-selective thianthrenation with a Catellani reaction provides access to 3,5-dimethylated arenes. The developed reaction is complementary to the previously discovered reductive ipso-alkylation of aryl thianthrenium salts and extends the possibilities for late-stage methylation of arenes with a single aryl thianthrenium salt.

Touch to text: Spatiotemporal evolution of braille letter representations in blind readers.

Visual deprivation does not silence the visual cortex, which is responsive to auditory, tactile, and other nonvisual tasks in blind persons. However, the underlying functional dynamics of the neural networks mediating such crossmodal responses remain unclear. Here, using braille reading as a model framework to investigate these networks, we presented sighted (N=13) and blind (N=12) readers with individual visual print and tactile braille alphabetic letters, respectively, during MEG recording.

Co-Catalyzed P-H Activation and Related Cp*Co(III) Phosphine Complexes.

This study reports that the well-known Co(III) precursor Co(η-Cp*)I(CO) () is an effective precatalyst for dehydrocoupling reactions of phosphines. Reaction monitoring by NMR, complemented by ESI-MS and EPR, suggests that Co(III) complexes containing secondary and primary phosphine ligands play an important role in this catalysis but that redox chemistry is also facile for these complexes, resulting in paramagnetic species. Representative examples of the mono(phosphine) complexes Co(η-Cp*)I(PRH) () and Co(η-Cp*)I(PRH) () and bis(phosphine) complexes [Co(η-Cp*)I(PRH)] I () have been prepared.

Extensive reference set and refined computational protocol for calculations of Fe Mössbauer parameters.

Mössbauer spectroscopy is a powerful technique for probing the local electronic structure of iron compounds, because it reports in an element-selective manner on both the oxidation state and coordination environment of the Fe ion. Computational prediction of the two main Mössbauer parameters, isomer shift () and quadrupole splitting (Δ), has long been targeted by quantum chemical studies, and useful protocols based on density functional theory have been proposed. Here we present an extensive curated reference set of Fe compounds that is considerably larger and more diverse than literature precedents.

Combined Multireference-Multiscale Approach to the Description of Photosynthetic Reaction Centers.

A first-principles description of the primary photochemical processes that drive photosynthesis and sustain life on our planet remains one of the grand challenges of modern science. Recent research established that explicit incorporation of protein electrostatics in excited-state calculations of photosynthetic pigments, achieved for example with quantum-mechanics/molecular-mechanics (QM/MM) approaches, is essential for a meaningful description of the properties and function of pigment-protein complexes. Although time-dependent density functional theory has been used productively so far in QM/MM approaches for the study of such systems, this methodology has limitations.

Closing Kok's cycle of nature's water oxidation catalysis.

The MnCaO cluster in photosystem II catalyzes water splitting through the S state cycle (i = 0-4). Molecular O is formed and the natural catalyst is reset during the final S → (S) → S transition. Only recently experimental breakthroughs have emerged for this transition but without explicit information on the S-state reconstitution, thus the progression after O release remains elusive.

Hyperbolic graph embedding of MEG brain networks to study brain alterations in individuals with subjective cognitive decline.

An expansive area of research focuses on discerning patterns of alterations in functional brain networks from the early stages of Alzheimer's disease, even at the subjective cognitive decline (SCD) stage. Here, we developed a novel hyperbolic MEG brain network embedding framework for transforming high-dimensional complex MEG brain networks into lower-dimensional hyperbolic representations. Using this model, we computed hyperbolic embeddings of the MEG brain networks of two distinct participant groups: individuals with SCD and healthy controls.

Elucidating substrate binding in the light-dependent protochlorophyllide oxidoreductase.

The Light-Dependent Protochlorophyllide Oxidoreductase (LPOR) catalyzes a crucial step in chlorophyll biosynthesis: the rare biological photocatalytic reduction of the double C[double bond, length as m-dash]C bond in the precursor, protochlorophyllide (Pchlide). Despite its fundamental significance, limited structural insights into the active complex have hindered understanding of its reaction mechanism. Recently, a high-resolution cryo-EM structure of LPOR in its active conformation challenged our view of pigment binding, residue interactions, and the catalytic process.

Spatiotemporal brain hierarchies of auditory memory recognition and predictive coding.

Our brain is constantly extracting, predicting, and recognising key spatiotemporal features of the physical world in order to survive. While neural processing of visuospatial patterns has been extensively studied, the hierarchical brain mechanisms underlying conscious recognition of auditory sequences and the associated prediction errors remain elusive. Using magnetoencephalography (MEG), we describe the brain functioning of 83 participants during recognition of previously memorised musical sequences and systematic variations.

Excitation landscape of the CP43 photosynthetic antenna complex from multiscale simulations.

Photosystem II (PSII), the principal enzyme of oxygenic photosynthesis, contains two integral light harvesting proteins (CP43 and CP47) that bind chlorophylls and carotenoids. The two intrinsic antennae play crucial roles in excitation energy transfer and photoprotection. CP43 interacts most closely with the reaction center of PSII, specifically with the branch of the reaction center (D1) that is responsible for primary charge separation and electron transfer.

Correlating Structure with Spectroscopy in Ascorbate Peroxidase Compound II.

Structural and spectroscopic investigations of compound II in ascorbate peroxidase (APX) have yielded conflicting conclusions regarding the protonation state of the crucial Fe(IV) intermediate. Neutron diffraction and crystallographic data support an iron(IV)-hydroxo formulation, whereas Mössbauer, X-ray absorption (XAS), and nuclear resonance vibrational spectroscopy (NRVS) studies appear consistent with an iron(IV)-oxo species. Here we examine APX with spectroscopy-oriented QM/MM calculations and extensive exploration of the conformational space for both possible formulations of compound II.

Comprehensive Evaluation of Models for Ammonia Binding to the Oxygen Evolving Complex of Photosystem II.

The identity and insertion pathway of the substrate oxygen atoms that are coupled to dioxygen by the oxygen-evolving complex (OEC) remains a central question toward understanding Nature's water oxidation mechanism. In several studies, ammonia has been used as a small "water analogue" to elucidate the pathway of substrate access to the OEC and to aid in determining which of the oxygen ligands of the tetramanganese cluster are substrates for O-O bond formation. On the basis of structural and spectroscopic investigations, five first-sphere binding modes of ammonia have been suggested, involving either substitution of an existing HO/OH/O group or addition as an extra ligand to a metal ion of the MnCaO cluster.

Localization of Brain Signals by Alternating Projection.

A popular approach for modeling brain activity in MEG and EEG is based on a small set of current dipoles, where each dipole represents the combined activation of a local area of the brain. Here, we address the problem of multiple dipole localization with a novel solution called Alternating Projection (AP). The AP solution is based on minimizing the least-squares (LS) criterion by transforming the multi-dimensional optimization required for direct LS solution, to a sequential and iterative solution in which one source at a time is localized, while keeping the other sources fixed.

Exploring Electrophilic Hydrophosphination via Metal Phosphenium Intermediates.

Two Mo(0) phosphenium complexes containing ancillary secondary phosphine ligands have been investigated with respect to their ability to participate in electrophilic addition at unsaturated substrates and subsequent P-H hydride transfer to "quench" the resulting carbocations. These studies provide stoichiometric "proof of concept" for a proposed new metal-catalyzed electrophilic hydrophosphination mechanism. The more strongly Lewis acidic phosphenium complex, [Mo(CO)(PRH)(PR)] (R=Ph, Tol), cleanly hydrophosphinates 1,1-diphenylethylene, benzophenone, and ethylene, while other substrates react rapidly to give products resulting from competing electrophilic processes.

The dual-path hypothesis for the emergence of anosognosia in Alzheimer's disease.

Although neurocognitive models have been proposed to explain anosognosia in Alzheimer's disease (AD), the neural cascade responsible for its origin in the human brain remains unknown. Here, we build on a mechanistic dual-path hypothesis that brings error-monitoring and emotional processing systems as key elements for self-awareness, with distinct impacts on the emergence of anosognosia in AD. Proceeding from the notion of anosognosia as a dimensional syndrome, varying between a lack of concern about one's own deficits (i.

Nature of S-States in the Oxygen-Evolving Complex Resolved by High-Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy.

Photosystem II, the water splitting enzyme of photosynthesis, utilizes the energy of sunlight to drive the four-electron oxidation of water to dioxygen at the oxygen-evolving complex (OEC). The OEC harbors a MnCaO cluster that cycles through five oxidation states S ( = 0-4). The S state is the last metastable state before the O evolution.

Hyperbolic graph embedding of MEG brain networks to study brain alterations in individuals with subjective cognitive decline.

An expansive area of research focuses on discerning patterns of alterations in functional brain networks from the early stages of Alzheimer's disease, even at the subjective cognitive decline (SCD) stage. Here, we developed a novel hyperbolic MEG brain network embedding framework for transforming high-dimensional complex MEG brain networks into lower-dimensional hyperbolic representations. Using this model, we computed hyperbolic embeddings of the MEG brain networks of two distinct participant groups: individuals with SCD and healthy controls.

LOCALIZATION OF SPATIALLY EXTENDED BRAIN SOURCES BY FLEXIBLE ALTERNATING PROJECTION (FLEX-AP).

Magnetoencephalography (MEG) and electroencephalography (EEG) are widely employed techniques for the measurement of neural activity with exceptional temporal resolution. Modeling the neural sources underlying these signals is of high interest for both neuroscience research and pathology. The method of Alternating Projection (AP) was recently shown to outperform the well-established recursively applied and projected multiple signal classification (RAP-MUSIC) algorithm.

Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal-organic framework.

In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O to form high-spin iron(IV) = O species remains an unrealized goal. Here, we report a metal-organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases.

Reaction Center Excitation in Photosystem II: From Multiscale Modeling to Functional Principles.

Oxygenic photosynthesis is the fundamental energy-converting process that utilizes sunlight to generate molecular oxygen and the organic compounds that sustain life. Protein-pigment complexes harvest light and transfer excitation energy to specialized pigment assemblies, reaction centers (RC), where electron transfer cascades are initiated. A molecular-level understanding of the primary events is indispensable for elucidating the principles of natural photosynthesis and enabling development of bioinspired technologies.