Computational Insights into the Mechanism of Lewis Acid-Catalyzed Alkene-Aldehyde Coupling.

The Lewis acid-catalyzed coupling of alkenes and aldehydes presents a modern, versatile synthetic alternative to classical carbonyl addition chemistry, offering exceptional regio- and stereoselectivity. In this work, we present a comprehensive computational investigation into the reaction mechanism of this transformation. Our findings confirm the occurrence of an enantioselective trans-annular [1,5]-hydride shift step and demonstrate that the enantioselectivity of the reaction arises predominantly from steric clashes between functional groups in the cyclization step.

Modelling sensory attenuation as Bayesian causal inference across two datasets.

Introduction: To interact with the environment, it is crucial to distinguish between sensory information that is externally generated and inputs that are self-generated. The sensory consequences of one's own movements tend to induce attenuated behavioral- and neural responses compared to externally generated inputs. We propose a computational model of sensory attenuation (SA) based on Bayesian Causal Inference, where SA occurs when an internal cause for sensory information is inferred.

Coordinated immune networks in leukemia bone marrow microenvironments distinguish response to cellular therapy.

Understanding how intratumoral immune populations coordinate antitumor responses after therapy can guide treatment prioritization. We systematically analyzed an established immunotherapy, donor lymphocyte infusion (DLI), by assessing 348,905 single-cell transcriptomes from 74 longitudinal bone marrow samples of 25 patients with relapsed leukemia; a subset was evaluated by both protein- and transcriptome-based spatial analysis. In acute myeloid leukemia (AML) DLI responders, we identified clonally expanded CD8 cytotoxic T lymphocytes with in vitro specificity for patient-matched AML.

A bi-kinase module sensitizes and potentiates plant immune signaling.

Systemic signaling is an essential hallmark of multicellular life. Pathogen encounter occurs locally but triggers organ-scale and organismic immune responses. In plants, elicitor perception provokes systemically expanding Ca and HO signals conferring immunity.

Chromosome-scale genome dynamics reveal signatures of independent haplotype evolution in the ancient asexual mite .

Some unique asexual species persist over time and contradict the consensus that sex is a prerequisite for long-term evolutionary survival. How they escape the dead-end fate remains enigmatic. Here, we generated a haplotype-resolved genome assembly on the basis of a single individual and collected genomic data from worldwide populations of the parthenogenetic diploid oribatid mite to identify signatures of persistence without sex.

Nontarget screening of a Siberian ice core reveals changes in the pre-industrial to industrial organic aerosol composition.

Glaciers serve as natural archives for reconstructing past changes of atmospheric aerosol concentration and composition. While most ice-core studies have focused on inorganic species, organic compounds, which can constitute up to 90% of the submicrometer aerosol mass, have been largely overlooked. To our knowledge, this study presents the first nontarget screening record of secondary organic aerosol species preserved in a Belukha ice core (Siberia, Russian Federation), ranging from the pre-industrial to the industrial period (1800-1980 CE).

Highly Nucleophilic Pyridinamide Anions in Apolar Organic Solvents due to Asymmetric Ion Pair Association.

Free ions in organic solvents of low polarity would be valuable tools for the activation of low-reactivity substrates. However, the formation of unreactive ion pairs at concentrations relevant for synthesis has prevented the success of this concept so far. On the example of highly nucleophilic pyridinamide phosphonium salts in dichloromethane, we show that asymmetric aggregation offers a solution to this general problem.

Estimating effective population size trajectories from time-series identity-by-descent segments.

Long, identical haplotypes shared between pairs of individuals, known as identity-by-descent (IBD) segments, result from recently shared co-ancestry. Various methods have been developed to utilize IBD sharing for demographic inference in contemporary DNA data. Recent methodological advances have extended the screening for IBD segments to ancient DNA (aDNA) data, making demographic inference based on IBD also possible for aDNA.

An analytical model of label-free nanoscale chemical imaging reveals avenues toward improved spatial resolution and sensitivity.

Atomic force microscopy-infrared spectroscopy (AFM-IR) is a photothermal scanning probe technique that combines nanoscale spatial resolution with the chemical analysis capability of mid-infrared spectroscopy. Using this hybrid technique, chemical identification down to the single molecule level has been demonstrated. However, the mechanism at the heart of AFM-IR, the transduction of local photothermal heating to cantilever deflection, is still not fully understood.

Protocol to generate dual-target compounds using a transformer chemical language model.

Here, we present a protocol to generate dual-target compounds (DT-CPDs) interacting with two distinct target proteins using a transformer-based chemical language model. We describe steps for installing software, preparing data, and pre-training the model on pairs of single-target compounds (ST-CPDs), which bind to an individual protein, and DT-CPDs. We then detail procedures for assembling ST- and corresponding DT-CPD data for specific protein pairs and evaluating the model's performance on hold-out test sets.

Influence of Unspecific Visual-Perceptual-Cognitive Task Constraints on Jump Ability and Reactive Strength in Federated Soccer Players.

Soccer players must react quickly and execute complex mental processes to adapt to competitive scenarios while maintaining peak physical performance. Perceptual-cognitive training methods integrate reaction tasks using nonspecific visual stimuli with game-like motor actions, but the impact on explosive strength responses is unclear. This study investigates the effect of nonspecific visual stimuli with varying perceptual-cognitive constraints on jump performance, including countermovement jump height, reactive strength index modified, action time, and reaction time.

First insights into the life history of the early Miocene deer Procervulus ginsburgi from Spain.

The small-sized cervid Procervulus is considered as the most basal member of the Cervidae and one of the earliest ruminants bearing antler-like appendages. The Iberian Miocene record of this stem-cervid is extensively documented and largely overlaps with the Miocene Climatic Optimum (MCO), a transient period of global warming of particular interest when comparing present and near future conditions. Despite receiving a substantial amount of attention, histological studies on Procervulus are very scarce and only limited to postcranial remains of Procervulus praelucidus from Germany (MN3).

A comparative analysis of perceptual noise in lateral and depth motion: Evidence from eye tracking.

The characterization of how precisely we perceive visual speed has traditionally relied on psychophysical judgments in discrimination tasks. Such tasks are often considered laborious and susceptible to biases, particularly without the involvement of highly trained participants. Additionally, thresholds for motion-in-depth perception are frequently reported as higher compared to lateral motion, a discrepancy that contrasts with everyday visuomotor tasks.

Regulatory and retrograde signaling networks in the chlorophyll biosynthetic pathway.

Plants, algae and photosynthetic bacteria convert light into chemical energy by means of photosynthesis, thus providing food and energy for most organisms on Earth. Photosynthetic pigments, including chlorophylls (Chls) and carotenoids, are essential components that absorb the light energy necessary to drive electron transport in photosynthesis. The biosynthesis of Chl shares several steps in common with the biosynthesis of other tetrapyrroles, including siroheme, heme and phycobilins.

Effects of an intervention targeting social media app use on well-being outcomes: A randomized controlled trial.

Background: Interventions targeting social media use show mixed results in improving well-being outcomes, particularly for persons with problematic forms of smartphone use. This study assesses the effectiveness of an intervention app in enhancing well-being outcomes and the moderating role of persons' perceptions about problematic smartphone use (PSU).

Methods: In a randomized controlled trial, N = 70 participants, allocated to the intervention (n = 35) or control condition (n = 35), completed weekly online surveys at baseline, post-intervention, and follow-up.

In situ Electron Paramagnetic Resonance Investigation of Isotope-selective Breathing in MIL-53 during Dihydrogen Adsorption.

The development of smart materials capable of separating dihydrogen isotopologues has risen recently. Among potential candidates, the flexible MIL-53 (Al) has been gaining attention due to its structural flexibility providing the so-called ''breathing mechanism'' that can be useful to separate hydrogen isotopologues selectively. In the present work, an in situ continuous wave electron paramagnetic resonance investigation has been proven as a sensitive technique to follow the isotopologue-selective adsorption-desorption of dihydrogen species on the paramagnetic metal-doped MIL-53 (Al0.

Self-healing behavior of metallopolymers in complex.

This current study focusses on the investigation of the self-healing abilities of metallopolymers containing different kinds of metal complexes, which were processed by direct digital light processing (DLP) based three-dimensional (3D) printing. For this purpose, 2‑phenoxyethyl acrylate is mixed with ligand-containing monomers either based on triphenylmethyl(trt)-histidine or terpyridine, respectively. Either zinc(II) or nickel(II) salts are successfully applied for a complexation of the ligand monomers in solution and, subsequently, photopolymerization is performed.

Impact of Repeated Glucocorticoid Oral Administration on the Urinary Steroid Profile.

The detection of endogenous anabolic androgenic steroids (EAAS) is performed with the Steroidal Module of the Athlete Biological Passport (ABP). Glucocorticoids (GC) could be a confounding factor to the ABP Steroidal Module because they inhibit the hypothalamic-pituitary-adrenal axis, and ABP metabolites have partial adrenal origin. In previous studies, single-dose systemic GC administrations have been shown to reduce the urinary ratios A/T and 5αdiol/E.

Confined growth by self-combustion of a Cu-based nanophase into mesostructured acid supports for DME production from CO2.

This work deals with the design of nanocomposite hydrogenation-dehydration bifunctional catalysts for the one-pot conversion of CO2 to dimethyl ether (DME), focusing on obtaining a high and homogeneous dispersion of a Cu-based CO2 hydrogenation phase into the pores of mesostructured supports. Particularly, three aluminosilicate mesostructured acid catalysts with catalytic activity towards methanol dehydration and featuring different porous structures (Al-MCM-41, Al-SBA-15, Al-SBA-16) were synthesized and used as supports to host a CuO/ZnO/ZrO2 (CZZ) CO2 hydrogenation catalyst for methanol synthesis. The use of a mesostructured support allows to maximize the exposed surface of the CO2 reduction function by nanostructuring it through its confinement within the mesochannels, thus obtaining nanocomposite bifunctional catalysts with an ultra-small hydrogenation nanophase.

Sterol-Targeted Laboratory Evolution Allows the Isolation of Thermotolerant and Respiratory-Competent Clones of the Industrial Yeast Saccharomyces cerevisiae.

Sterol composition plays a crucial role in determining the ability of yeast cells to withstand high temperatures, an essential trait in biotechnology. Using a targeted evolution strategy involving fluconazole (FCNZ), an inhibitor of the sterol biosynthesis pathway, and the immunosuppressant FK506, we aimed to enhance thermotolerance in an industrial baker's yeast population by modifying their sterol composition. This approach yielded six isolates capable of proliferating in liquid YPD with μ values ranging from 0.

Acute lipid droplet accumulation induced by the inhibition of the phospholipase DDHD2 does not affect the level, solubility, or phosphoserine-129 status of α-synuclein.

α-Synuclein (αS) is a 140 amino-acid neuronal protein highly enriched in presynaptic nerve terminals. Its progressive accumulation in Lewy bodies and neurites is the hallmark of Parkinson's disease (PD). A growing number of studies highlights a critical interplay between lipid metabolism and αS biology.

Up-flow anaerobic sludge blanket bioreactor for the production of carboxylates: effect of inocula on process performance and microbial communities.

This research investigated the acidogenic fermentation (AF) of sugar cane molasses in an up-flow anaerobic sludge blanket (UASB) reactor for the production of carboxylates. The first step was to assess the optimum process temperature (25, 35 or 55 ºC) using two different granular inocula, one from a brewery company (BGS) and other from a paper plant company (PGS). These experiments determined that the most suitable temperature for carboxylates production was 25 ºC, obtaining higher bioconversions (27.

Pollen-Derived Fatty Acids and Amino Acids Mediate Variance in Pollinator Visitation.

Pollinators help maintain functional landscapes and are sensitive to floral nutritional quality. Both proteins and lipids influence pollinator foraging, but the role of individual biochemical components in pollen remains unclear. We conducted an experiment comprising common garden plots of six plant species (Asteraceae, Rosaceae, Onagraceae, Boraginaceae, and Plantaginaceae).

Proteomic Variation in the Oral Secretion of Spodoptera exigua and Spodoptera littoralis Larvae in Response to Different food Sources.

The Spodoptera genus is defined as the pest-rich genus because it contains some of the most destructive lepidopteran crop pests, characterized by a wide host range. During feeding, the caterpillars release small amounts of oral secretion (OS) onto the wounded leaves. This secretion contains herbivore-induced molecular patterns (HAMPs) that activate the plant defense response, as well as effectors that may inhibit or diminish the plant's anti-herbivory response.

ATM Expression and Activation in Ataxia Telangiectasia Patients with and without Class Switch Recombination Defects.

Background: Ataxia telangiectasia mutated (ATM) kinase plays a critical role in DNA double-strand break (DSB) repair. Ataxia telangiectasia (A-T) patients exhibit abnormalities in immunoglobulin isotype expression and class switch recombination (CSR). This study investigates the role of residual ATM kinase expression and activity in the severity of A-T disease.