bluuebunny/crossref_metadata_2025_split huggingface dataset:
Microglia internalize tau monomers and fibrils using distinct receptors but similar mechanisms
Authors: Falkon Kristian F. , Danford Liliana , Gutierrez Kuri Eduardo , Esquinca‐Moreno Paulina , Peña Señeriz Yaren L. , Smith Sabrina , Wickline Jessica L. , Louwrier Ariel , McPhail Jacob A. , Sayre Naomi L. , Hopp Sarah C. 
Published: December 2024

AbstractINTRODUCTIONAlzheimer's disease (AD) and other tauopathies are characterized by intracellular aggregates of microtubule‐associated protein tau that are actively released and promote proteopathic spread. Microglia engulf pathological proteins, but how they endocytose tau is unknown.METHODSWe measured endocytosis of different tau species by microglia after pharmacological modulation of macropinocytosis or clathrin‐mediated endocytosis (CME) or antagonism/genetic depletion of known tau receptors heparan‐sulfate proteoglycans (HSPGs) and low‐density lipoprotein receptor‐related protein 1 (LRP1).RESULTSDynamin inhibition decreased microglial endocytosis of all tested tau species. Meanwhile, HSPG antagonism blocked only fibril uptake, and LRP1 antagonism or genetic depletion inconsistently inhibited the endocytosis of fibrils and monomers. Cre recombinase robustly enhanced tau uptake with partial selectivity for fibrils.DISCUSSIONThese data show that microglia take up both tau monomers and aggregates via a dynamin‐dependent form of endocytosis (eg, CME) but may differ in using HSPGs for entry depending on species.Highlights
Microglial endocytosis of tau monomers and fibrils is dynamin‐dependent.
HSPG antagonism blocks microglial uptake of tau fibrils but not monomers.
LRP1 antagonism or knockdown inconsistently inhibits tau uptake.
TAT‐Cre stimulates semi‐selective uptake of fibrils over monomers.
Increased White Matter Aerobic Glycolysis in Multiple Sclerosis
Authors: Brier Matthew R , Judge Bradley , Ying Chunwei , Salter Amber , An Hongyu , Patel Aakash , Wang Qing , Wang Yong , Cross Anne H , Naismith Robert T , Benzinger Tammie LS , Goyal Manu S 
Published: December 2024

ObjectiveDespite treatments which reduce relapses in multiple sclerosis (MS), many patients continue to experience progressive disability accumulation. MS is associated with metabolic disruptions and cerebral metabolic stress predisposes to tissue injury and possibly impaired remyelination. Additionally, myelin homeostasis is metabolically expensive and reliant on glycolysis. We investigated cerebral metabolic changes in MS and when in the disease course they occurred, and assessed their relationship with microstructural changes.MethodsThis study used combined fluorodeoxyglucose (FDG) positron emission tomography (PET) and magnetic resonance imaging (MRI) to measure cerebral metabolic rate of glucose and oxygen, thereby quantifying glycolysis. Twelve healthy controls, 20 patients with relapsing MS, and 13 patients with non‐relapsing MS were studied. Relapsing patients with MS were treatment naïve and scanned pre‐ and post‐initiation of high efficacy disease modifying therapy.ResultsIn normal appearing white matter, we observed increased glucose utilization and reduced oxygen utilization in newly diagnosed MS, consistent with increased glycolysis. Increased glycolysis was greater in patients with a longer disease duration course and higher disability. Among newly diagnosed patients, different treatments had differential impacts on glucose utilization. Last, whereas hypermetabolism within lesions was clearly associated with inflammation, no such relationship was found within normal appearing white matter.InterpretationIncreased white matter glycolysis is a prominent feature of cerebral metabolism in MS. It begins early in the disease course, increases with disease duration and is independent of microstructural evidence of inflammation in normal appearing white matter. Optimization of the metabolic environment may be an important component of therapies designed to reduce progressive disability. ANN NEUROL 2024
Air‐Mediated Biomimetic Synthesis of Polyhydroxyalkanoate with C4 Diol
Authors: Xie Huilin , Zhong Kaibin , Niu Shihao , Li Xiaoxu , Hu Zexu , Xiao Guang , Huang Yifu , Zhang Hongjie , Liu Yuan , Zhang Hefeng , Cai Qiuquan 
Published: December 2024

AbstractPoly(4‐hydroxybutyrate) (P4HB) is a high‐performance, well‐recyclable, and biodegradable polyhydroxyalkanoate (PHA). However, conventional bioproduction of homopolymeric P4HB involves complex and costly processes with C4 feedstocks, particularly 1,4‐butanediol (BDO), and enzyme‐coenzyme systems in genetically engineered bacteria. An alternative extracellular chemical route utilizing aerial oxidation of BDO offers cost and energy benefits but struggle with conversion efficiency. Inspired by efficient intracellular oxidation of primary alcohols, we propose a ruthenium‐phosphine synergistic catalytic system that mimics enzyme‐coenzyme functionality. This system effectively catalyzed the air‐mediated, solvent‐free oxidation of BDO to produce γ‐butyrolactone (γ‐BL) and oligomeric P4HB, with a space‐time yield (10.37 g [γ‐BL unit] g−1 catalyst h−1) surpassing the values (<5.5) of previous approaches. The oligomer‐containing products were reversibly converted to γ‐BL and then to P4HB (28.9 kDa) via ring‐opening polymerization, exceeding reported values (<16 kDa). This study provides the potential for large‐scale synthesis of high‐value PHAs from diverse non‐grain‐based diols, offering economic and environmental advantages.
Borane‐Mediated Highly Secondary Selective Deoxyfluorination of Alcohols
Authors: Willcox Dominic R. , Cironis Nojus , Winfrey Laura , Kirschner Sven , Nichol Gary S. , Thomas Stephen P. , Ingleson Michael J. 
Published: December 2024

AbstractOrganofluorine compounds are vital across multiple sectors, hence highly selective methods to install fluorine are of considerable importance. The deoxyfluorination of alcohols is a key approach to prepare organofluorine compounds, however, a highly secondary (2°)‐selective deoxyfluorination of alcohols has not been realized to date. Herein, we report that borane‐mediated deoxyfluorination results in high 2°‐selectivity in inter‐ and intra‐molecular competition reactions versus primary (1°), tertiary (3°) and even benzylic (Bn) alcohols. This is an operationally simple method using only commercial reagents (e.g., Et3N ⋅ 3HF) that starts from the alcohol which is converted to the O‐alkyl‐N‐H‐isourea in situ. The origin of the high 2°‐selectivity was elucidated to be due to the relative barriers to carbodiimide elimination from the O‐alkyl‐N‐(BR2)‐isoureas. As the selectivity controlling step does not involve fluoride, this borane‐mediated approach can be applied to other nucleophiles, as demonstrated by 2°‐selective deoxychlorination using HCl occurring in preference to substitution of 1° and Bn analogues. This borane‐mediated nucleophilic substitution therefore provides a new approach to circumvent the selectivity limitations inherent in classical SN2 and SN1 type reactions.
Auf dem Weg zur Nutzung von CO2‐Quellen mit Niedriger Konzentration durch Direkte Selektive Elektrokatalytische Reduktion
Authors: Mahbub Muhammad Adib Abdillah , Das Debanjan , Wang Xin , Lu Guilong , Muhler Martin , Schuhmann Wolfgang 
Published: December 2024

AbstractDie direkte CO2‐Reduktionsreaktion (CO2RR) aus Rauchgas mit verschiedenen CO2‐Konzentrationen könnte die zusätzliche Energie für Vorkonzentrationsprozesse zu hochkonzentriertem CO2 als Ausgangsmaterial minimieren. Wir untersuchen die Herausforderungen für die CO2RR, die durch niedrige CO2‐Konzentrationen verursacht werden, und stellen Strategien für den Einfluss des gewählten Elektrokatalysatormaterials und die Auswahl des Elektrolyten vor, um eine hohe CO‐Selektivität zu erreichen. Wir führen den Gasdiffusionselektroden in einem Modell‐Durchflusselektrolyseur kontinuierlich CO2 gemischt mit N2 (dem typischen Verdünnungsmittel im Rauchgas) in verschiedenen Verhältnissen zu. Der Betrieb der CO2RR bei niedrigeren CO2‐Konzentrationen führt zu einer Verschiebung des Überpotentials zu mehr kathodischen Werten. Wir zeigen, dass aktivere Katalysatoren eine hohe CO‐Selektivität bis hinunter zu 5 % CO2 aufrechterhalten können, indem Katalysatoren auf NiCu‐Basis verwendet werden. NiCu erreicht seine Grenze, wenn die CO2‐Konzentration auf 2 % gesenkt wird, was auf die geringe CO2‐Verfügbarkeit und die Konkurrenz der Carbonatbildung zurückzuführen ist. Durch den Einsatz von nahezu neutralen Elektrolyten mit einer hohen Pufferkapazität konnten wir eine hohe Faradaysche Effizienz bei niedrigen Überspannungen und eine höhere CO2‐Ausnutzung bei niedriger CO2‐Konzentration erzielen.
Pooled Nanoparticle Screening Using a Chemical Barcoding Approach
Authors: Vaidya Katherine , Regan Michael S. , Lin James , Houle Jenna , Gupta Aanchal , Stopka Sylwia A. , Agar Nathalie Y. R. , Hammond Paula T. , Boehnke Natalie 
Published: December 2024

AbstractWe report the development of a small molecule‐based barcoding platform for pooled screening of nanoparticle delivery. Using aryl halide‐based tags (halocodes), we achieve high‐sensitivity detection via gas chromatography coupled with mass spectrometry or electron capture. This enables barcoding and tracking of nanoparticles with minimal halocode concentrations and without altering their physicochemical properties. To demonstrate the utility of our platform for pooled screening, we synthesized a halocoded library of polylactide‐co‐glycolide (PLGA) nanoparticles and quantified uptake in ovarian cancer cells in a pooled manner. Our findings correlate with conventional fluorescence‐based assays. Additionally, we demonstrate the potential of halocodes for spatial mapping of nanoparticles using mass spectrometry imaging (MSI). Halocoding presents an accessible and modular nanoparticle screening platform capable of quantifying delivery of pooled nanocarrier libraries in a range of biological settings.
High‐Throughput Combinatorial Metal Complex Synthesis
Authors: Welsh A. , Husbands D. , Frei A. 
Published: December 2024

AbstractHigh‐throughput combinatorial metal complex synthesis has emerged as a powerful tool for rapidly generating and screening diverse libraries of metal complexes, enabling accelerated discovery in fields such as catalysis, medicinal chemistry, and materials science. By systematically combining building blocks under mild and efficient conditions, researchers can explore broad chemical spaces, increasing the likelihood of identifying complexes with desired properties. This method streamlines hit identification and optimisation, especially when integrated with high‐throughput screening and data‐driven approaches like machine learning. Despite challenges such as scalability and purity control, recent advancements in automation and predictive modelling are enhancing the efficiency of combinatorial synthesis, opening new avenues for the development of metal‐based catalysts, therapeutic agents, and functional materials.
Selective Electroreduction of CO2 to CO over Ultrawide Potential Window via Implanting Active Site with Long‐Range P Regulation on Periodic Pores
Authors: Chen Datong , Wang Fengliang , Liu Yang , Lyu Wenyuan , Zhao Xin , Fang Ruiqi , Chen Liyu , Li Yingwei 
Published: December 2024

AbstractElectroreduction of CO2 to CO represents a highly promising way for artificial carbon cycling, but obtaining high selectivity over a wide potential window remains a challenge due to the sluggish CO generation and diffusion kinetics. Here we report an integration of long‐range P modified bismuth atomic site on an ordered macroporous carbon skeleton with mesoporous “wall” (MW‐BiN3‐POMC) for efficient electroreduction of CO2. In‐depth in situ investigations with theoretical computations reveal that the incorporation of long‐range P atom is able to strengthen the orbital interaction between the C 2p of CO2 and Bi 6p, thereby establishing an electronic transport bridge for the activation of CO2 molecule. Additionally, the ordered macropore with mesoporous wall effectively facilitates the diffusion of CO. As a result, MW‐BiN3‐POMC exhibits an ultrawide potential window of 1000 mV for high CO selectivity (>90 %) and a maximal CO partial current density of 414 mA cm−2. Moreover, MW‐BiN3‐POMC can also be employed as the cathode to integrate the solar‐driven electrolytic cell (anode of Co3O4‐OMC) toward CO2 reduction coupled with 5‐hydroxymethylfurfural oxidation to simultaneously yield CO and 2,5‐furandicarboxylic acid.
A Dynamic Metal‐Organic Radical Emission System
Authors: Li Xiang , Wang Yuan , Baryshnikov Glib V. , Sahalianov Ihor , Ågren Hans , Tanuma Yuri , Zhang Zhiyun , Qian Cheng , Cong Muyu , Yi Tao , Wu Hongwei 
Published: December 2024

AbstractDeveloping new organic radical emission systems and regulating their luminescence properties presents a significant challenge. Herein, we build dynamic and multi‐emission band radical luminescence systems by co‐assembling inorganic metal salts with carbonyl compounds in ionic liquids. After the assembling, dual‐band, and excitation wavelength‐dependent emission was observed upon ultraviolet light irradiation, one emission band originates from carbonyl radical after light irradiation, the other band from the ligand‐metal charge transfer (LMCT) state, which benefits from the charge transfer from the radicals to the metal salts. The dual emission centers also introduce excitation wavelength‐dependent properties for the molecules. In addition, three‐band emission covering the visible and near‐infrared regions can be shown when two or three kinds of metal ions are simultaneously doped into the radical system driven by the ligand‐metal‐metal charge transfer (LMMCT). Interestingly, visible light can quickly quench the radical emission of systems, thus realizing a dynamic luminescence. The LMMCT effect and strong supramolecular interactions significantly improve the photoluminescence quantum yield by up to 67.2 %. Moreover, such materials can be successfully used for detecting radioactive metal ions and information encryption. This study develops a platform for manufacturing various metal‐organic radical emission systems with diverse properties.
Striking Impact of Solvent Polarity on the Strength of Hydrogen‐Bonded Complexes: A Nexus Between Theory and Experiment
Authors: Lo Rabindranath , Manna Debashree , Vacek Jaroslav , Bouř Petr , Wu Tao , Osifová Zuzana , Socha Ondřej , Dračínský Martin , Hobza Pavel 
Published: December 2024

AbstractThe binding free energy of hydrogen‐bonded complexes is generally inversely proportional to the solvent dielectric constant. This occurs because the solvent‐accessible surface area of the complex is always smaller than that of the individual subsystems, leading to a reduction in solvation energy. The present study explores the potential for stabilizing hydrogen‐bonded complexes in a solvent with higher polarity. Contrary to the established understanding, we have demonstrated that the hydrogen‐bonded complex (CH3CH2COOH⋅⋅⋅2,4,6‐trimethylpyridine) can be better stabilized in a solvent with higher polarity. In this case, a significant charge transfer between the subsystems results in an increased dipole moment of the complex, leading to its stabilization in a more polar solvent. The expected inverse relationship between binding free energy and solvent dielectric constant is observed when the charge transfer between the subsystems is low. Thus, the magnitude of the charge transfer between subsystems is possibly the key factor in determining the stabilization or destabilization of H‐bonded complexes in different solvents. Here, we present a comprehensive study that combines experimental and theoretical approaches, including nuclear magnetic resonance (NMR), infrared (IR) spectroscopies and quantum chemical calculations to validate the findings.
Breaking Performance Barriers in KBe2BO3F2 (KBBF) Analogs by Functional Group Self‐Polymerization
Authors: Zeng Wei , Tian Yao , Zeng Hongmei , Lin Zhien , Zou Guohong 
Published: December 2024

AbstractEnhancing the conversion efficiency of all‐solid‐state lasers through the rational design of crystal materials with superior linear and nonlinear optical (NLO) properties remains a formidable challenge. Herein, we present a novel approach to optimizing these properties in KBe2BO3F2 (KBBF)‐analog crystals via functional group self‐polymerization. This strategy led to the synthesis of two new optical crystals: noncentrosymmetric CsAs2O3Br and centrosymmetric CsAs4O6Br. By incorporating highly optically active [AsO3]3− units into the classical 2D [Be2BO3F]∞− framework, we facilitated the self‐assembly of [As2O3]∞ layers, forming a densely packed and highly ordered structure that enhances macroscopic optical activity. CsAs2O3Br exhibited an extraordinary second‐harmonic generation (SHG) response, 20.5 times stronger than KH2PO4 (KDP), while CsAs4O6Br demonstrated exceptional birefringence (0.26 at 546 nm), setting new performance benchmarks among KBBF analogs. Theoretical analyses reveal that these superior properties arise from the efficient alignment and high density of self‐polymerized functional units. This work represents a significant advancement in the design of high‐performance UV NLO materials, particularly for fourth‐harmonic generation, and paves the way for future innovations in photonic technologies, including solar‐blind UV laser systems and advanced photonic devices.
DNA‐Mimikry‐Foldamer‐Erkennung eines chromosomalen Proteins
Authors: Deepak Deepak , Wu Jiaojiao , Corvaglia Valentina , Allmendinger Lars , Scheckenbach Michael , Tinnefeld Philip , Huc Ivan 
Published: December 2024

AbstractEs wurden helikale aromatische Oligoamid‐Foldamere mit anionischen Seitenketten synthetisiert, die die Gesamtform und Ladungsoberflächenverteilung der DNA nachahmen. Ihre Wechselwirkungen mit dem chromosomalen Protein Sac7d, einem nicht‐sequenzselektiven DNA‐Binder, der die DNA knickt, wurden mittels Oberflächenplasmonenresonanzspektroskopie (SPR), isotherme Titrationskalorimetrie (ITC), Zirkulardichroismus (CD), Schmelzkurvenanalyse, Rasterkraftmikroskopie (AFM) und Kernspinresonanz (NMR), sowie durch Röntgenkristallographie untersucht. Es zeigte sich, dass die Foldamere besser an Sac7d binden als ein DNA‐Duplex vergleichbarer Länge. Die Wechselwirkung ist diastereoselektiv und findet an der DNA‐Bindungsstelle statt. Die Kristallographie zeigte, dass die DNA‐Mimikry‐Foldamere einen eigenen Bindungsmodus haben und dass sie an Sac7d binden können, ohne geknickt zu werden.
Performance and Stability of Corundum‐type In2O3 Catalyst for Carbon Dioxide Hydrogenation to Methanol
Authors: Gili Albert , Brösigke Georg , Javed Mudassar , Dal Molin Emiliano , Isbrücker Philipp , Repke Jens‐Uwe , Hess Franziska , Gurlo Aleksander , Schomäcker Reinhard , Bekheet Maged F. 
Published: December 2024

AbstractCarbon dioxide hydrogenation to methanol is a key chemical reaction to store energy in chemical bonds, using carbon dioxide as an energy sink. Indium oxide is amongst the most promising candidates for replacing the copper and zinc oxide catalyst, which is industrially applied for syngas mixtures but less idoneous for educts with carbon dioxide due to instability reasons. The polymorph of indium oxide and the operating conditions remain to be optimized for optimal and stable performance. Indium oxide catalysts containing different rhombohedral and cubic phase ratios were synthesized using a solvothermal method and evaluated in an ideally mixed gas phase reactor. The pure rhombohedral catalyst shows the best performance in terms of yield to methanol, selectivity, and stability. The phase stability was assessed using synchrotron in situ XRD and Rietveld refinement, shedding light on the stability of the different phases at extended operating conditions. Depending on the flow rate, temperature, and hydrogen partial pressure, a rhombohedral to cubic transition occurs, ultimately yielding inactive metallic indium. If present, cubic In2O3 serves as nuclei to induce the cubic to rhombohedral transition, hampering performance. These results allow for a more rational catalyst design and fine‐tuning of the operating conditions to ensure optimal and stable performance.
Complementary Reducing Agents are Responsible for Temporally Distinct Nucleation and Growth Phases During the Polyol Synthesis of Ag Nanocubes
Authors: Canning Griffin A. , Ogozaly Susanna , Pekarcik Matthew , Lieb Christopher A. , Jharimune Suprita , Pfukwa Rueben , Klumperman Bert , Rioux Robert M. 
Published: December 2024

AbstractEthylene glycol or one of its oxidation products are believed to serve as reducing agents in the shape‐controlled synthesis of Ag nanocubes (NCs) by the polyol process. The identity of end‐groups of polyvinylpyrrolidone (PVP) impacts shape control with alcohol and aldehyde moieties serving as a primary Ag reducing agent. We explored the role of PVP end‐groups in the polyol process by measuring the dependence of particle number density of Ag NCs produced on the initial concentration(s) of Ag and PVP using small angle x‐ray scattering and statistically large particle size distributions analyzed by scanning electron microscopy. The number density of Ag NCs is strongly dependent on the starting concentration of PVP chains demonstrating PVP end‐groups play an important role in the nucleation of NCs. The concentration of Ag+ is 2 orders of magnitude higher than the end‐groups suggesting ethylene glycol must participate in the reduction of Ag+ during growth. Perturbation experiments and analysis of resultant particle size distribution reveal nucleation is fast relative to growth of NCs, reinforcing the synergy between PVP end‐groups and ethylene glycol. The evidence demonstrates PVP end‐groups and ethylene glycol are tandem reducing agents operative in temporally distinct phases of the polyol synthesis of Ag NCs.
sp Carbon Disrupting Axial Symmetry of Local Electric Field for Biomimetic Construction of Three‐Dimensional Geometric and Electronic Structure in Nanozyme for Sensing and Microplastic Degradation
Authors: Sun Yujian , Wang Chenguang , Li Haoxin , Wang Kai , Bai Qiang , Zhang Guoli , Feng Shuishui , Wang Lina , Zhu Zhiling , Sui Ning 
Published: December 2024

AbstractThe catalytic efficiency of natural enzymes depends on the precise electronic interactions between active centers and cofactors within a three‐dimensional (3D) structure. Single‐atom nanozymes (SAzymes) attempt to mimic this structure by modifying metal active sites with molecular ligands. However, SAzymes struggle to match the catalytic efficiency of natural enzymes due to constraints in active site proximity, quantity, and the inability to simulate electron transfer processes driven by internal electronic structures of natural enzymes. This study introduces a universal spatial engineering strategy in which molecular ligands are replaced with graphdiyne (GDY) to induce d‐π orbital hybridization with copper nanoparticles (Cu NPs), leading to an asymmetric electron‐rich distribution along the longitudinal axis that mimics the local electric field of natural laccase. Moreover, multiple sp bonds within GDY scaffold effectively anchor Cu NPs, facilitating the construction of 3D geometric structure similar to that of natural laccase. An enzymatic activity of 82.53 U mg−1 is achieved, 4.72 times higher than that of natural laccase. By reconstructing both 3D structures and local electric fields of natural enzymes through d‐π orbital hybridization, this approach enhances electron interactions between cofactors, active centers, and substrates, and offers a versatile framework for biomimetic design of nanozymes.