bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cognitive profile in idiopathic autonomic failure: relation with white matter hyperintensities and neurofilament levels
Authors: Cani Ilaria , Sambati Luisa , Bartiromo Fiorina , Asioli Gian Maria , Baiardi Simone , Belotti Laura M. B. , Giannini Giulia , Guaraldi Pietro , Quadalti Corinne , Romano Luciano , Lodi Raffaele , Parchi Piero , Cortelli Pietro , Tonon Caterina , Calandra‐Buonaura Giovanna 
Published: May 2022

AbstractObjectiveTo disclose the nature of cognitive deficits in a cohort of patients with idiopathic autonomic failure (IAF) by exploring the relation among cognitive functions, cardiovascular autonomic failure (AF) and clinical progression to another α‐synucleinopathy (phenoconversion).MethodsWe retrospectively identified all patients with a clinical diagnosis of IAF who underwent a comprehensive neuropsychological evaluation, clinical examination and cardiovascular autonomic tests from the IAF‐BO cohort. Brain magnetic resonance imaging (MRI) studies and cerebrospinal fluid (CSF) analysis, including neurofilament light chain (NfL), Alzheimer disease core biomarkers, and α‐synuclein seeding activity were further evaluated when available.Correlations among cognitive functions, clinical features, cardiovascular AF, cerebral white matter hyperintensities (WMH) load, and CSF biomarkers were estimated using Spearman correlation coefficient.ResultsThirteen out of 30 (43%) patients with IAF displayed cognitive deficits (CI) mainly concerning executive functioning. Seven out of 30 (23%) met the criteria for mild cognitive impairment (MCI).The diagnosis of CI and MCI was not associated with phenoconversion or autonomic function parameters, including duration and severity of neurogenic orthostatic hypotension, presence and severity of supine hypertension, and nocturnal dipper profile.Twenty patients underwent a brain MRI and CSF analysis. MCI was related to WMH load (r = 0.549) and NfL levels (r = 0.656), while autonomic function parameters were not associated with either WMH or NfL levels.InterpretationCardiovascular AF and phenoconversion, underlying the spreading of neurodegeneration to the central nervous system, were not independent drivers of cognitive dysfunction in IAF. We identified WMH load and NfL levels as potential biomarkers of the neural network disruption associated with cognitive impairment in patients with IAF.
Response of plasmamicroRNAsto nusinersen treatment in patients withSMA
Authors: Zaharieva Irina T. , Scoto Mariacristina , Aragon‐Gawinska Karolina , Ridout Deborah , Doreste Bruno , Servais Laurent , Muntoni Francesco , Zhou Haiyan 
Published: May 2022

AbstractObjectiveSpinal muscular atrophy (SMA) is a common genetic cause of infant mortality. Nusinersen treatment ameliorates the clinical outcome of SMA, however, some patients respond well, while others have limited response. We investigated microRNAs in blood samples from SMA patients and their response to nusinersen treatment evaluating the potential of circulating microRNAs as biomarkers for SMA.MethodsIn a discovery cohort study, microRNA next‐generation sequencing was performed in blood samples from SMA patients (SMA type 2,n = 10; SMA type 3,n = 10) and controls (n = 7). The dysregulated microRNAs were further analysed in the therapeutic response cohort comprised of SMA type 1 patients (n = 22) who had received nusinersen treatment, at three time points along the treatment course (baseline, 2 and 6 months of treatment). The levels of the studied microRNAs were correlated to the SMA clinical outcome measures.ResultsIn the discovery cohort, 69 microRNAs were dysregulated between SMA patients and controls. In the therapeutic response cohort, the baseline plasma levels of miR‐107, miR‐142‐5p, miR‐335‐5p, miR‐423‐3p, miR‐660‐5p, miR‐378a‐3p and miR‐23a‐3p were associated with the 2 and 6 months response to nusinersen treatment. Furthermore, the levels of miR‐107, miR‐142‐5p, miR‐335‐5p, miR‐423‐3p, miR‐660‐5p and miR‐378‐3p at 2 months of treatment were associated with the response after 6 months of nusinersen treatment.InterpretationBlood microRNAs could be used as biomarkers to indicate SMA patients’ response to nusinersen and to monitor the efficacy of the therapeutic intervention. In addition, some of these microRNAs provide insight into processes involved in SMA that could be exploited as novel therapeutic targets.
Atomic Heterointerface Engineering of Ni2P‐NiSe2 Nanosheets Coupled ZnP‐Based Arrays for High‐Efficiency Solar‐Assisted Water Splitting
Authors: Chang Kai , Tran Duy Thanh , Wang Jingqiang , Prabhakaran Sampath , Kim Do Hwan , Kim Nam Hoon , Lee Joong Hee 
Published: May 2022

AbstractIn this study, heterogeneous nickel phosphide‐nickel selenide (Ni2P‐NiSe2) nanosheets are constructed to coat zinc phosphide‐based nanorods (ZnP NRs) under a unique core@shell architecture, which acts as a highly active multifunctional catalyst toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The catalyst exhibits an overpotential of 79 mV at 10 mA cm–2 for HER and 326 mV at 100 mA cm–2 for OER in freshwater under an alkaline condition. The formation of an open 3D channel architecture derived from highly conductive ZnP@Ni2P‐NiSe2 nanorods attached nickel foam generates more exposed active sites and promotes fast mass transport. In addition, density functional theory study reveals a synergistic effect between Ni2P and NiSe2 phase to reduce adsorption free energy and increase the electronic conductivity, thereby accelerating the catalytic reaction kinetics. An electrolyzer of the ZnP@Ni2P‐NiSe2(+,‐) requires only cell voltages of 1.54 V (1.43 V) and 1.51 V (1.44 V) to deliver 10 mA cm–2 in freshwater and mimic seawater at 25 °C (75 °C), respectively, along with prospective long‐term stability. Furthermore, the solar energy‐assisted water splitting process demonstrates a solar‐to‐hydrogen efficiency of 19.75%, implying that the catalyst is an effective and low‐cost candidate for water splitting.
Resolving the Role of Configurational Entropy in Improving Cycling Performance of Multicomponent Hexacyanoferrate Cathodes for Sodium‐Ion Batteries
Authors: Ma Yanjiao , Hu Yang , Pramudya Yohanes , Diemant Thomas , Wang Qingsong , Goonetilleke Damian , Tang Yushu , Zhou Bei , Hahn Horst , Wenzel Wolfgang , Fichtner Maximilian , Ma Yuan , Breitung Ben , Brezesinski Torsten 
Published: May 2022

AbstractMn‐based hexacyanoferrate (Mn‐HCF) cathodes for Na‐ion batteries usually suffer from poor reversibility and capacity decay resulting from unfavorable phase transitions and structural degradation during cycling. To address this issue, the high‐entropy concept is here applied to Mn‐HCF materials, significantly improving the sodium storage capabilities of this system via a solid‐solution mechanism with minor crystallographic changes upon de‐/sodiation. Complementary structural, electrochemical, and computational characterization methods are used to compare the behavior of high‐, medium‐, and low‐entropy multicomponent Mn‐HCFs resolving, to our knowledge for the first time, the link between configurational entropy/compositional disorder (entropy‐mediated suppression of phase transitions, etc.) and cycling performance/stability in this promising class of next‐generation cathode materials.
Data‐Driven High‐Throughput Rational Design of Double‐Atom Catalysts for Oxygen Evolution and Reduction
Authors: Wu Lianping , Guo Tian , Li Teng 
Published: May 2022

AbstractSurging interests exist in double‐atom catalysts (DACs), which not only inherit the advantages of single‐atom catalysts (SACs) (e.g., ultimate atomic utilization, high activity, and selectivity) but also overcome the drawbacks of SACs (e.g., low loading and isolated active site). The design of DACs, however, remains cost‐prohibitive for both experimental and computational studies, due to their huge design space. Herein, by means of density functional theory (DFT) and topological information‐based machine‐learning (ML) algorithms, we present a data‐driven high‐throughput design principle to evaluate the stability and activity of 16 767 DACs for oxygen evolution (OER) and oxygen reduction (ORR) reactions. The rational design reveals 511 types of DACs with OER activity superior to IrO2(110), 855 types of DACs with ORR activity superior to Pt (111), and 248 bifunctional DACs with high catalytic performance for both OER and ORR. An intrinsic descriptor is revealed to correlate the catalytic activity of a DAC with the electronic structures of the DAC and its bonding carbon surface structure. This data‐driven high‐throughput approach not only yields remarkable prediction precision (>0.926 R‐squared) but also enables a notable 144 000‐fold reduction of screening time compared with pure DFT calculations, holding promise to drastically accelerate the design of high‐performance DACs.
Patient‐Specific Self‐Powered Metamaterial Implants for Detecting Bone Healing Progress
Authors: Barri Kaveh , Zhang Qianyun , Swink Isaac , Aucie Yashar , Holmberg Kyle , Sauber Ryan , Altman Daniel T. , Cheng Boyle C. , Wang Zhong Lin , Alavi Amir H. 
Published: May 2022

AbstractThere is an unmet need for developing a new class of smart medical implants with novel properties and advanced functionalities. Here, the concept of “self‐aware implants” is proposed to enable the creation of a new generation of multifunctional metamaterial implantable devices capable of responding to their environment, empowering themselves, and self‐monitoring their condition. These functionalities are achieved via integrating nano energy harvesting and mechanical metamaterial design paradigms. Various aspects of the proposed concept are highlighted by developing proof‐of‐concept interbody spinal fusion cage implants with self‐sensing, self‐powering, and mechanical tunability features. Bench‐top testing is performed using synthetic biomimetic and human cadaver spine models to evaluate the electrical and mechanical performance of the developed patient‐specific metamaterial implants. The results show that the self‐aware cage implants can diagnose bone healing process using the voltage signals generated internally through their built‐in contact‐electrification mechanisms. The voltage and current generated by the implants under the axial compression forces of the spine models reach 9.2 V and 4.9 nA, respectively. The metamaterial implants can serve as triboelectric nanogenerators to empower low‐power electronics. The capacity of the proposed technology to revolutionize the landscape of implantable devices and to achieve better surgical outcomes is further discussed.
An Anode‐Free Zn–Graphite Battery
Authors: Wang Gang , Zhu Minshen , Chen Guangbo , Qu Zhe , Kohn Benjamin , Scheler Ulrich , Chu Xingyuan , Fu Yubin , Schmidt Oliver G. , Feng Xinliang 
Published: May 2022

AbstractThe anode‐free battery concept is proposed to pursue the aspiration of energy‐dense, rechargeable metal batteries, but this has not been achieved with dual‐ion batteries. Herein, the first anode‐free Zn–graphite battery enabled by efficient Zn plating–stripping onto a silver‐coated Cu substrate is demonstrated. The silver coating guides uniform Zn deposition without dendrite formation or side reaction over a wide range of electrolyte concentrations, enabling the construction of anode‐free Zn cells. In addition, the graphite cathode operates efficiently under reversible bis(trifluoromethanesulfonyl)imide anion (TFSI−) intercalation without anodic corrosion. An extra high‐potential TFSI− intercalation plateau is recognized at 2.75 V, contributing to the high capacity of graphite cathode. Thanks to efficient Zn plating–stripping and TFSI− intercalation–deintercalation, an anode‐free Zn–graphite dual‐ion battery that exhibits impressive cycling stability with 82% capacity retention after 1000 cycles is constructed. At the same time, a specific energy of 79 Wh kg−1 based on the mass of cathode and electrolyte is achieved, which is over two times higher than conventional Zn–graphite batteries (<30 Wh kg−1).
At their own pace: Optimal walking speed in children and adolescents
Authors: Mateos Ana , Zorrilla‐Revilla Guillermo , Rodríguez Jesús 
Published: May 2022

AbstractObjectivesAn important factor for human walking behavior is the speed at which an individual—adult or non‐adult—is able to move at a minimum energetic cost. Our aim was to assess the extent to which juveniles walking with adults force the group to set a pace that is energetically too costly for adults by comparing the optimal walking speed of juveniles and adults.Materials and methodsAn experimental study was carried out indoors in a sample of 74 children and adolescents of both sexes, between 7 and 14 years of age. Volunteers walked on a treadmill at six different speeds, and the gross cost of transport (CoT), minimum gross energy cost (minCoT), and optimal locomotion speed (OLS) were determined for each individual. These values were compared with the optimal values for adults, as reported in the literature.ResultsOur results show that OLS is similar in boys and girls, and that there are no sex differences in minCoT. Older individuals, as a consequence of their larger size, spend more energy at their optimal speed than younger children.DiscussionJuveniles are not a real burden for the rest of the group in foraging societies, neither in energetic terms nor in locomotor efficiency, being able to achieve optimal walking speeds similar to adults. The so‐called energetic dilemma for sex‐mixed walking groups does not affect juveniles when moving together with adults or in sex‐mixed parties.
Metathese Reaktionen eines NHC‐stabilisierten Phosphaborens
Authors: Koner Abhishek , Morgenstern Bernd , Andrada Diego M. 
Published: May 2022

AbstractDie ungesättigte BP‐Einheit stellt durch ihre neuartige Reaktivität und ihre einzigartigen physikalischen Eigenschaften eine attraktive funktionelle Gruppe dar. Nichtsdestotrotz ist ihre Anwendung begrenzt durch die sperrige Natur der B/P‐Schutzgruppen, welche erforderlich sind, um Oligomerisation zu vermeiden. Wir berichten hiermit von der Synthese und Isolation einesN‐heterozyklischen Carben‐ (NHC) stabilisierten Phosphaborens, welches eine Trimethylsilyl‐ (TMS) Funktionalität am endständigen P trägt, ein bei Raumtemperatur stabiler kristalliner Feststoff, zugänglich durch einfache NHC‐induzierte Trimethylsilylchlorid‐ (TMSCl) Eliminierung des Phosphinoboran‐Präkursors. Diese Phosphaborenverbindung, die eine genuine B=P‐Bindung enthält, zeigt die außergewöhnliche Fähigkeit, P‐zentrierte Metathese Reaktionen einzugehen, was die Isolierung einer Reihe neuartiger Phosphaborene erlaubt. Röntgenkristallographische Analyse, UV/Vis‐Spektroskopie und DFT‐Rechnungen liefern Einblicke in die B=P Bindungssituation.
Fast‐Scanning Potential‐Gated Organic Electrochemical Transistors for Highly Sensitive Sensing of Dopamine in Living Rat Brain
Authors: Li Weiqi , Jin Jing , Xiong Tianyi , Yu Ping , Mao Lanqun 
Published: May 2022

AbstractDeveloping techniques for the highly sensitive assay of neurotransmitters is essential for understanding physiological and pathological processes. Here, we demonstrate a fast‐scanning potential (FSP)‐gated organic electrochemical transistor (OECT): for the highly sensitive sensing of dopamine (DA) in a living rat brain. The configuration combines the selectivity of fast‐scan cyclic voltammetry (FSCV) with the high sensitivity of an OECT. The combined use of FSP as a gating mode and transconductance (gm) as a sensing parameter further improve the sensing performance in terms of sensitivity, limit of detection, reproducibility, and stability. The FSP‐OECT exhibits a sensitivity of 0.899 S M−1 and a low limit of detection down to 5 nM and was validated for in vivo monitoring of the basal level and electrically stimulated release of DA.
“Like Recycles Like”: Selective Ring‐Closing Depolymerization of Poly(L‐Lactic Acid) to L‐Lactide
Authors: Cederholm Linnea , Wohlert Jakob , Olsén Peter , Hakkarainen Minna , Odelius Karin 
Published: May 2022

AbstractChemical recycling of poly(L‐lactic acid) to the cyclic monomer L‐lactide is hampered by low selectivity and by epimerization and elimination reactions, impeding its use on a large scale. The high number of side reactions originates from the high ceiling temperature (Tc) of L‐lactide, which necessitates high temperatures or multistep reactions to achieve recycling to L‐lactide. To circumvent this issue, we utilized the impact of solvent interactions on the monomer–polymer equilibrium to decrease theTcof L‐lactide. Analyzing the observedTcin different solvents in relation to their Hildebrand solubility parameter revealed a “like recycles like” relationship. The decreasedTc, obtained by selecting solvents that interact strongly with the monomer (dimethyl formamide or the green solvent γ‐valerolactone), allowed chemical recycling of high‐molecular‐weight poly(L‐lactic acid) directly to L‐lactide, within 1–4 h at 140 °C, with >95 % conversion and 98–99 % selectivity. Recycled L‐lactide was isolated and repolymerized with high control over molecular weight and dispersity, closing the polymer loop.
Regio‐ und enantioselektive, intermolekulare Aminofluorierung von Alkenen durch Iod(I)/Iod(III)‐Katalyse**
Authors: Schäfer Michael , Stünkel Timo , Daniliuc Constantin G. , Gilmour Ryan 
Published: May 2022

AbstractDie regio‐ und enantioselektive, intermolekulare vicinale Fluoraminierung von α‐CF3‐Styrolen wurde durch enantioselektive II/IIII‐Katalyse erreicht. Unter Nutzung von C2‐symmetrischen, Resorcinol‐basierten Aryl Iodid‐Katalysatoren war es möglich, das kurzlebige Iodonium‐Zwischenprodukt mit einfachen Nitrilen abzufangen, die sowohl als Lösungsmittel als auch als Nucleophil fungieren. Die in situ Ritter‐Reaktion bietet direkten Zugang zu den entsprechenden Amiden (>25 Beispiele, bis zu 89 % Ausbeute und 93 : 7 e.r.). Dieses Paradigma der Hauptgruppenkatalyse kehrt die intrinsische Regioselektivität des unkatalysierten Prozesses um und bietet so einen einfachen Zugang zu tertiären, benzylischen Stereozentren, die sowohl eine CF3‐Gruppe als auch ein Fluor tragen. Es können privilegierte Phenethylamin‐Pharmakophore erzeugt werden, bei denen die vollständige lokale partielle Ladungsumkehr vorliegt (CF3δ−/Fδ− versus CH3δ+/Hδ+). Kristallographische Analysen von repräsentativen β‐Fluoramid‐Produkten zeigen Konformationen, die den stereoelektronischen Gauche‐Effekt verdeutlichen.
Ultrafast Dynamics of Photochemical Nitrile Imine Formation
Authors: Flesch Stefan , Vöhringer Peter 
Published: May 2022

AbstractThe chemical reactivity of nitrile imines is of great utility in organic synthesis with applications rapidly expanding into the materials and life sciences. Yet, our understanding of the electronic and molecular structures of nitrile imines remains incomplete and the elementary mechanism of their photoinduced generation is entirely unknown. Here, femtosecond infrared spectroscopy after 266 nm‐excitation of 2,5‐diphenyltetrazole has been carried out to temporally resolve the formation and structural relaxation dynamics of the nascent diphenylnitrile imine in liquid solution under ambient conditions. The infrared‐spectroscopic evolution is interpreted by an initial sequence of intersystem crossings within 250 fs followed by the cleavage of N2with formation of a structurally relaxed nitrile imine on the adiabatic ground‐state singlet surface within a few tens of picoseconds. The infrared spectrum supports the notion of a “floppy” nitrile imine molecule whose equilibrium character ranges from fully propargylic to fully allenic in the room temperature liquid solution.
Ball Milling Solid‐State Synthesis of Highly Crystalline Prussian Blue Analogue Na2−xMnFe(CN)6 Cathodes for All‐Climate Sodium‐Ion Batteries
Authors: Peng Jian , Gao Yun , Zhang Hang , Liu Zhengguang , Zhang Wang , Li Li , Qiao Yun , Yang Weishen , Wang Jiazhao , Dou Shixue , Chou Shulei 
Published: May 2022

AbstractWith a series of merits, Prussian blue analogs (PBAs) have been considered as superior cathode materials for sodium‐ion batteries (SIBs). Their commercialization, however, still suffers from inferior stability, considerable [Fe(CN)6] defects and interstitial water in the framework, which are related to the rapid crystal growth. Herein, a “water‐in‐salt” nanoreactor is proposed to synthesize highly crystallized PBAs with decreased defects and water, which show both superior specific capacity and rate capability in SIBs. The air‐stability, all‐climate, and full‐cell properties of our PBA have also been evaluated, and it exhibits enhanced electrochemical performance and higher volume yield than its counterpart synthesized via the water‐based co‐precipitation method. Furthermore, their highly reversible sodium‐ion storage behavior has been measured and identified via multiple in situ techniques. This work could pave the way for the PBA‐based SIBs in grid‐scale energy‐storage systems.
Sustainable synthesis of highly diastereoselective & fluorescent active spirooxindoles catalyzed by copper oxide nanoparticle immobilized on microcrystalline cellulose
Authors: Kumar Bhupender , Babu Nagendra J. , Chowhan Raju L. 
Published: May 2022

AbstractComposites of copper oxide nanoparticles immobilized on microcrystalline cellulose (Cu2O@MCC) were synthesized and studied for their catalytic activity toward 1,3‐dipolar cycloaddition reaction. Azomethine ylide was in situ generated from isatin and 1,2,3,4‐tetrahydroisoquinoline (THIQ) and styrylisoxazoles/chalcones used as dipolarphiles in one‐pot synthesis of novel spiro polycyclic heterocyclic compounds. Cu2O@MCC showed excellent catalytic activity on 20 mg of composite with 30% loading of copper on MCC. The scale‐up and recyclability experiment on the 10 mmol scale revealed the sustainability of composite even after four consecutive cycles. The products were fluorescent active, obtained in good to excellent yield with high regio and diastereoselectivity. The relevant features of the developed protocol are eco‐friendly with a wide range of substrate scope and shorter reaction time.
The Wnt gene family in Tenebrio molitor and other coleopterans
Authors: Yang Lin , Li Guang‐Ya , Li Xing‐Yan , Wu Chao‐Yan , Wang Jun , Song Qi‐Sheng , Stanley David , Wei Shu‐Jun , Zhu Jia‐Ying 
Published: May 2022

AbstractThe Wnt gene family is involved in a wide range of developmental processes. Despite its significance, the evolution and function of Wnt genes remain largely unclear. Here, an exhaustive survey of Wnt genes was conducted in Tenebrio molitor and 17 other beetle genomes. A total of 146 Wnt genes were identified, creating a comprehensive coleopteran Wnt gene catalog. Comparative genomics indicates that dynamic evolutionary patterns of Wnt gene loss and duplication occurred in Coleoptera, leading to the diverse Wnt gene repertoire in various beetles. A striking loss of particular Wnt gene subfamilies occurs in Coleoptera. Remarkably, Wnt gene duplication was discovered for the first time in insects. Further analysis of Wnt gene expression in T. molitor indicates that each Wnt gene, including the duplicated ones, has a unique spatial or temporal expression pattern. The current study provides valuable insight into the evolution and functional validation of Wnt genes in Coleoptera.
Relativistic perihelion shift of Mercury revisited
Authors: Křížek Michal 
Published: May 2022

AbstractIn 1915, Albert Einstein derived a formula for an additional relativistic perihelion shift of Mercury. We give several critical comments of how this formula is treated, since the perihelion shift of Mercury is an ill‐conditioned problem. We also present various sources of nonnegligible errors, which should be taken into account.