bluuebunny/crossref_metadata_2025_split huggingface dataset:
Magnetically Driven Powerless Lighting Device with Kirigami Structured Magneto–Mechanoluminescence Composite
Authors: Listyawan Michael Abraham , Song Hyunseok , Jung Ji Yun , Shin Joonchul , Hwang Geon‐Tae , Song Hyun‐Cheol , Ryu Jungho 
Published: April 2023

AbstractThe energy crisis and global shift toward sustainability drive the need for sustainable technologies that utilize often‐wasted forms of energy. A multipurpose lighting device with a simplistic design that does not need electricity sources or conversions can be one such futuristic device. This study investigates the novel concept of a powerless lighting device driven by stray magnetic fields induced by power infrastructure for obstruction warning light systems. The device consists of mechanoluminescence (ML) composites of a Kirigami‐shaped polydimethylsiloxane (PDMS) elastomer, ZnS:Cu particles, and a magneto–mechano‐vibration (MMV) cantilever beam. Finite element analysis and luminescence characterization of the Kirigami structured ML composites are discussed, including the stress–strain distribution map and comparisons between different Kirigami structures based on stretchability and ML characteristic trade‐offs. By coupling a Kirigami‐structured ML material and an MMV cantilever structure, a device that can generate visible light as luminescence from a magnetic field can be created. Significant factors that contribute to luminescence generation and intensity are identified and optimized. Furthermore, the feasibility of the device is demonstrated by placing it in a practical environment. This further proves the functionality of the device in harvesting weak magnetic fields into luminescence or light, without complicated electrical energy conversion steps.
Generation of Long‐Lived Excitons in Room‐Temperature Phosphorescence 2D Organic and Inorganic Hybrid Perovskites for Ultrafast and Low Power‐Consumption Nonvolatile Photomemory
Authors: Chen Jian‐Cheng , Lu Yu‐Dao , Chen Jung‐Yao 
Published: April 2023

AbstractRoom‐temperature phosphorescence (RTP) two‐dimensional (2D) organic‐inorganic hybrid perovskites (OIHPs) that possess superior stability and efficient triplet energy transfer between inorganic parts and organic cations have been seen as promising materials in optoelectronic devices. However, the development of RTP 2D OIHP‐based photomemory has not been explored yet. In this work, the spatially addressable RTP 2D OIHPs‐based nonvolatile flash photomemory is first investigated to explore the function of triplet excitons in elevating the performance of photomemory. Thanks to the triplet excitons generated in RTP 2D OIHP, extremely low photo‐programming time of 0.7 ms, multilevel behavior of minimum 7 bits (128 levels), remarkable photoresponsivity of 19.10 AW−1 and significantly low power consumption of 6.79 × 10−8 J per bit can be achieved. The current study provides a new prospective in understanding triplet excitons function in nonvolatile photomemory.
Examining the role of the excess shelter deduction in the Supplemental Nutrition Assistance Program benefit formula
Authors: Ismail Mehreen S. , Ver Ploeg Michele , Chomitz Virginia , Wilde Parke 
Published: April 2023

AbstractThe Supplemental Nutrition Assistance Program's (SNAP) excess shelter deduction acknowledges that high shelter expenses can compete with food spending. We examined whether the deduction facilitates benefit targeting. We estimated that 48%–67% of SNAP households received the deduction, with the likelihood varying by region, household composition, and housing tenure. Households living in the Northeast or renting unsubsidized housing were especially likely to face limits on the deduction amount. According to our results, the excess shelter deduction likely helps households obtain higher SNAP benefit allotments albeit to a limited extent.
The evolutionary history of rice azaleas (Rhododendron tschonoskii alliance) involved niche evolution to a montane environment
Authors: Yoichi Watanabe , Tamaki Ichiro , Oh Sang‐Hun , Nagano Atsushi J. , Uehara Koichi , Tomaru Nobuhiro , Abe Harue 
Published: April 2023

AbstractPremiseThe formation of isolated montane geography on islands promotes evolution, speciation, and then radiation if there are ecological changes. Thus, investigating evolutionary histories of montane species and associated ecological changes may help efforts to understand how endemism formed in islands’ montane floras. To explore this process, we investigated the evolutionary history of the Rhododendron tschonoskii alliance, which grows in montane environments of the Japanese archipelago and the Korean Peninsula.MethodsWe studied the five species in the R. tschonoskii alliance and 30 outgroup species, using genome‐wide single‐nucleotide polymorphisms and cpDNA sequences, in association with environmental analyses.ResultsThe monophyletic R. tschonoskii alliance diverged since the late Miocene. Species in the alliance currently inhabit a cold climatic niche that is largely different from that of the outgroup species. We observed clear genetic and niche differentiations between the taxa of the alliance.ConclusionsThe association of the alliance's evolution with the formation of cooler climates on mountains indicates that it was driven by global cooling since the mid‐Miocene and by rapid uplift of mountains since the Pliocene. The combination of geographic and climatic isolation promoted high genetic differentiation between taxa, which has been maintained by climatic oscillations since the Quaternary.
Recent Progress in Arylmetalative Cyclization/Annulation of Functionalized Alkynes with Organoboranes
Authors: Rajesh Manda , Kumar Gadi Ranjith 
Published: April 2023

AbstractAchieving complex molecular assemblies in modular modes is always one of the top priorities of the organic chemist. Cyclization/annulation of functionalized alkynes through carbo metalation has an impactful swath in synthetic organic chemistry. There have recently been considerable contributions in this arena uncovering several new chemical spaces towards new solutions for various fields of biology. On the other hand, organoboronic reagents are fascinating reactive chemprobs, are partake in a broad range of chemical transformations. Particularly utility of these reagents in the carbo‐metalation of alkynes is the subject of high perusal in organic chemistry. To this degree, tuning various transition‐metal catalysts with organoboranes and functionalized alkynes is an intriguing subject for the synthesis of various classes of acyclic and cyclic adducts. Mechanistically, these arylative cyclizations proceed through initial aryl‐metalation on alkynes which provides alkenyl metal species, that concomitantly react with the pendent electrophile. The stereo‐ and regioselective reactivity of this C‐metal is steered by chelation with the coordinating group and/or electrophile on alkyne. In this review, we focused on the critical achievements of the field with the emphasis on the stereoselective capture of the vinyl metal complex with a pendent electrophile. In this field, compilation of the detailed mechanistic pathways in this realm would be helpful to find the gaps and hence to discover novel transformations.
Synthesis of Fused Lactones through Transition‐Metal‐Catalyzed peri C−H Functionalization
Authors: Nishida Ayako , Inai Yasuhito , Usuki Yoshinosuke , Satoh Tetsuya 
Published: April 2023

AbstractThe rhodium(III)‐catalyzed dehydrogenative cyclization of 9‐anthracenecarboxylic acids and 2‐substituted 1‐naphthoic acids proceeds through peri C−H bond cleavages to produce fused lactones. These aromatic carboxylic acids also undergo dehydrogenative coupling with styrenes and successive Wacker‐type cyclization under palladium catalysis to construct 3‐benzylidenebenzo[de]isochromen‐1‐one frameworks.
The structural and social determinants of Alzheimer's disease related dementias
Authors: Adkins‐Jackson Paris B. , George Kristen M. , Besser Lilah M. , Hyun Jinshil , Lamar Melissa , Hill‐Jarrett Tanisha G. , Bubu Omonigho M. , Flatt Jason D. , Heyn Patricia C. , Cicero Ethan C. , Zarina Kraal A. , Pushpalata Zanwar Preeti , Peterson Rachel , Kim Boeun , Turner Robert W. , Viswanathan Jaya , Kulick Erin R. , Zuelsdorff Megan , Stites Shana D. , Arce Rentería Miguel , Tsoy Elena , Seblova Dominika , Ng Ted K.S. , Manly Jennifer J. , Babulal Ganesh 
Published: April 2023

AbstractIntroductionThe projected growth of Alzheimer's disease (AD) and AD‐related dementia (ADRD) cases by midcentury has expanded the research field and impelled new lines of inquiry into structural and social determinants of health (S/SDOH) as fundamental drivers of disparities in AD/ADRD.MethodsIn this review, we employ Bronfenbrenner's ecological systems theory as a framework to posit how S/SDOH impact AD/ADRD risk and outcomes.ResultsBronfenbrenner defined the “macrosystem” as the realm of power (structural) systems that drive S/SDOH and that are the root cause of health disparities. These root causes have been discussed little to date in relation to AD/ADRD, and thus, macrosystem influences, such as racism, classism, sexism, and homophobia, are the emphasis in this paper.DiscussionUnder Bronfenbrenner's macrosystem framework, we highlight key quantitative and qualitative studies linking S/SDOH with AD/ADRD, identify scientific gaps in the literature, and propose guidance for future research.HighlightsEcological systems theory links structural/social determinants to AD/ADRD.Structural/social determinants accrue and interact over the life course to impact AD/ADRD.Macrosystem is made up of societal norms, beliefs, values, and practices (e.g., laws).Most macro‐level determinants have been understudied in the AD/ADRD literature.
Expanding the use of brief cognitive assessments to detect suspected early‐stage cognitive impairment in primary care
Authors: Mattke Soeren , Batie Donnie , Chodosh Joshua , Felten Kristen , Flaherty Ellen , Fowler Nicole R. , Kobylarz Fred A. , O'Brien Kelly , Paulsen Russ , Pohnert Anne , Possin Katherine L. , Sadak Tatiana , Ty Diane , Walsh Amy , Zissimopoulos Julie M. 
Published: April 2023

AbstractIntroductionMild cognitive impairment remains substantially underdiagnosed, especially in disadvantaged populations. Failure to diagnose deprives patients and families of the opportunity to treat reversible causes, make necessary life and lifestyle changes and receive disease‐modifying treatments if caused by Alzheimer's disease. Primary care, as the entry point for most, plays a critical role in improving detection rates.MethodsWe convened a Work Group of national experts to develop consensus recommendations for policymakers and third‐party payers on ways to increase the use of brief cognitive assessments (BCAs) in primary care.ResultsThe group recommended three strategies to promote routine use of BCAs: providing primary care clinicians with suitable assessment tools; integrating BCAs into routine workflows; and crafting payment policies to encourage adoption of BCAs.DisscussionSweeping changes and actions of multiple stakeholders are necessary to improve detection rates of mild cognitive impairment so that patients and families may benefit from timely interventions.
Electrical Pulse‐Driven Periodic Self‐Repair of Cu‐Ni Tandem Catalyst for Efficient Ammonia Synthesis from Nitrate
Authors: Bu Yongguang , Wang Chao , Zhang Wenkai , Yang Xiaohan , Ding Jie , Gao Guandao 
Published: April 2023

AbstractElectrocatalytic nitrate reduction sustainably produces ammonia and alleviates water pollution, yet is still challenging due to the kinetic mismatch and hydrogen evolution competition. Cu/Cu2O heterojunction is proven effective to break the rate‐determining NO3−‐to‐NO2− step for efficient NH3 conversion, while it is unstable due to electrochemical reconstruction. Here we report a programmable pulsed electrolysis strategy to achieve reliable Cu/Cu2O structure, where Cu is oxidized to CuO during oxidation pulse, then regenerating Cu/Cu2O upon reduction. Alloying with Ni further modulates hydrogen adsorption, which transfers from Ni/Ni(OH)2 to N‐containing intermediates on Cu/Cu2O, promoting NH3 formation with a high NO3−‐to‐NH3 Faraday efficiency (88.0±1.6 %, pH 12) and NH3 yield rate (583.6±2.4 μmol cm−2 h−1) under optimal pulsed conditions. This work provides new insights to in situ electrochemically regulate catalysts for NO3−‐to‐NH3 conversion.
Smart Materials Based on Synthetic Host Molecules: The Role of Host–Guest Chemistry in the Fabrication and Application
Authors: Liu Peiren , Fang Fang , Wang Haochen , Khashab Niveen M. 
Published: April 2023

AbstractStimuli‐responsive or smart materials have recently shown a significant impact on the frontier of material science and engineering. The exponential development of synthetic host molecules (SHMs) over the last decades and their corresponding host–guest chemistry, have empowered researchers with new opportunities to design and construct tailored or guest‐specific smart materials. In this Minireview, we present the recent advancements in synthetic host based smart materials, ranging from the fabrication strategies to the state‐of‐art applications including adsorption, separation, luminescence, self‐healing and actuation. The role that the host–guest chemistry plays in these systems is highlighted throughout to give a better prospective of the available possibilities for emerging materials of future economies.
Charge Separation in Metal‐Organic Framework Enables Heterogeneous Thiol Catalysis
Authors: Cheng Shengxian , Ouyang Jing , Li Muqing , Diao Yingxue , Yao Jiachen , Li Fengxing , Lee Yat‐For , SUNG Herman Ho‐Yung , Williams Ian , Xu Zhengtao , Quan Yangjian 
Published: April 2023

AbstractPhotoinduced metal–organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr‐TPDCS‐1, consisting of Zr6‐clusters and TPDCS linkers (TPDCS=3,3′′,5,5′′‐tetramercapto[1,1′:4′,1′′‐terphenyl]‐4,4′′‐dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr6‐cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram‐scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl‐radical catalysis.
Mechanismus der CO Oxidation an einem molekular‐definierten Kupfer‐Einzelatom‐Katalysator auf einer metallorganischen Gerüstverbindung
Authors: Abdel‐Mageed Ali M. , Rungtaweevoranit Bunyarat , Impeng Sarawoot , Bansmann Joachim , Rabeah Jabor , Chen Shilong , Häring Thomas , Namuangrak Supawadee , Faungnawakij Kajornsak , Brückner Angelika , Behm R. Jürgen 
Published: April 2023

AbstractIn der Heterogenen Katalyse ist die Aufklärung des Reaktionsmechanismus essentiell für die systematische Optimierung der Katalysatoren, aber aufgrund der unbekannten Natur der aktiven Zentren herausfordernd. Für einen molekular‐definierten, auf einer metallorganischen Gerüstverbindung (UiO‐66) geträgerten Kupfer‐Einzelatom‐Katalysators konnten wir ein detailliertes mechanistisches Bild der CO Oxidation erarbeiten. Basierend auf einer Kombination von in situ/operando Spektroskopien, kinetischen Messungen inklusive kinetischer Isotopeneffekte sowie Dichtefunktional‐Theorie basierten Rechnungen konnten wir den aktiven Platz, Reaktionsintermediate und Übergangszustände des dominierenden Reaktionszyklus sowie Veränderungen in den Cu Oxidations‐ und Spinzuständen während der Reaktion identifizieren. Die Reaktion verläuft über die reaktive Dissoziation von adsorbiertem O2, durch Reaktion von O2,ad mit koadsorbiertem COad, als ratenlimitierendem Schritt. Das verbleibende O Atom, das das Cu Zentrum mit einem benachbarten Zr4+ Ion verbindet, wird in einem zweiten aktivierten Schritt abreagiert.
Donor‐Acceptor Aminocyclobutane Monoesters: Synthesis and Silylium‐Catalyzed (4+2) Annulation with Indoles
Authors: Robert Emma G. L. , Pirenne Vincent , Wodrich Matthew D. , Waser Jérôme 
Published: April 2023

AbstractA convenient one‐step synthesis of β‐aminocyclobutane monoesters starting from commercially available reagents is reported. The obtained strained rings undergo (4+2) dearomative annulation with indole partners using silylium catalysis. This organocatalyzed annulation provided tricyclic indolines with four new stereocenters in up to quantitative yield and >95 : 5 diastereoselectivity and can proceed both intra‐ and intermolecularly. When performed intramolecularly, the tetracyclic structure of either akuamma or malagasy alkaloids was obtained selectively depending on the temperature of the reaction. This divergent outcome could be rationalized based on DFT calculations.
Deciphering Reversible Homogeneous Catalysis of the Electrochemical H2 Evolution and Oxidation: Role of Proton Relays and Local Concentration Effects**
Authors: Reuillard Bertrand , Costentin Cyrille , Artero Vincent 
Published: April 2023

AbstractNickel bisdiphosphine complexes bearing pendant amines form a unique series of catalysts (so‐called DuBois’ catalysts) capable of bidirectional/reversible electrocatalytic oxidation and production of dihydrogen. This unique behaviour is directly linked to the presence of proton relays installed close to the metal center. We report here for the arginine derivative [Ni(P2CyN2Arg)2]6+ on a mechanistic model and its kinetic treatment that may apply to all DuBois’ catalysts and show that it allows for a good fit of experimental data measured at different pH values, catalyst concentrations and partial hydrogen pressures. The bidirectionality of catalysis results from balanced equilibria related to hydrogen uptake/evolution on one side and (metal)‐hydride installation/capture on the other side, both controlled by concentration effects resulting from the presence of proton relays and connected by two square schemes corresponding to proton‐coupled electron transfer processes. We show that the catalytic bias is controlled by the kinetic of the H2 uptake/evolution step. Reversibility does not require that the energy landscape be flat, with redox transitions occurring at potentials up to 250 mV away for the equilibrium potential, although such large deviations from a flat energy landscape can negatively impacts the rate of catalysis when coupled with slow interfacial electron transfer kinetics.
Unveiling One‐to‐One Correspondence Between Excited Triplet States and Determinate Interactions by Temperature‐Controllable Blue‐Green‐Yellow Afterglow
Authors: Liu Xiuxing , Liao Qiuyan , Yang Jie , Li Zhen , Li Qianqian 
Published: April 2023

AbstractPhosphorescence of organic materials is highly dependent on intermolecular interactions, for the sensitive triplet excitons toward environment and aggregated structures. However, until now, relationship between phosphorescence and intermolecular interactions is still unclear for complicated influence factors and uncontrollable aggregated behaviors. Herein, taking temperature as the controlled variable, the afterglow can continuously change from blue to green, then to yellow, even achieve the white emission with deuteration process. It is mainly due to the hierarchical architectures of molecular aggregates with rational distribution of intermolecular interactions, as well as gradually unlocking process of interactions with different energies. Accordingly, the one‐to‐one correspondence between the determinate interactions and excited triplet states have been established, guiding accurate design of desirable phosphorescence materials by hierarchical control of aggregated structures.
Dynamic Hydrogen‐Bonded Zinc Adeninate Framework (ZAF) for Immobilization of Catalytic DNA
Authors: Baslyman Walaa S. , Alahmed Othman , Chand Santanu , Qutub Somayah , Khashab Niveen M. 
Published: April 2023

AbstractEffective immobilization and delivery of genetic materials is at the forefront of biological and medical research directed toward tackling scientific challenges such as gene therapy and cancer treatment. Herein we present a biologically inspired hydrogen‐bonded zinc adeninate framework (ZAF) consisting of zinc adeninate macrocycles that self‐assemble into a 3D framework through adenine‐adenine interactions. ZAF can efficiently immobilize DNAzyme with full protection against enzyme degradation and physiological conditions until it is successfully delivered into the nucleus. As compared to zeolitic imidazolate frameworks (ZIFs), ZAFs are twofold more biocompatible with a significant loading efficiency of 96 %. Overall, our design paves the way for expanding functional hydrogen‐bonding‐based systems as potential platforms for the loading and delivery of biologics.
Synthesis of Sequence‐specific Poly(ester‐carbonate) Copolymers via Chemoselective Terpolymerization Controlled by the Stoichiometric Ratio of Phosphazene/Triethylborane
Authors: Ma Yukun , You Xiaoxia , Zhang Jinbo , Wang Xiaowu , Kou Xinhui , Liu Shaofeng , Zhong Ronglin , Li Zhibo 
Published: April 2023

AbstractChemoselective terpolymerization can produce polymer materials with diverse compositions and sequential structures, and thus have attracted considerable attention in the field of polymer synthesis. However, the intrinsic complexity of three‐component system also brings great chanllenge, in regard to the reactivity and selectivity of different monomers. Herein, we report the terpolymerization of CO2/epoxide/anhydride by a binary organocatalytic C3N3‐Py‐P3/TEB (triethylborane) system. Both the activity and chemoselectivity were highly dependent upon the molar ratio of C3N3‐Py‐P3 to TEB, and sequence‐controlled poly(ester‐carbonate) copolymers were readily synthesized through one‐pot/one‐step methodology by tuning the stoichiometric ratio of phosphazene/TEB. In particular, C3N3‐Py‐P3/TEB with a molar ratio of 1/0.5 exhibited an unprecedentedly high chemoselectivity for ring‐opening alternating copolymerization (ROAC) of cyclohexene oxide (CHO) and phthalic anhydride (PA) first and then ROAC of CO2/CHO. Thus, well‐defined triblock polycarbonate‐b‐polyester‐b‐polycarbonate copolymers can be produced from the mixture of CO2, CHO and PA using a bifunctional initiator. With C3N3‐Py‐P3/TEB=1/1, tapered copolymers were obtained, while random copolymers with high content of polycarbonate (PC) were synthesized with further increasing the amount of TEB. The mechanism of the unexpected chemoselectivity was further investigated by DFT calculations.
Modern Strategies for Carbon Isotope Exchange
Authors: Labiche Alexandre , Malandain Augustin , Molins Maxime , Taran Frédéric , Audisio Davide 
Published: April 2023

AbstractIn contrast to stable and natural abundant carbon‐12, the synthesis of organic molecules with carbon (radio)isotopes must be conceived and optimized in order to navigate through the hurdles of radiochemical requirements, such as high costs of the starting materials, harsh conditions and radioactive waste generation. In addition, it must initiate from the small cohort of available C‐labeled building blocks. For long time, multi‐step approaches have represented the sole available patterns. On the other side, the development of chemical reactions based on the reversible cleavage of C−C bonds might offer new opportunities and reshape retrosynthetic analysis in radiosynthesis. This review aims to provide a short survey on the recently emerged carbon isotope exchange technologies that provide effective opportunity for late‐stage labeling. At present, such strategies have relied on the use of primary and easily accessible radiolabeled C1‐building blocks, such as carbon dioxide, carbon monoxide and cyanides, while the activation principles have been based on thermal, photocatalytic, metal‐catalyzed and biocatalytic processes.