bluuebunny/crossref_metadata_2025_split huggingface dataset:
Applications of artificial intelligence in clinical laboratory genomics
Authors: Aradhya Swaroop , Facio Flavia M. , Metz Hillery , Manders Toby , Colavin Alexandre , Kobayashi Yuya , Nykamp Keith , Johnson Britt , Nussbaum Robert L. 
Published: July 2023

AbstractThe transition from analog to digital technologies in clinical laboratory genomics is ushering in an era of “big data” in ways that will exceed human capacity to rapidly and reproducibly analyze those data using conventional approaches. Accurately evaluating complex molecular data to facilitate timely diagnosis and management of genomic disorders will require supportive artificial intelligence methods. These are already being introduced into clinical laboratory genomics to identify variants in DNA sequencing data, predict the effects of DNA variants on protein structure and function to inform clinical interpretation of pathogenicity, link phenotype ontologies to genetic variants identified through exome or genome sequencing to help clinicians reach diagnostic answers faster, correlate genomic data with tumor staging and treatment approaches, utilize natural language processing to identify critical published medical literature during analysis of genomic data, and use interactive chatbots to identify individuals who qualify for genetic testing or to provide pre‐test and post‐test education. With careful and ethical development and validation of artificial intelligence for clinical laboratory genomics, these advances are expected to significantly enhance the abilities of geneticists to translate complex data into clearly synthesized information for clinicians to use in managing the care of their patients at scale.
Transition‐Metal‐Free Synthesis of N‐Heterocyclic Compounds via Multi‐Component Reactions
Authors: Boruah Dhruba Jyoti , Borkotoky Lodsna , Newar Uma Devi , Maurya Ram Awatar , Yuvaraj Panneerselvam 
Published: July 2023

AbstractMulticomponent reactions (MCRs) have emerged as powerful tools in synthetic chemistry for the efficient synthesis of diverse molecular scaffolds, particularly nitrogen‐containing heterocycles. Despite their numerous advantages, the use of transition metal catalysts or additives in MCRs can present limitations due to cost, toxicity, and environmental concerns. In recent years, there has been a growing interest in transition metal‐free MCRs for the synthesis of N‐heterocyclic compounds. This review provides a comprehensive and concise overview of the recent advancements in transition metal‐free MCRs for the synthesis of valuable N‐heterocycles over the past five years. The review is systematically organized, categorizing the discussed MCRs based on the size of the heterocyclic ring and the number of nitrogen atoms. Only MCRs that result in the formation of heterocyclic rings containing at least one nitrogen atom are included, while the derivatization of N‐heterocycles using transition metal‐free MCRs falls outside the scope of this review. By highlighting the recent developments in this field, this review aims to showcase the potential and significance of transition metal‐free MCRs as sustainable and efficient strategies for accessing N‐heterocyclic compounds. The elimination of transition metals not only simplifies the reaction conditions but also contributes to greener and more environmentally friendly synthetic approaches. This review serves as a valuable resource for researchers interested in the design and application of transition metal‐free MCRs in the synthesis of nitrogen‐containing heterocycles.
The various meanings and uses of bone “remodeling” in biological anthropology: A review
Authors: Wei Xuan , Cooper David M. L. 
Published: July 2023

AbstractObjectivesIn modern bone biology, the term “remodeling” generally refers to internal bone turnover that creates secondary osteons. However, it is also widely used by skeletal biologists, including biological anthropologists as a catch‐all term to refer to different skeletal changes. In this review, we investigated how “remodeling” is used across topics on skeletal biology in biological anthropology to demonstrate potential problems with such pervasive use of a generalized term.MethodsUsing PubMed and Google Scholar, we selected and reviewed 205 articles that use the term remodeling to describe skeletal processes and have anthropological implications. Nine edited volumes were also reviewed as examples of collaborative work by different experts to demonstrate the diverse and extensive use of the term remodeling.ResultsFour general meanings of bone “remodeling” were identified, namely, internal turnover, functional adaptation, fracture repair, and growth remodeling. Additionally, remodeling is also used to refer to a broad array of pathological skeletal changes.DiscussionAlthough we initially identified four general meanings of bone remodeling, they are not mutually exclusive and often occur in combination. The term “remodeling” has become an extensively used catch‐all term to refer to different processes and outcomes of skeletal changes, which inevitably lead to misunderstanding and a loss of information. Such ambiguity and confusion are potentially problematic as the field of biological anthropology becomes increasingly multidisciplinary. Therefore, we advocate for precise, context‐specific definitions and explanations of bone remodeling as it continues to be used across disciplines within and beyond biological anthropology.
Molecular Engineering of Cation Solvation Structure for Highly Selective Carbon Dioxide Electroreduction
Authors: Ni Wenpeng , Guan Yongji , Chen Houjun , Zhang Yan , Wang Shuangyin , Zhang Shiguo 
Published: July 2023

AbstractBalancing the activation of H2O is crucial for highly selective CO2 electroreduction (CO2RR), as the protonation steps of CO2RR require fast H2O dissociation kinetics, while suppressing hydrogen evolution (HER) demands slow H2O reduction. We herein proposed one molecular engineering strategy to regulate the H2O activation using aprotic organic small molecules with high Gutmann donor number as a solvation shell regulator. These organic molecules occupy the first solvation shell of K+ and accumulate in the electrical double layer, decreasing the H2O density at the interface and the relative content of proton suppliers (free and coordinated H2O), suppressing the HER. The adsorbed H2O was stabilized via the second sphere effect and its dissociation was promoted by weakening the O−H bond, which accelerates the subsequent *CO2 protonation kinetics and reduces the energy barrier. In the model electrolyte containing 5 M dimethyl sulfoxide (DMSO) as an additive (KCl‐DMSO‐5), the highest CO selectivity over Ag foil increased to 99.2 %, with FECO higher than 90.0 % within −0.75 to −1.15 V (vs. RHE). This molecular engineering strategy for cation solvation shell can be extended to other metal electrodes, such as Zn and Sn, and organic molecules like N,N‐dimethylformamide.
Nano‐Impact Electrochemistry Reveals Kinetics Information of Metal‐Ion Battery Materials with Multiple Redox Centers
Authors: Xu Wei , Zheng Jia‐Jia , Li Yu‐An , Gao Xingfa , Ji Xiaobo , Zhou Yi‐Ge 
Published: July 2023

AbstractPrussian blue (PB) has emerged as a promising cathode material in aqueous batteries. It possesses two distinct redox centers, and the potassium ions (K+) are unevenly distributed throughout the compound, adding complexity to the interpretation of the K+ insertion/de‐insertion kinetic mechanism. Traditional ensemble‐averaged measurements are limited in uncovering the precise kinetic information of the PB particles, as the results are influenced by the construction of the porous composite electrode and the redox behavior from different particles. In this study, the electrochemical processes of individual PB particles were investigated using nano‐impact electrochemistry. By varying the potentials, different types of transient current signals were obtained that revealed the kinetic mechanism of each oxidation/reduction reaction in combination with theoretical simulation. Additionally, a partially contradictory conclusion between single‐particle analysis and the ensemble‐averaged measurement was discussed. These findings contribute to a better understanding of the electrochemical processes of cathode materials with multiple redox centers, which facilitates the development of effective strategies to optimize these materials.
Coupling Titanium and Chromium Catalysis in a Reaction Network for the Reprogramming of [BH4]− as Electron Transfer and Hydrogen Atom Transfer Reagent for Radical Chemistry
Authors: Heinz Michael , Weiss Gregor , Shizgal Grigoriy , Panfilova Anastasia , Gansäuer Andreas 
Published: July 2023

AbstractWe describe a unique catalytic system with an efficient coupling of Ti‐ and Cr‐catalysis in a reaction network that allows the use of [BH4]− as stoichiometric hydrogen atom and electron donor in catalytic radical chemistry. The key feature is a relay hydrogen atom transfer from [BH4]− to Cr generating the active catalysts under mild conditions. This enables epoxide reductions, regiodivergent epoxide opening and radical cyclizations that are not possible with cooperative catalysis with radicals or by epoxide reductions via Meinwald rearrangement and ensuing carbonyl reduction. No typical SN2‐type reactivity of [BH4]− salts is observed.
Fragment‐Screening und schnelle mikromolare Detektion mit einem Benchtop‐NMR‐Spektrometer ermöglicht durch photoinduzierte Hyperpolarisation
Authors: Stadler Gabriela R. , Segawa Takuya F. , Bütikofer Matthias , Decker Venita , Loss Sandra , Czarniecki Barbara , Torres Felix , Riek Roland 
Published: August 2023

AbstractFragmentbasiertes Wirkstoffdesign ist eine gut etablierte Strategie für rationales Arzneimitteldesign, wobei die Kernspinresonanzspektroskopie (NMR) auf Hochfeldspektrometern als Referenzmethode für das Screening und die Hit‐Validierung dient. Hochfeld‐NMR‐Spektrometer sind jedoch nicht nur teuer, sondern erfordern auch eine spezielle Wartung, einen speziellen Raum und sind auf die Kühlung mit flüssigem Helium angewiesen, was angesichts der wiederkehrenden weltweiten Heliumknappheit kritisch geworden ist. Wir schlagen eine Alternative zum Hochfeld‐NMR‐Screening vor, indem wir den kürzlich entwickelten Ansatz des Fragment‐Screenings durch photoinduzierte hyperpolarisierte NMR auf einem kryogenfreien 80‐MHz‐Benchtop‐NMR‐Spektrometer anwenden, der Signalverstärkungen von bis zu drei Größenordnungen ermöglicht. Es wird gezeigt, dass es möglich ist, mit einem Benchtop‐NMR‐Spektrometer bei niedrigen mikromolaren Konzentrationen sowohl von Proteinen als auch von Liganden neue Hits zu entdecken und die Entwicklung von Medikamenten einzuleiten. Der vorgestellte Ansatz arbeitet mit höherer Geschwindigkeit als moderne Hochfeld‐NMR‐Ansätze und weist eine Nachweisgrenze im nanomolaren Bereich auf. Die photoinduzierte Hyperpolarisation ist bekanntlich kostengünstig und einfach zu implementieren, was der Philosophie von Benchtop‐NMR‐Spektrometern sehr entgegenkommt. Diese Ergebnisse ebnen den Weg für den Einsatz von Benchtop‐NMRunter nahezu physiologischen Bedingungen für die Entwicklung von Arzneimitteln und weitere Life‐Science‐Anwendungen.
Lichtinduzierte, metallfreie Erzeugung von Cyanocarbenen aus Alkinyltriazenen für die Synthese von Nitrilderivaten
Authors: Michel Elena , Grieser Fabian F. , Mackenroth Alexandra V. , Schukin Michael , Krämer Petra , Tahir Shaista , Rominger Frank , Rudolph Matthias , Hashmi A. Stephen K. 
Published: July 2023

AbstractDie Chemie der Alkinyltriazene ist ein aufstrebendes Gebiet für organische Chemiker, und insbesondere säureinduzierte nukleophile Funktionalisierungen, entweder direkt oder nach einer vorherigen Reaktion mit aromatischen Triazenen unter Ausschluss von Stickstoff, ebneten den Weg für erfolgreiche Strategien. Im Gegensatz dazu ist das chemische Verhalten von Alkinyltriazenen bei einer Bestrahlung mit Licht noch unbekannt. Wir stellen hier die erste Photoaktivierung von Alkinyltriazenen vor, die ein ungewöhnliches Reaktivitätsmuster auslöst, bei dem die N1−N2‐Bindung der Triazeneinheit gespalten wird, was zu einem einzigartigen Zugang zu Cyanocarbenen aus einem leicht verfügbaren, stabilen und unempfindlichen Vorläufer führt. Dies ermöglicht den Zugang zu verschiedenen Nitrilverbindungen ohne die Verwendung eines toxischen Cyanierungsmittels, indem das Reaktivitätsmuster von Carbenen ausgenutzt wird. Durch Variation der Reaktionsbedingungen und Lichtquellen können verschiedene Substitutionsmuster selektiv und in guter Ausbeute unter milden und metallfreien Bedingungen erhalten werden, wodurch die Alkinyltriazen‐Einheit als photozugängliches Methylennitril‐Synthon eingeführt wird. Mit diesem Synthon werden Unterklassen wie α‐Alkoxynitrile, α‐Aminonitrile und α‐Cyanohydrazone leicht verfügbar. Diese weisen synthetisch wertvolle Substitutionsmuster für die Synthese von Arzneimitteln, Zwischenprodukten für die Totalsynthese und die Aminosäuresynthese auf.
Tribochemically Controlled Atom Transfer Radical Polymerization Enabled by Contact Electrification
Authors: Wang Chen , Zhao Ruoqing , Fan Wenru , Li Lei , Feng Haoyang , Li Zexuan , Yan Ci , Shao Xiaoyang , Matyjaszewski Krzysztof , Wang Zhenhua 
Published: July 2023

AbstractTraditional mechanochemically controlled reversible‐deactivation radical polymerization (RDRP) utilizes ultrasound or ball milling to regenerate activators, which induce side reactions because of the high‐energy and high‐frequency stimuli. Here, we propose a facile approach for tribochemically controlled atom transfer radical polymerization (tribo‐ATRP) that relies on contact‐electro‐catalysis (CEC) between titanium oxide (TiO2) particles and CuBr2/tris(2‐pyridylmethylamine (TPMA), without any high‐energy input. Under the friction induced by stirring, the TiO2 particles are electrified, continuously reducing CuBr2/TPMA into CuBr/TPMA, thereby conversing alkyl halides into active radicals to start ATRP. In addition, the effect of friction on the reaction was elucidated by theoretical simulation. The results indicated that increasing the frequency could reduce the energy barrier for the electron transfer from TiO2 particles to CuBr2/TPMA. In this study, the design of tribo‐ATRP was successfully achieved, enabling CEC (ca. 10 Hz) access to a variety of polymers with predetermined molecular weights, low dispersity, and high chain‐end fidelity.
NH4+ Charge Carrier Coordinated H‐Bonded Organic Small Molecule for Fast and Superstable Rechargeable Zinc Batteries
Authors: Song Ziyang , Miao Ling , Lv Yaokang , Gan Lihua , Liu Mingxian 
Published: July 2023

AbstractOrganic small molecules as high‐capacity cathodes for Zn‐organic batteries have inspired numerous interests, but are trapped by their easy‐dissolution in electrolytes. Here we knit ultrastable lock‐and‐key hydrogen‐bonding networks between 2, 7‐dinitropyrene‐4, 5, 9, 10‐tetraone (DNPT) and NH4+ charge carrier. DNPT with octuple‐active carbonyl/nitro centers (H‐bond acceptor) are redox‐exclusively accessible for flexible tetrahedral NH4+ ions (H‐bond donator) but exclude larger and rigid Zn2+, due to a lower activation energy (0.14 vs. 0.31 eV). NH4+ coordinated H‐bonding chemistry conquers the stability barrier of DNPT in electrolyte, and gives fast diffusion kinetics of non‐metallic charge carrier. A stable two‐step 4e− NH4+ coordination with DNPT cathode harvests a high capacity (320 mAh g−1), a high‐rate capability (50 A g−1) and an ultralong life (60,000 cycles). This finding points to a new paradigm for H‐bond stabilized organic small molecules to design advanced zinc batteries.
Thiophene‐Containing Covalent Organic Frameworks for Overall Photocatalytic H2O2 Synthesis in Water and Seawater
Authors: Yue Jie‐Yu , Song Li‐Ping , Fan Yan‐Fei , Pan Zi‐Xian , Yang Peng , Ma Yu , Xu Qing , Tang Bo 
Published: August 2023

AbstractH2O2 is a significant chemical widely utilized in the environmental and industrial fields, with growing global demand. Without sacrificial agents, simultaneous photocatalyzed H2O2 synthesis through the oxygen reduction reaction (ORR) and water oxidation reaction (WOR) dual channels from seawater is green and sustainable but still challenging. Herein, two novel thiophene‐containing covalent organic frameworks (TD‐COF and TT‐COF) were first constructed and served as catalysts for H2O2 synthesis via indirect 2e− ORR and direct 2e− WOR channels. The photocatalytic H2O2 production performance can be regulated by adjusting the N‐heterocycle modules (pyridine and triazine) in COFs. Notably, with no sacrificial agents, just using air and water as raw materials, TD‐COF exhibited high H2O2 production yields of 4060 μmol h−1 g−1 and 3364 μmol h−1 g−1 in deionized water and natural seawater, respectively. Further computational mechanism studies revealed that the thiophene was the primary photoreduction unit for ORR, while the benzene ring (linked to the thiophene by the imine bond) was the central photooxidation unit for WOR. The current work exploits thiophene‐containing COFs for overall photocatalytic H2O2 synthesis via ORR and WOR dual channels and provides fresh insight into creating innovative catalysts for photocatalyzing H2O2 synthesis.
Progress and Perspectives on the Development of Pouch‐Type Lithium Metal Batteries
Authors: Jie Yulin , Tang Chao , Xu Yaolin , Guo Youzhang , Li Wanxia , Chen Yawei , Jia Haojun , Zhang Jing , Yang Ming , Cao Ruiguo , Lu Yuhao , Cho Jaephil , Jiao Shuhong 
Published: July 2023

AbstractLithium (Li) metal batteries (LMBs) are the “holy grail” in the energy storage field due to their high energy density (theoretically >500 Wh kg−1). Recently, tremendous efforts have been made to promote the research & development (R&D) of pouch‐type LMBs toward practical application. This article aims to provide a comprehensive and in‐depth review of recent progress on pouch‐type LMBs from full cell aspect, and to offer insights to guide its future development. It will review pouch‐type LMBs using both liquid and solid‐state electrolytes, and cover topics related to both Li and cathode (including LiNixCoyMn1‐x‐yO2, S and O2) as both electrodes impact the battery performance. The key performance criteria of pouch‐type LMBs and their relationship in between are introduced first, then the major challenges facing the development of pouch‐type LMBs are discussed in detail, especially those severely aggravated in pouch cells compared with coin cells. Subsequently, the recent progress on mechanistic understandings of the degradation of pouch‐type LMBs is summarized, followed with the practical strategies that have been utilized to address these issues and to improve the key performance criteria of pouch‐type LMBs. In the end, it provides perspectives on advancing the R&Ds of pouch‐type LMBs towards their application in practice.
Effective Activation of Strong C−Cl Bonds for Highly Selective Photosynthesis of Bibenzyl via Homo‐Coupling
Authors: Yang Qingning , Li Xiyi , Chen Lu , Han Xiaoyu , Wang Feng Ryan , Tang Junwang 
Published: July 2023

AbstractCarbon‐carbon (C−C) coupling of organic halides has been successfully achieved in homogeneous catalysis, while the limitation, e.g., the dependence on rare noble metals, complexity of the metal‐ligand catalylst and the poor catalyst stability and recyclability, needs to be tackled for a green process. The past few years have witnessed heterogeneous photocatalysis as a green and novel method for organic synthesis processes. However, the study on C−C coupling of chloride substrates is rare due to the extremely high bond energy of C−Cl bond (327 kJ mol−1). Here, we report a robust heterogeneous photocatalyst (Cu/ZnO) to drive the homo‐coupling of benzyl chloride with high efficiency, which achieves an unprecedented high selectivity of bibenzyl (93 %) and yield rate of 92 % at room temperature. Moreover, this photocatalytic process has been validated for C−C coupling of 10 benzylic chlorides all with high yields. In addition, the excellent stability has been observed for 8 cycles of reactions. With detailed characterization and DFT calculation, the high selectivity is attributed to the enhanced adsorption of reactants, stabilization of intermediates (benzyl radicals) for the selective coupling by the Cu loading and the moderate oxidation ability of the ZnO support, besides the promoted charge separation and transfer by Cu species.
Preliminary description of a lateMiddle Pleistocenemammalian fauna prior to the extinction ofGigantopithecus blackifrom theYixiantian Cave, Guangxi ZAR, South China
Authors: Pan Yue , Zhang Yingqi , Yang Liyun , Takai Masanaru , Harrison Terry , Westaway Kira , Jin Changzhu 
Published: July 2023

AbstractIn recent years, nearly 20 cave sites with rich assemblages of mammalian fossils have been found and excavated in the Chongzuo area, Guangxi Zhuang Autonomous Region, China. Their ages are distributed throughout the entire Pleistocene Epoch. These discoveries have greatly facilitated our understanding of the evolution of theStegodon‐Ailuropodafauna and the environmental context of human evolution in southern China. Here, we present a preliminary report on a diverse late Middle Pleistocene mammalian fauna from the Yixiantian Cave in southern China, which is a typical representative of theStegodon‐Ailuropodafauna (sensu lato). The fossil mammals are represented by isolated dental remains only. In 2010 and 2011, two seasons of systematic excavations at the Yixiantian Cave yielded a total of 4,958 identifiable mammalian teeth. They were identified as belonging to 37 species and 6 orders of mammals. In addition, the tooth type of all the teeth representing each species was also determined where possible. A single fragmentary molar was identified as belonging toGigantopithecus blacki, indicating that its population had declined sharply at this time and was on the brink of extinction. Description of the Yixiantian fauna will not only help better characterize the composition of theStegodon‐Ailuropodafauna during the late Middle Pleistocene, but also clarify our understanding of the paleoenvironmental context at a time just prior to the extinction ofG. blacki.
Dinuclear Zinc‐Catalyzed Asymmetric Desymmetrization of Cyclopentendiones: Access to Functional Cyclopentanediones Bearing an All‐carbon Quaternary Stereocenter
Authors: Du Si‐Si , Zhai Ying‐Hui , Zhang Cui , Wang Min‐Can , Jia Shi‐Kun , Mei Guang‐Jian , Hua Yuan‐Zhao 
Published: August 2023

AbstractThe success in the identification of the two enantioisomeric surfaces of electrophiles by dinuclear zinc catalysts is disclosed. This protocol realizes a dinuclear zinc‐cocatalyzed desymmetrization of cyclopentendiones using α‐hydroxy aryl ketones as nucleophiles through Michael addition reaction. Under mild conditions, a series of functional cyclopentanediones bearing multiple stereogenic centers including an all‐carbon quaternary stereocenter, were obtained in moderate to good yields with excellent stereoselectivities.