bluuebunny/crossref_metadata_2025_split huggingface dataset:
Wnt3a‐Loaded Hydroxyapatite Nanowire@Mesoporous Silica Core−Shell Nanocomposite Promotes the Regeneration of Dentin−Pulp Complex via Angiogenesis, Oxidative Stress Resistance, and Odontogenic Induction of Stem Cells
Authors: Luo Nan , Deng Yu‐Wei , Wen Jin , Xu Xiao‐Chen , Jiang Rui‐Xue , Zhan Jing‐Yu , Zhang Yu , Lu Bing‐Qiang , Chen Feng , Chen Xi 
Published: April 2023

AbstractPulp exposure often leads to pulp necrosis, root fractures, and ultimate tooth loss. The repair of the exposure site with pulp capping treatment is of great significance to preserving pulp vitality, but its efficacy is impaired by the low bioactivity of capping materials and cell injuries from the local accumulation of oxidative stress. This study develops a Wnt3a‐loaded hydroxyapatite nanowire@mesoporous silica (Wnt3a‐HANW@MpSi) core−shell nanocomposite for pulp capping treatments. The ultralong and highly flexible hydroxyapatite nanowires provide the framework for the composites, and the mesoporous silica shell endows the composite with the capacity of efficiently loading/releasing Wnt3a and Si ions. Under in vitro investigation, Wnt3a‐HANW@MpSi not only promotes the oxidative stress resistance of dental pulp stem cells (DPSCs), enhances their migration and odontogenic differentiation, but also exhibits superior properties of angiogenesis in vitro. Revealed by the transcriptome analysis, the underlying mechanisms of odontogenic enhancement by Wnt3a‐HANW@MpSi are closely related to multiple biological processes and signaling pathways toward pulp/dentin regeneration. Furthermore, an animal model of subcutaneous transplantation demonstrates the significant reinforcement of the formation of dentin–pulp complex‐like tissues and blood vessels by Wnt3a‐HANW@MpSi in vivo. These results indicate the promising potential of Wnt3a‐HANW@MpSi in treatments of dental pulp exposure.
Weaving Aerogels into 3D Ordered Hyperelastic Hybrid Carbon Assemblies
Authors: Guo Hele , Fei Qingyang , Lian Meng , Zhu Tianyi , Fan Wei , Li Yueming , Sun Li , de Jong Flip , Chu Kaibin , Zong Wei , Zhang Chao , Liu Tianxi 
Published: April 2023

AbstractThe development of a 3D carbon assembly with a combination of extraordinary electrochemical and mechanical properties is desirable yet challenging. Herein, an ultralight and hyperelastic nanofiber‐woven hybrid carbon assembly (NWHCA) is fabricated by nanofiber weaving of isotropic porous and mechanical brittle quasi‐aerogels. Upon subsequent pyrolysis, metallogel‐derived quasi‐aerogel hybridization and nitrogen/phosphorus co‐doping are integrated into the NWHCA. Finite element simulation indicates that the 3D lamella–bridge architecture of NWHCA with the quasi‐aerogel hybridization contributes to resisting plastic deformation and structural damage under high compression, experimentally demonstrated by complete deformation recovery at 80% compression and unprecedented fatigue resistance (>94% retention after 5000 cycles). Due to the superelasticity and quasi‐aerogel integration, the zinc–air battery assembled based on NWHCA shows excellent electrochemical performance and flexibility. A proof‐of‐concept integrated device is presented, in which the flexible battery powers a piezoresistive sensor, using the NWHCA as the air cathode and the elastic conductor respectively, which can detect full‐range and sophisticated motions while attached to human skin. The nanofiber weaving strategy allows the construction of lightweight, superelastic, and multifunctional hybrid carbon assemblies with great potential in wearable and integrated electronics.
Aerobic Coupling of Organophosphonium Salts with Alkenes: Catalyst‐Free C(sp3)−C(sp2) Bond Formation
Authors: Guo Meng‐Meng , Qin Gan‐Qi , Jiang Xin‐Yu , Xu Hao , Ma Mengtao , Shen Zhi‐Liang , Chu Xue‐Qiang 
Published: April 2023

AbstractAn aerobic coupling of benzhydryl phosphonium salts with simple alkenes for accessing trisubstituted olefins is developed under metal‐free, catalyst‐free, and additive‐free conditions. New C(sp3)−C(sp2) bond is constructed via the C−P and C−H bond functionalization by synergistically using O2 as a “green” oxidant and DMSO as a promoter. The method also distinguishes itself by its broad substrate scope and synthetic potential. Particularly, the use of 1,3,5‐trimethoxybenzene fragment in the resulting products as a carbon‐based leaving group for further transformations is proved to be feasible.
Sympathetic Innervation Regulates Osteocyte‐Mediated Cortical Bone Resorption during Lactation
Authors: Guo Qiaoyue , Chen Ningrong , Qian Cheng , Qi Cheng , Noller Kathleen , Wan Mei , Liu Xiaonan , Zhang Weixin , Cahan Patrick , Cao Xu 
Published: April 2023

AbstractBone undergoes constant remodeling by osteoclast bone resorption coupled with osteoblast bone formation at the bone surface. A third major cell type in the bone is osteocytes, which are embedded in the matrix, are well‐connected to the lacunar network, and are believed to act as mechanical sensors. Here, it is reported that sympathetic innervation directly regulates lacunar osteocyte‐mediated bone resorption inside cortical bone. It is found that sympathetic activity is elevated in different mouse models of bone loss, including lactation, ovariectomy, and glucocorticoid treatment. Further, during lactation elevated sympathetic outflow induces netrin‐1 expression by osteocytes to further promote sympathetic nerve sprouting in the cortical bone endosteum in a feed‐forward loop. Depletion of tyrosine hydroxylase‐positive (TH+) sympathetic nerves ameliorated osteocyte‐mediated perilacunar bone resorption in lactating mice. Moreover, norepinephrine activates β‐adrenergic receptor 2 (Adrb2) signaling to promote secretion of extracellular vesicles (EVs) containing bone‐degrading enzymes for perilacunar bone resorption and inhibit osteoblast differentiation. Importantly, osteocyte‐specific deletion of Adrb2 or treatment with a β‐blocker results in lower bone resorption in lactating mice. Together, these findings show that the sympathetic nervous system promotes osteocyte‐driven bone loss during lactation, likely as an adaptive response to the increased energy and mineral demands of the nursing mother.
Microwatt Volatile Optical Bistability via Nanomechanical Nonlinearity
Authors: Papas Dimitrios , Ou Jun‐Yu , Plum Eric , Zheludev Nikolay I. 
Published: April 2023

AbstractMetastable optically controlled devices (optical flip‐flops) are needed in data storage, signal processing, and displays. Although nonvolatile memory relying on phase transitions in chalcogenide glasses has been widely used for optical data storage, beyond that, weak optical nonlinearities have hindered the development of low‐power bistable devices. This work reports a new type of volatile optical bistability in a hybrid nano‐optomechanical device, comprising a pair of anchored nanowires decorated with plasmonic metamolecules. The nonlinearity and bistability reside in the mechanical properties of the acoustically driven nanowires and are transduced to the optical response by reconfiguring the plasmonic metamolecules. The device can be switched between bistable optical states with microwatts of optical power and its volatile memory can be erased by removing the acoustic signal. The demonstration of hybrid nano‐optomechanical bistability opens new opportunities to develop low‐power optical bistable devices.
Composite Nanocoatings of Biomedical Magnesium Alloy Implants: Advantages, Mechanisms, and Design Strategies
Authors: Li Dan , Dai Danni , Xiong Gege , Lan Shuquan , Zhang Chao 
Published: April 2023

AbstractThe rapid degradation of magnesium (Mg) alloy implants erodes mechanical performance and interfacial bioactivity, thereby limiting their clinical utility. Surface modification is among the solutions to improve corrosion resistance and bioefficacy of Mg alloys. Novel composite coatings that incorporate nanostructures create new opportunities for their expanded use. Particle size dominance and impermeability may increase corrosion resistance and thereby prolong implant service time. Nanoparticles with specific biological effects may be released into the peri‐implant microenvironment during the degradation of coatings to promote healing. Composite nanocoatings provide nanoscale surfaces to promote cell adhesion and proliferation. Nanoparticles may activate cellular signaling pathways, while those with porous or core–shell structures may carry antibacterial or immunomodulatory drugs. Composite nanocoatings may promote vascular reendothelialization and osteogenesis, attenuate inflammation, and inhibit bacterial growth, thus increasing their applicability in complex clinical microenvironments such as those of atherosclerosis and open fractures. This review combines the physicochemical properties and biological efficiency of Mg‐based alloy biomedical implants to summarize the advantages of composite nanocoatings, analyzes their mechanisms of action, and proposes design and construction strategies, with the purpose of providing a reference for promoting the clinical application of Mg alloy implants and to further the design of nanocoatings.
Intermetallics Based on Sodium Chalcogenides Promote Stable Electrodeposition–Electrodissolution of Sodium Metal Anodes
Authors: Wang Yixian , Dong Hui , Katyal Naman , Vishnugopi Bairav S. , Singh Manish K. , Hao Hongchang , Liu Yijie , Liu Pengcheng , Mukherjee Partha P. , Henkelman Graeme , Watt John , Mitlin David 
Published: April 2023

AbstractSodiophilic micro‐composite films of sodium‐chalcogenide intermetallics (Na2Te and Na2S) and Cu particles are fabricated onto commercial copper foam current collectors (Na2Te@CF and Na2S@CF). For the first time a controllable capacity thermal infusion process is demonstrated. Enhanced wetting by the metal electrodeposition leads to state‐of‐the‐art electrochemical performance. For example, Na2Te@CF‐based half‐cells demonstrate stable cycling at 6 mA cm−2 and 6 mAh cm−2, corresponding to 54 µm of Na electrodeposited/electrodissolved by geometric area. Sodium metal batteries with Na3V2 (PO4)3 cathodes are stable at 30C (7 mA cm−2) and for 10 000 cycles at 5C and 10C. Cross‐sectional cryogenic focused ion beam (cryo‐FIB) microscopy details deposited and remnant dissolved microstructures. Sodium metal electrodeposition onto Na2Te@CF is dense, smooth, and free of dendrites or pores. On unmodified copper foam, sodium grows in a filament‐like manner, not requiring cycling to achieve this geometry. Substrate–metal interaction critically affects the metal–electrolyte interface, namely the thickness and morphology of the solid electrolyte interphase. Density functional theory and mesoscale simulations provide insight into support‐adatom energetics, nucleation response, and early‐stage morphological evolution. On Na2Te sodium atomic dispersion is thermodynamically more stable than isolated clusters, leading to conformal adatom coverage of the surface.
Understanding the CH activation of methane over single‐atom alloy catalysts by density functional theory calculations
Authors: Zhou Wenyu , Chen Yuping , Tan Luxi , Tang Qing , Lu Chenyang , Dong Lichun 
Published: April 2023

AbstractAs an important rate‐determining step in the oxidation of methane, the catalytic behaviors of single‐atom alloys (SAAs) on the CH activation reactions have not been fully understood. In this work, density functional theory calculations are performed to investigate the CH activation of methane on a series of SAAs with Cu(111/100) and Ag(111/100) as hosts. The reaction energies and the barriers for the CH dissociation reaction follow the traditional Brønsted–Evans–Polanyi (BEP) relationship, but the deviation from this linearity fitting is relatively large. To better describe the catalytic activity, a new nonlinear binary function is proposed to correlate the reaction barrier with the adsorption energies of *H and *CH3 products, which has higher correlation than the BEP relationship, and showed more accurate predictions of the CH activation reaction for unknown SAAs catalysis. Such mode might be able to extend to other catalyst systems to achieve large‐scale catalyst screening.
Interfacial Engineering of Magnesiophilic Coordination Layer Stabilizes Mg Metal Anode
Authors: Liu Yuan , Zhao Wanyu , Pan Zhenghui , Fan Zhengqing , Zhang Meng , Zhao Xiaoli , Chen Jianping , Yang Xiaowei 
Published: April 2023

AbstractRechargeable magnesium batteries (RMBs) are seriously plagued by the direct exposure of the Mg anode to the electrolyte components, leading to spontaneous and electrochemical side reactions and interfacial passivation. Herein, a benign coordination layer is constructed at the Mg/electrolyte interface where aniline with a strong magnesiophilic amine group and high stability to Mg is chosen as representative, which has higher adsorption energy than DME (1,2‐dimethoxyethane) and trace water. This Mg coordination environment mitigates side reactions, forming a non‐passivating interface consisting of aniline and much fewer by‐products after several cycles. Therefore, the Mg symmetrical cell operates with a low overpotential and uniform Mg0 deposition. This interfacial coordination can also be adopted for Mg anode protection in various electrolyte cases of Mg(TFSI)2 electrolyte systems.
Functional Nanopores Enabled with DNA
Authors: Xing Yongzheng , Rottensteiner Alexia , Ciccone Jonah , Howorka Stefan 
Published: April 2023

AbstractMembrane‐spanning nanopores are used in label‐free single‐molecule sensing and next‐generation portable nucleic acid sequencing, and as powerful research tools in biology, biophysics, and synthetic biology. Naturally occurring protein and peptide pores, as well as synthetic inorganic nanopores, are used in these applications, with their limitations. The structural and functional repertoire of nanopores can be considerably expanded by functionalising existing pores with DNA strands and by creating an entirely new class of nanopores with DNA nanotechnology. This review outlines progress in this area of functional DNA nanopores and outlines developments to open up new applications.
Organocatalytic Atroposelective Cross‐Coupling of 1‐Azonaphthalenes and 2‐Naphthols
Authors: Da Bing‐Chao , Wang Yong‐Bin , Cheng Jun Kee , Xiang Shao‐Hua , Tan Bin 
Published: April 2023

AbstractAtroposelective cross‐coupling is one of the most appealing routes to construct axially chiral binaphthyl molecules due to the modular and succinct nature. Although transition‐metal‐catalyzed cross‐couplings offer reliable synthetic means, alternative reaction modes that could be applied to broader substrate range without their pre‐functionalization is highly desirable. Herein we show that the application of chiral Brønsted acid catalyst as organocatalyst could accomplish cross‐coupling of 1‐azonaphthalenes and 2‐naphthols with high efficiency, exclusive C4‐selectivity as well as excellent enantioselectivity and functional group compatibility. The identification of acylimidazolinone auxiliary for azo activating group, effective remote catalyst control and arene resonance effect synergistically play key roles in the development of this method. The utility is further demonstrated by transformations of the products into other binaphthyl compounds with perfectly retained axial chirality.
Mechanistic Insight into Anion‐Binding Catalytic Living Cationic Polymerization
Authors: Li Maosheng , Li Hongyu , Zhang Xiaoyong , Wang Xianhong , Tao Youhua 
Published: April 2023

AbstractExploiting non‐covalent interactions to catalyze challenging ionic polymerizations is an ambitious goal but is in its infancy. We recently demonstrated non‐covalent anion‐binding catalysis as an effective methodology to enable living cationic polymerization (LCP) of vinyl ethers in an environmentally benign manner. Here, we further elucidate the structure‐reactivity relationships of the elaborately designed seleno‐cyclodiphosph(V)azanes catalysts and the roles of anion‐binding interactions by a combined theoretical DFT study and experimental study. The investigation suggests that the distinct cis‐cyclodiphosph(V)azane framework combined with “selenium effect” and electron‐withdrawing 3,5‐(CF3)2‐Phenyl substitution pattern in catalyst enables a critical contribution to accessing excellent stability, anion affinity and solubility under polymerization conditions. Thus, the catalyst could leverage anion‐binding interactions to precisely control reversible and transient dormant‐active species equilibrium, allowing it to dynamically bind, recognize and pre‐organize propagating ionic species and monomer, thereby facilitating efficient chain propagation and minimizing irreversible chain transfer events under mild conditions. The more in‐depth understanding of the mechanism for anion‐binding catalytic LCP reported herein should help to guide future catalyst design and to extend this concept to broader polymerization systems where ionic species serve as crucial intermediates.
Simultaneous Ring Contraction and Expansion Reaction: Electrosynthesis of Heterocycle‐Fused Fulleroids and Photovoltaic Application
Authors: Yin Zheng‐Chun , Li Mingjie , Niu Chuang , Wang Wei‐Feng , Liu Wen‐Rui , Zhang Qian‐Wen , Wang Guan‐Wu 
Published: April 2023

AbstractSimultaneous electrochemical ring contraction and expansion reactions remain unexplored to date. Herein, the reductive electrosynthesis of heterocycle‐fused fulleroids from fullerotetrahydropyridazines and electrophiles in the presence of a trace amount of oxygen has been achieved with concurrent ring contraction and ring expansion. When trifluoroacetic acid and alkyl bromides are employed as electrophiles, heterocycle‐fused fulleroids with a 1,1,2,6‐configuration are regioselectively formed. In contrast, heterocycle‐fused fulleroids with a 1,1,4,6‐configuration are regioselectively produced as two separable stereoisomers if phthaloyl chloride is used as the electrophile. The reaction proceeds through multiple steps of electroreduction, heterocycle ring‐opening, oxygen oxidation, heterocycle contraction, fullerene cage expansion, and nucleophilic addition. The structures of these fulleroids have been determined by spectroscopic data and single‐crystal X‐ray diffraction analyses. The observed high regioselectivities have been rationalized by theoretical calculations. Representative fulleroids have been applied in organic solar cells as the third component and exhibit good performance.
Merging Styrene and Diene Structures to a Cyclic Diene: Anionic Polymerization of 1‐Vinylcyclohexene (VCH)
Authors: Hahn Christoph , Rauschenbach Moritz , Frey Holger 
Published: April 2023

AbstractWe report the first anionic polymerization of 1‐vinylcyclohexene (VCH). This structure may be considered as an intermediate between dienes and styrene. The polymerization of this cyclic 1,2‐disubstituted 1,3‐diene proceeded quantitatively in cyclohexane at 25 °C with sec‐butyllithium as an initiator. The obtained polymers have well‐controlled molecular weights in the range of 5 to 142 kg mol−1, controlled by the molar ratio of monomer and initiator, with narrow molecular weight distributions (Đ<1.07–1.20). In situ 1H NMR kinetic characterization revealed a weak gradient structure for the copolymers of styrene and VCH, (rSty=2.55, rVCH=0.39). P(VCH) obtained in cyclohexane with sec‐BuLi as an initiator showed both 1,4‐ and 3,4‐incorporation mode (ratio: 64 : 36). It was demonstrated that the microstructure of the resulting P(VCH) can be altered by the addition of a modifier (THF), resulting in increasing 3,4‐microstructure (up to 78 %) and elevated glass‐transition temperature up to 89 °C. Thus, the monomer VCH polymerizes carbanionically like a diene, however leading to rigid polymers with high glass transition temperature, which provides interesting options for combination with other dienes to well‐defined polymer architectures and materials.
DNA Nanotechnology for Investigating Mechanical Signaling in the Immune System
Authors: Hu Yuesong , Duan Yuxin , Salaita Khalid 
Published: April 2023

AbstractImmune recognition occurs at specialized cell‐cell junctions when immune cells and target cells physically touch. In this junction, groups of receptor‐ligand complexes assemble and experience molecular forces that are ultimately generated by the cellular cytoskeleton. These forces are in the range of piconewton (pN) but play crucial roles in immune cell activation and subsequent effector responses. In this minireview, we will review the development of DNA based molecular tension sensors and their applications in mapping and quantifying mechanical forces experienced by immunoreceptors including T‐cell receptor (TCR), Lymphocyte function‐associated antigen (LFA‐1), and the B‐cell receptor (BCR) among others. In addition, we will highlight the use of DNA as a mechanical gate to manipulate mechanotransduction and decipher how mechanical forces regulate antigen discrimination and receptor signaling.
A General Preparation of Solid Solution‐Oxide Heterojunction Photocatalysts through Metal–Organic Framework Transformation Induced Pre‐nucleation
Authors: Wei Jiaxu , Mu Xijiao , Hu Yang , Liu Liangliang , Wu Xiaoxia , Liu Qingyi , Zhang Tong , Peng Yong , Cao Jing , Yan Chun‐Hua , Tang Yu 
Published: April 2023

AbstractSolid solution‐oxide heterostructures combine the advantages of solid solution and heterojunction materials to improve electronic structure and optical properties by metal doping, and enhance charge separation and transfer in semiconductor photocatalysts by creating a built‐in electric field. Nevertheless, the effective design and synthesis of these materials remains a significant challenge. Here, we develop a generally applicable strategy that leverages the transformable properties of metal–organic frameworks (MOFs) to prepare solid solution‐oxide heterojunctions with controllable structural and chemical compositions. The process consists of three main steps. First, MOFs with different topological structures and metal centers are transformed, accompanied by pre‐nucleation of a metal oxide. Second, solid solution is prepared through calcination of the transformed MOFs. Finally, a heterojunction is formed by combining solid solution with another metal oxide group through endogenous overflow. DFT calculations and study on carrier dynamics show that the structure of the material effectively prevents electrons from returning to the bulk phase, exhibiting superior photocatalytic reduction performance of CO2. This study is expected to promote the controllable synthesis and research of MOF‐derived heterojunctions.
Site‐Selective C−H Functionalization of Carbazoles
Authors: Elsaid Mazen , Ge Robbie , Liu Chong , Maiti Debabrata , Ge Haibo 
Published: April 2023

AbstractCarbazole alkaloids hold great potential in pharmaceutical and material sciences. However, the current approaches for C1 functionalization of carbazoles rely on the use of a pre‐installed directing group, severely limiting their applicability and hindering their overall efficiency. Herein, we report for the first time the development of direct Pd‐catalyzed C−H alkylation and acylation of carbazoles assisted by norbornene (NBE) as a transient directing mediator. Notably, the involvement of a six‐membered palladacycle intermediate was suggested in this case, representing the first example of such intermediacy within the extensively studied Pd/norbornene reactions realm.