bluuebunny/crossref_metadata_2025_split huggingface dataset:
Versatile Thermally Activated Delayed Fluorescence Emitters via Non‐conjugated Extension Strategy Enabling OLEDs with Efficiency Over 37%
Authors: Ma Zhiwei , Wang Yuyuan , Pu Junrong , Li Gaoyu , Mao Zhu , Zhao Juan , Yang Zhiyong , Su Shi‐Jian , Chi Zhenguo 
Published: December 2023

AbstractIn recent years, thermally activated delayed fluorescence (TADF) materials with high horizontal dipole ratios (Θ//) have attracted enormous attention in constructing high‐efficiency organic light–emitting diodes (OLEDs). However, the common strategy to improve Θ// based on extending π‐conjugation tends to induce bathochromic emission shift, and emitters with Θ// exceeding 90% are rarely reported. Herein, a non‐conjugated extension strategy is developed to promote molecular horizontal dipole orientation. By simply modifying the spiro‐acridine with extra 9‐phenylcarbazole groups, two high‐efficiency and versatile TADF emitters 36DPCZSFAC‐TRZ and 36DPCZSFAC‐PYPM are constructed without bathochromic emission shift, and state‐of‐the‐art ultra‐high Θ// of 92% and 96% are achieved, respectively. More fascinatingly, due to the special spiro molecular structures, the TADF emitters hold distinguished merits of aggregation‐induced emission property, near unitary photoluminescence quantum yields, fast reverse intersystem crossing rates, and enhanced charge‐carrier transport property, which enable outstanding external quantum efficiency values of up to 22.1/20.9% and 37.4/34.2% in non‐doped/doped OLEDs for 36DPCZSFAC‐TRZ and 36DPCZSFAC‐PYPM, respectively, demonstrating their great potentials in the fabrication of high‐efficiency OLEDs.
Tattoo‐Like Multi‐Color Physically Unclonable Functions
Authors: Kiremitler N. Burak , Esidir Abidin , Drake Gryphon A. , Yazici Ahmet Faruk , Sahin Furkan , Torun Ilker , Kalay Mustafa , Kelestemur Yusuf , Demir Hilmi Volkan , Shim Moonsub , Mutlugun Evren , Onses M. Serdar 
Published: December 2023

AbstractAdvanced anti‐counterfeiting and authentication approaches are in urgent need of the rapidly digitizing society. Physically unclonable functions (PUFs) attract significant attention as a new‐generation security primitive. The challenge is design and generation of multi‐color PUFs that can be universally applicable to objects of varied composition, geometry, and rigidity. Herein, tattoo‐like multi‐color fluorescent PUFs are proposed and demonstrated. Multi‐channel optical responses are created by electrospraying of polymers that contain semiconductor nanocrystals with precisely defined photoluminescence. The universality of this approach enables the use of dot and dot‐in‐rod geometries with unique optical characteristics. The fabricated multi‐color PUFs are then transferred to a target object by using a temporary tattoo approach. Digitized keys generated from the red, green and blue fluorescence channels facilitate large encoding capacity and rapid authentication. Feature matching algorithms complement the authentication by direct image comparison, effectively alleviating constraints associated with imaging conditions. The strategy that paves the way for the development of practical, cost‐effective, and secure anticounterfeiting systems is presented.
Ultra‐Pure Chiral Third Harmonic Generation Enabled by Mie‐Resonant Dielectric Dimer
Authors: Liu Xingguang , Li Junqing , Zhao Rui , Zhang Yingjie , Chen Chen , Dong Yongkang 
Published: December 2023

AbstractTailoring chiroptical responses at the nanoscale is crucial for on‐chip compact polarization manipulation and enantiomer sensing. Efficient chiral second and third harmonic generation has been successfully demonstrated from bulk materials to metamaterials. Here, pronounced linear and nonlinear circular dichroisms are obtained by rotating a dielectric nanocylinder dimer. It is revealed that the giant chiroptical effects originate from multipolar Mie resonances on the dimer, especially the magnetic dipole resonance. The calculated nonlinear g‐factor can reach −1.975 in the visible regime, indicating an ultra‐pure chiral third harmonic generation in the ultraviolet band. The presented results open new horizons for enhancing and modulating the linear and nonlinear chiroptical responses of nanostructures and can find potential applications in lasing and sensing.
Accelerating Uranium Extraction from Water via Synergy of Adsorption and Filtration by MOF Hybrid Membrane
Authors: Zhang Yifan , Gao Jian , Deng Ziqi , Li Ziming , Wang Fengju , Chen Shusen , Deng Pengyang 
Published: December 2023

AbstractIn this paper, novel UiO‐66‐AO‐based adsorption‐filtration hybrid membranes (UAMs) are prepared via an irradiation‐mediated growth strategy to simultaneously improve water flux and accelerate uranium extraction from water resources. The UAM shows an equilibrium adsorption that is four times faster than UiO‐66‐AO powder and an adsorption capacity that is over two times higher. UAM also achieves a record synergy of high flux and high uranium removal ratio from simulated seawater (1358.8 L m−2 h−1, 84.5%) by one‐time filtration under ambient temperature and pressure (the adsorption is 1.83 mg g−1 in 90 min). The excellent uranium extraction performance is attributed to the unique UAM structure, in which water flows through the channels of thin metal‐organic framework (MOF) film without blocking by substrate leading to the high flux during filtration, and the full contact of uranium with abundant exposed active sites promotes the adsorption. This work will be conducive to overcoming the bottleneck problems of uranium extraction from water resources.
Ultrabroadband High Photoresponsivity at Room Temperature Based on Quasi‐1D Pseudogap System (TaSe4)2I
Authors: Li Jialin , Li Qing , Mi Junjian , Xu Zhuan , Xie Yu , Tang Wei , Zhu Huanfeng , Li Linjun , Tong Limin 
Published: December 2023

AbstractNarrow bandgap materials have garnered significant attention within the field of broadband photodetection. However, the performance is impeded by diminished absorption near the bandgap, resulting in a rapid decline in photoresponsivity within the mid‐wave infrared (MWIR) and long‐wave infrared (LWIR) regions. Furthermore, they mostly worked in cryogenic temperature. Here, without the assistance of any complex structure and special environment, it is realized high responsivity covering ultra‐broadband wavelength range (Ultraviolet (UV) to LWIR) in a single quasi‐1D pseudogap (PG) system (TaSe4)2I nanoribbon, especially high responsivity (From 23.9 to 8.31 A W−1) within MWIR and LWIR region at room temperature (RT). Through direct probing the carrier relaxation process with broadband time‐resolved transient absorption spectrum measurement, the underlying mechanism of majorly photoconductive effect is revealed, which causes an increased spectral weight extended to PG region. This work paves the way for realizing high‐performance uncooled MWIR and LWIR detection by using quasi‐1D PG materials.
Potassium‐Rich Iron Hexacyanoferrate/Carbon Cloth Electrode for Flexible and Wearable Potassium‐Ion Batteries
Authors: Li Xinyue , Zhang Xiaolin , Xu Junmin , Duan Zhixia , Xu Yue , Zhang Xiaosheng , Zhang Lingling , Wang Ye , Chu Paul K. 
Published: December 2023

AbstractThe fast development of flexible and wearable electronics increases the demand for flexible secondary batteries, and the emerging high‐performance K‐ion batteries (KIBs) have shown immense promise for the flexible electronics due to the abundant and cost‐effective potassium resources. However, the implementation of flexible cathodes for KIBs is hampered by the critical issues of low capacity, rapid capacity decay with cycles, and limited initial Coulombic efficiency. To address these pressing issues, a freestanding K‐rich iron hexacyanoferrate/carbon cloth (KFeHCF/CC) electrode is designed and fabricated by cathodic deposition. This innovative binder‐free and self‐supporting KFeHCF/CC electrode not only provides continuous conductive channels for electrons, but also accelerates the diffusion of potassium ions through the active electrode–electrolyte interface. Moreover, the nanosized potassium iron hexacyanoferrate particles limit particle fracture and pulverization to preserve the structure and stability during cycling. As a result, the K‐rich KFeHCF/CC electrode shows a reversible discharging capacity of 110.1 mAh g−1 at 50 mA g−1 after 100 cycles in conjunction with capacity retention of 92.3% after 1000 cycles at 500 mA g−1. To demonstrate the commercial feasibility, a flexible tubular KIB is assembled with the K‐rich KFeHCF/CC electrode, and excellent flexibility, capacity, and stability are observed.
Fundamental Understanding and Quantification of Capacity Losses Involving the Negative Electrode in Sodium‐Ion Batteries
Authors: Ma Le Anh , Buckel Alexander , Hofmann Andreas , Nyholm Leif , Younesi Reza 
Published: December 2023

AbstractKnowledge about capacity losses related to the solid electrolyte interphase (SEI) in sodium‐ion batteries (SIBs) is still limited. One major challenge in SIBs is that the solubility of SEI species in liquid electrolytes is comparatively higher than the corresponding species formed in Li‐ion batteries. This study sheds new light on the associated capacity losses due to initial SEI formation, SEI dissolution and subsequent SEI reformation, charge leakage via SEI and subsequent SEI growth, and diffusion‐controlled sodium trapping in electrode particles. By using a variety of electrochemical cycling protocols, synchrotron‐based X‐ray photoelectron spectroscopy (XPS), gas chromatography coupled with mass spectrometry (GC‐MS), and proton nuclear magnetic resonance (1H‐NMR) spectroscopy, capacity losses due to changes in the SEI layer during different open circuit pause times are investigated in nine different electrolyte solutions. It is shown that the amount of capacity lost depends on the interplay between the electrolyte chemistry and the thickness and stability of the SEI layer. The highest capacity loss is measured in NaPF6 in ethylene carboante mixed with diethylene carbonate electrolyte (i.e., 5 µAh h−1/2pause or 2.78 mAh g·h−1/2pause) while the lowest value is found in NaTFSI in ethylene carbonate mixed with dimethoxyethance electrolyte (i.e., 1.3 µAh h−1/2pause or 0.72 mAh g·h−1/2pause).
An Autologous Macrophage‐Based Phenotypic Transformation‐Collagen Degradation System Treating Advanced Liver Fibrosis
Authors: Duan Bo‐Wen , Liu Yan‐Jun , Li Xue‐Na , Han Meng‐Meng , Yu Hao‐Yuan , Hong He‐Yuan , Zhang Ling‐Feng , Xing Lei , Jiang Hu‐Lin 
Published: December 2023

AbstractIn advanced liver fibrosis (LF), macrophages maintain the inflammatory environment in the liver and accelerate LF deterioration by secreting proinflammatory cytokines. However, there is still no effective strategy to regulate macrophages because of the difficulty and complexity of macrophage inflammatory phenotypic modulation and the insufficient therapeutic efficacy caused by the extracellular matrix (ECM) barrier. Here, AC73 and siUSP1 dual drug‐loaded lipid nanoparticle is designed to carry milk fat globule epidermal growth factor 8 (MFG‐E8) (named MUA/Y) to effectively inhibit macrophage proinflammatory signals and degrade the ECM barrier. MFG‐E8 is released in response to the high reactive oxygen species (ROS) environment in LF, transforming macrophages from a proinflammatory (M1) to an anti‐inflammatory (M2) phenotype and inducing macrophages to phagocytose collagen. Collagen ablation increases AC73 and siUSP1 accumulation in hepatic stellate cells (HSCs) and inhibits HSCs overactivation. Interestingly, complete resolution of liver inflammation, significant collagen degradation, and HSCs deactivation are observed in methionine choline deficiency (MCD) and CCl4 models after tail vein injection of MUA/Y. Overall, this work reveals a macrophage‐focused regulatory treatment strategy to eliminate LF progression at the source, providing a new perspective for the clinical treatment of advanced LF.
Structure Prediction and Genome Mining‐Aided Discovery of the Bacterial C‐Terminal Tryptophan Prenyltransferase PalQ
Authors: Miyata Azusa , Ito Sohei , Fujinami Daisuke 
Published: December 2023

AbstractPost‐translational prenylations, found in eukaryotic primary metabolites and bacterial secondary metabolites, play crucial roles in biomolecular interactions. Employing genome mining methods combined with AlphaFold2‐based predictions of protein interactions, PalQ , a prenyltransferase responsible for the tryptophan prenylation of RiPPs produced by Paenibacillus alvei, is identified. PalQ differs from cyanobactin prenyltransferases because of its evolutionary relationship to isoprene synthases, which enables PalQ to transfer extended prenyl chains to the indole C3 position. This prenylation introduces structural diversity to the tryptophan side chain and also leads to conformational dynamics in the peptide backbone, attributed to the cis/trans isomerization that arises from the formation of a pyrrolidine ring. Additionally, PalQ exhibited pronounced positional selectivity for the C‐terminal tryptophan. Such enzymatic characteristics offer a toolkit for peptide therapeutic lipidation.
Boosting Thermoelectric Performance of Bi2Te3 Material by Microstructure Engineering
Authors: Wang Guoxiang , Meng Fanzheng , Chen Yingqi , Lotnyk Andriy , Shen Xiang 
Published: December 2023

AbstractDue to the intrinsic contradiction of electrical conductivity and Seebeck coefficient in thermoelectric materials, the enhancement for the power factor (PF) is limited. Since the PF decides the output power, strategies to the enhancement of PF are of paramount importance. In this work, Bi2Te3/Sb and Bi2Te3/W multilayer films are proposed to enhance the thermoelectric properties. Both systems possess extremely high conductivity of ≈5.6 × 105 S m−1. Moreover, the electrical conductivity and Seebeck coefficient simultaneously increase as temperature rising, showing the overcome of the intrinsic contradiction. This results in ultrahigh PFs of 1785 µWm−1 K−2 for Bi2Te3/W and of 1566 µWm−1 K−2 for Bi2Te3/Sb at 600 K. Thermal heating of the Bi2Te3/Sb multilayer system shows compositional changes with subsequent formation of Bi‐Te‐Sb phases, Sb‐rich Bi‐Te precipitates, and cavities. Contrary, the multilayer structure of the Bi2Te3/W films is maintained, while Bi2Te3 grains of high‐crystalline quality are confined between the W layers. In addition, bilayer defects in Bi2Te3 and smaller cavities at the interface to W layers are also observed. Thus, compositional and confinement effects as well as structural defects result in the ultrahigh PF. Overall, this work demonstrates the strategies on how to obtain ultrahigh PFs of commercial Bi2Te3 material by microstructure engineering using multilayer structures.
Morpholine Scaffolds’ Preparation for Foldamers’ Design and Construction
Authors: Schiaroli Nicola , Loro Camilla , Colombo Sara , Broggini Gianluigi , Papis Marta , Foschi Francesca 
Published: December 2023

AbstractThis review highlights the advances in the synthesis of morpholine building blocks useful for artificial oligomers synthesis and peptide foldamers or biopolymers. Both morpholino nucleosides and morpholine derived from amino acids have been considered focusing on the preparation of antisense strands, peptides and bio‐based materials.
Comparing the Pathology, Clinical, and Demographic Characteristics of Younger and Older‐Onset Multiple Sclerosis
Authors: Knowles Sarah , Middleton Rod , Cooze Benjamin , Farkas Ildiko , Leung Yeung Yeung , Allen Kelsey , Winslade Molly , Owen David R.J. , Magliozzi Roberta , Reynolds Richard , Neal James W. , Pearson Owen , Nicholas Richard , Pickrell W. Owen , Howell Owain W. ,   the UK MS Register Research Group
Published: December 2023

ObjectiveOlder people with multiple sclerosis (MS) have a less active radiological and clinical presentation, but many still attain significant levels of disability; but what drives worsening disability in this group?MethodsWe used data from the UK MS Register to characterize demographics and clinical features of late‐onset multiple sclerosis (LOMS; symptom onset at ≥50 years), compared with adult‐onset MS (AOMS; onset 18–49 years). We performed a pathology study of a separate MS cohort with a later onset (n = 18, mean age of onset 54 years) versus AOMS (n = 23, mean age of onset 29 years).ResultsIn the Register cohort, there were 1,608 (9.4%) with LOMS. When compared with AOMS, there was a lower proportion of women, a higher proportion of primary progressive MS, a higher level of disability at diagnosis (median MS impact scale 36.7 vs. 28.3, p < 0.001), and a higher proportion of gait‐related initial symptoms. People with LOMS were less likely to receive a high efficacy disease‐modifying treatment and attained substantial disability sooner. Controlling for age of death and sex, neuron density in the thalamus and pons decreased with onset‐age, whereas actively demyelinating lesions and compartmentalized inflammation was greatest in AOMS. Only neuron density, and not demyelination or the extent of compartmentalized inflammation, correlated with disability outcomes in older‐onset MS patients.InterpretationThe more progressive nature of older‐onset MS is associated with significant neurodegeneration, but infrequent inflammatory demyelination. These findings have implications for the assessment and treatment of MS in older people. ANN NEUROL 2024;95:471–486
Stabilizing Undercoordinated Zn Active Sites through Confinement in CeO2 Nanotubes for Efficient Electrochemical CO2 Reduction
Authors: Guo Si‐Tong , Du Yu‐Wei , Luo Huihua , Zhu Ziyin , Ouyang Ting , Liu Zhao‐Qing 
Published: December 2023

AbstractZn‐based catalysts hold great potential to replace the noble metal‐based ones for CO2 reduction reaction (CO2RR). Undercoordinated Zn (Znδ+) sites may serve as the active sites for enhanced CO production by optimizing the binding energy of *COOH intermediates. However, there is relatively less exploration into the dynamic evolution and stability of Znδ+ sites during CO2 reduction process. Herein, we present ZnO, Znδ+/ZnO and Zn as catalysts by varying the applied reduction potential. Theoretical studies reveal that Znδ+ sites could suppress HER and HCOOH production to induce CO generation. And Znδ+/ZnO presents the highest CO selectivity (FECO 70.9 % at −1.48 V vs. RHE) compared to Zn and ZnO. Furthermore, we propose a CeO2 nanotube with confinement effect and Ce3+/Ce4+ redox to stabilize Znδ+ species. The hollow core–shell structure of the Znδ+/ZnO/CeO2 catalyst enables to extremely expose electrochemically active area while maintaining the Znδ+ sites with long‐time stability. Certainly, the target catalyst affords a FECO of 76.9 % at −1.08 V vs. RHE and no significant decay of CO selectivity in excess of 18 h.
Structural Control of Highly Efficient Thermally Activated Delayed Fluorescence in Carbene Zinc(II) Dithiolates**
Authors: Mitra Mousree , Mrózek Ondřej , Putscher Markus , Guhl Jasper , Hupp Benjamin , Belyaev Andrey , Marian Christel M. , Steffen Andreas 
Published: December 2023

AbstractLuminescent metal complexes based on earth abundant elements are a valuable target to substitute 4d/5d transition metal complexes as triplet emitters in advanced photonic applications. Whereas CuI complexes have been thoroughly investigated in the last two decades for this purpose, no structure‐property‐relationships for efficient luminescence involving triplet excited states from ZnII complexes are established. Herein, we report on the design of monomeric carbene zinc(II) dithiolates (CZT) featuring a donor‐acceptor‐motif that leads to highly efficient thermally activated delayed fluorescence (TADF) with for ZnII compounds unprecedented radiative rate constants kTADF=1.2×106 s−1 at 297 K. Our high‐level DFT/MRCI calculations revealed that the relative orientation of the ligands involved in the ligand‐to‐ligand charge transfer (1/3LLCT) states is paramount to control the TADF process. Specifically, a dihedral angle of 36–40° leads to very efficient reverse intersystem‐crossing (rISC) on the order of 109 s−1 due to spin‐orbit coupling (SOC) mediated by the sulfur atoms in combination with a small ΔES1‐T1 of ca. 56 meV.
Synthetic Strategies for the Selective Functionalization of Carbon Nanodots Allow Optically Communicating Suprastructures
Authors: Bartolomei Beatrice , Sbacchi Maria , Rosso Cristian , Günay‐Gürer Ayse , Zdražil Lukáš , Cadranel Alejandro , Kralj Slavko , Guldi Dirk M. , Prato Maurizio 
Published: December 2023

AbstractThe surface of Carbon Nanodots (CNDs) stands as a rich chemical platform, able to regulate the interactions between particles and external species. Performing selective functionalization of these nanoscale entities is of practical importance, however, it still represents a considerable challenge. In this work, we exploited the organic chemistry toolbox to install target functionalities on the CND surface, while monitoring the chemical changes on the material's outer shell through nuclear magnetic resonance spectroscopy. Following this, we investigated the use of click chemistry to covalently connect CNDs of different nature en‐route towards covalent suprastructures with unprecedent molecular control. The different photophysical properties of the connected particles allowed their optical communication in the excited state. This work paves the way for the development of selective and addressable CND building blocks which can act as modular nanoscale synthons that mirror the long‐established reactivity of molecular organic synthesis.
Constructing Interfacial Oxygen Vacancy and Ruthenium Lewis Acid–Base Pairs to Boost the Alkaline Hydrogen Evolution Reaction Kinetics
Authors: Qin Qing , Jang Haeseong , Jiang Xiaoli , Wang Liu , Wang Xuefeng , Kim Min Gyu , Liu Shangguo , Liu Xien , Cho Jaephil 
Published: December 2023

AbstractSimultaneous optimization of the energy level of water dissociation, hydrogen and hydroxide desorption is the key to achieving fast kinetics for the alkaline hydrogen evolution reaction (HER). Herein, the well‐dispersed Ru clusters on the surface of amorphous/crystalline CeO2‐δ (Ru/ac‐CeO2‐δ) is demonstrated to be an excellent electrocatalyst for significantly boosting the alkaline HER kinetics owing to the presence of unique oxygen vacancy (VO) and Ru Lewis acid–base pairs (LABPs). The representative Ru/ac‐CeO2‐δ exhibits an outstanding mass activity of 7180 mA mgRu−1 that is approximately 9 times higher than that of commercial Pt/C at the potential of −0.1 V (V vs RHE) and an extremely low overpotential of 21.2 mV at a geometric current density of 10 mA cm−2. Experimental and theoretical studies reveal that the VO as Lewis acid sites facilitate the adsorption of H2O and cleavage of H‐OH bonds, meanwhile, the weak Lewis basic Ru clusters favor for the hydrogen desorption. Importantly, the desorption of OH from VO sites is accelerated via a water‐assisted proton exchange pathway, and thus boost the kinetics of alkaline HER. This study sheds new light on the design of high‐efficiency electrocatalysts with LABPs for the enhanced alkaline HER.
π–π Interaction‐Induced Organic Long‐wavelength Room‐Temperature Phosphorescence for In Vivo Atherosclerotic Plaque Imaging
Authors: Zhang Yufan , Li Jisen , Zhao Jiliang , Li Xuefei , Wang Zhimei , Huang Yicheng , Zhang Hongkai , Liu Qian , Lei Yunxiang , Ding Dan 
Published: December 2023

AbstractRoom‐temperature phosphorescent (RTP) materials have great potential for in vivo imaging because they can circumvent the autofluorescence of biological tissues. In this study, a class of organic‐doped long‐wavelength (≈600 nm) RTP materials with benzo[c][1,2,5] thiadiazole as a guest was constructed. Both host and guest molecules have simple structures and can be directly purchased commercially at a low cost. Owing to the long phosphorescence wavelength of the doping system, it exhibited good tissue penetration (10 mm). Notably, these RTP nanoparticles were successfully used to image atherosclerotic plaques, with a signal‐to‐background ratio (SBR) of 44.52. This study provides a new approach for constructing inexpensive red organic phosphorescent materials and a new method for imaging cardiovascular diseases using these materials.