bluuebunny/crossref_metadata_2025_split huggingface dataset:
Energetics and Structural Transitions of Nonequivalent Polytypes for FCC and HCP Metals
Authors: Liu ZhongQiang , Kong XiangMu , Ding Feng 
Published: September 2024

AbstractAlthough metal nanomaterials with unconventional phases have attracted extensive attention, the lack of information on the characteristics of metal polytypes hinders the development of related research. In this work, the energetics of nonequivalent polytypes for bulk face‐centered cubic (Li, Al, Ca, Cu, Sr, Rh, Pd, Ag, Ir, Pt, Au, and Pb) and hexagonal close‐packed metals (Be, Na, Mg, Sc, Ti, Zn, Cd, Y, Zr, Tc, Ru, Hf, Re, Os, and Tl) is systematically reported. For each metal, the structural properties and energies for its polytypes with up to the periodic stacking length of L = 10 is obtained by DFT calculation. The variation tendency of the energy differences between 3C and 2H polytypes is summarized in the Periodic Table of Elements. Generally, the ratio c/(La) increases when metal crystals except Ir, Rh, Zn, and Cd leave away from their ground‐state structure. It is found that the energy difference between polytypes originates from various interactions between the two types of atomic layers: the k layer and the h layer. The work is helpful to understand not only the structural transitions in bulk metals, such as Li, Na, Sr, Ti, Al, Pb, Y, Re, and Tl, but also the evolutions of Au nanomaterials.
Perovskite Nanocrystals Initiate One‐Step Oxygen Tolerant PET‐RAFT Polymerization of Highly Loaded, Efficient Plastic Nanocomposites
Authors: Bellotti Valentina , Carulli Francesco , Mecca Sara , Zaffalon Matteo L. , Erroi Andrea , Catalano Federico , Boventi Matteo , Infante Ivan , Rossi Francesca , Beverina Luca , Brovelli Sergio , Simonutti Roberto 
Published: September 2024

AbstractLead halide perovskite nanocrystals (LHP‐NCs) incorporated within polymer matrices have emerged as promising materials for various photonic applications. However, challenges persist in achieving high‐quality nanocomposites due to low monomer conversion yields, restricted LHP‐NCs loadings, and difficulty in maintaining NCs integrity post‐polymerization. A novel protocol for synthesizing LHP‐NCs/poly(methyl methacrylate) nanocomposites in a single step via the NC‐initiated photoinduced electron transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) method is presented. Polymerization initiation mediated by NCs surfaces under blue light enables the fabrication of homogeneous nanocomposites with NCs loadings up to 7% w/w and ≈90% monomer conversion even in the presence of oxygen. This process preserves the optical quality of the NCs and passivates NCs surface defects, resulting in nanocomposites exhibiting near unity luminescence efficiencies. The potential of this approach for producing highly loaded nanocomposites for radiation detection is validated by radioluminescence measurements showing light yield values of 6000 ph MeV−1 and fast scintillation dynamics with effective lifetime of 490 ps, showing promise for time‐of‐flight radiometry.
Safe, Facile, and Straightforward Fabrication of Poly(N‐vinyl imidazole)/Polyacrylonitrile Nanofiber Modified Separator as Efficient Polysulfide Barrier Toward Durable Lithium–Sulfur Batteries
Authors: Lin Chenxiao , Feng Ping , Wang Daiqing , Chen Xiaoqin , Fang Yuning , Gao Yiwei , Zheng Yong , Yan Yan , Liu Mingkai 
Published: September 2024

AbstractLithium–sulfur (Li–S) batteries are gaining tremendous attention as promising energy storage solutions due to their impressive energy density and the affordability of sulfur. However, the practical use of Li–S batteries encounter major obstacles such as the polysulfide shuttle effect, which leads to capacity loss and decreased cycling stability. Herein, a polyethylene imidazole/polyacrylonitrile (PVIMPAN) nanofibers‐modified Celgard separator is constructed via a facile electrospinning strategy and used as a polysulfides barrier for Li–S batteries. The electron‐deficient imidazole groups introduced on the surface of PVIMPAN separators create a barrier that prevents polysulfide shuttling and extends cycle life. Additionally, the developed PVIMPAN separator exhibits a significantly enhanced Li+ transfer number of 0.60, compared to the commercial Celgard separator (0.20). This enhancement can be attributed to the strong binding energy between imidazole groups and bis(trifluoromethanesulphonyl)imide anion, leading to improved Li plating and stripping performance. Consequently, incorporating the PVIMPAN separator into Li–S batteries enable the achievement of a discharge capacity of 786.0 mAh g−1 with close to 100% Coulombic efficiency after 500 cycles at 1C (25 °C). It is believed that this work can provide valuable insights for designing suitable and robust separators for metal–sulfur batteries.
Advanced MXene/Graphene Oxide/Lignosulfonate Inks for 3D Printing Thick Electrodes with Vertically Aligned Pores to Dually Boost Mass Loading and Areal Capacitance
Authors: Ye Haichuan , He Yuan , You Tingting , Xu Feng 
Published: September 2024

AbstractDirect ink writing 3D printing, using ink extrusion, promises to transform conventional 2D thin electrodes into 3D thick architectures for high‐performance supercapacitors. However, formulating 3D printing inks and designing 3D architectures for electrodes remain challenges. In this work, a novel MXene/graphene oxide/lignosulfonate (MGL) ink with excellent rheological properties is developed for 3D printing MGL thick electrodes with vertically aligned architectures. The MGL ink exhibited excellent shear‐thinning properties for smooth 3D printing and shape retention after printing. The 3D‐printed MGL thick electrode, with a thickness of up to 4 mm, achieved a breakthrough mass loading of 72.1 mg cm−2, resulting in an extremely high areal capacitance of 8.6 F cm−2 that is 9.6 times greater than the value observed for the bulk MGL electrode (0.9 F cm−2). Additionally, supercapacitors using the 3D MGL electrode achieved an energy density of 505.3 µWh cm−2, significantly surpassing the value for bulk MGL electrode (52.8 µWh cm−2). This enhancement is attributed to the efficient design of the electrodes, where vertically aligned pores in the 3D MGL electrode enhanced ion transfer and reaction kinetics. This study demonstrates an innovative approach for formulating inks and provides guidance for designing 3D thick electrodes with rapid ion transport and excellent electrochemical performance.
From Nanozymes to Multi‐Purpose Nanomaterials: The Potential of Metal–Organic Frameworks for Proteomics Applications
Authors: Swinnen Siene , de Azambuja Francisco , Parac‐Vogt Tatjana N. 
Published: September 2024

AbstractMetal‐organic frameworks (MOFs) have the potential to revolutionize the biotechnological and medical landscapes due to their easily tunable crystalline porous structure. Herein, the study presents MOFs' potential impact on proteomics, unveiling the diverse roles MOFs can play to boost it. Although MOFs are excellent catalysts in other scientific disciplines, their role as catalysts in proteomics applications remains largely underexplored, despite protein cleavage being of crucial importance in proteomics protocols. Additionally, the study discusses evolving MOF materials that are tailored for proteomics, showcasing their structural diversity and functional advantages compared to other types of materials used for similar applications. MOFs can be developed to seamlessly integrate into proteomics workflows due to their tunable features, contributing to protein separation, peptide enrichment, and ionization for mass spectrometry. This review is meant as a guide to help bridge the gap between material scientists, engineers, and MOF chemists and on the other side researchers in biology or bioinformatics working in proteomics.
Carrier–Carrier Repulsion Limits the Conductivity of N‐Doped Organic Semiconductors
Authors: Yang Xuwen , Ye Gang , Liu Jian , Chiechi Ryan C. , Koster L. Jan Anton 
Published: September 2024

AbstractMolecular doping is a key strategy to enhance the electrical conductivity of organic semiconductors. Typically, the electrical conductivity shows a maximum value upon increased doping, after which the conductivity decreases. This decrease in conductivity is commonly attributed to unfavorable changes in the morphology. However, in recent simulation work, has shown, that the conductivity—at high doping—is instead limited by electron–electron repulsion rather than by morphology, at least for some material combinations. Based on the simulations, this limitation is expected to show up in the dependence of the Seebeck coefficient versus carrier density: the Seebeck coefficient will follow Heike's formula if carrier–carrier repulsion limits the conductivity. Here, the electrical conductivity and Seebeck coefficient are measured as a function of doping for a series of n‐type organic semiconductors. Additionally, the resulting carrier density is measured using metal‐insulator‐semiconductor diodes, which link dopant loading and the number of charge carriers. At high carrier densities, the Seebeck coefficient indeed follows Heike's formula, confirming that the conductivity is limited by carrier–carrier repulsion rather than by morphological effects. This study shows that current models of hopping transport in organic semiconductors may be incomplete. As a result, this study offers novel insights in the design of organic semiconductors.
High‐Entropy Metal‐Organic Frameworks (HEMOFs): A New Frontier in Materials Design for CO2 Utilization
Authors: Sikma R. Eric , Vogel Dayton J. , Reyes Raphael A. , Meyerson Melissa L. , Kotula Paul G. , Gallis Dorina F. Sava 
Published: September 2024

AbstractHigh‐entropy materials (HEMs) emerged as promising candidates for a diverse array of chemical transformations, including CO2 utilization. However, traditional HEMs catalysts are nonporous, limiting their activity to surface sites. Designing HEMs with intrinsic porosity can open the door toward enhanced reactivity while maintaining the many benefits of high configurational entropy. Here, a synergistic experimental, analytical, and theoretical approach to design the first high‐entropy metal‐organic frameworks (HEMOFs) derived from polynuclear metal clusters is implemented, a novel class of porous HEMs that is highly active for CO2 fixation under mild conditions and short reaction times, outperforming existing heterogeneous catalysts. HEMOFs with up to 15 distinct metals are synthesized (the highest number of metals ever incorporated into a single MOF) and, for the first time, homogenous metal mixing within individual clusters is directly observed via high‐resolution scanning transmission electron microscopy. Importantly, density functional theory studies provide unprecedented insight into the electronic structures of HEMOFs, demonstrating that the density of states in heterometallic clusters is highly sensitive to metal composition. This work dramatically advances HEMOF materials design, paving the way for further exploration of HEMs and offers new avenues for the development of multifunctional materials with tailored properties for a wide range of applications.
Molten Salt‐Assisted Synthesis of Catalysts for Energy Conversion
Authors: Chen Ding , Mu Shichun 
Published: September 2024

AbstractA breakthrough in manufacturing procedures often enables people to obtain the desired functional materials. For the field of energy conversion, designing and constructing catalysts with high cost‐effectiveness is urgently needed for commercial requirements. Herein, the molten salt‐assisted synthesis (MSAS) strategy is emphasized, which combines the advantages of traditional solid and liquid phase synthesis of catalysts. It not only provides sufficient kinetic accessibility, but effectively controls the size, morphology, and crystal plane features of the product, thus possessing promising application prospects. Specifically, the selection and role of the molten salt system, as well as the mechanism of molten salt assistance are analyzed in depth. Then, the creation of the catalyst by the MSAS and the electrochemical energy conversion related application are introduced in detail. Finally, the key problems and countermeasures faced in breakthroughs are discussed and look forward to the future. Undoubtedly, this systematical review and insights here will promote the comprehensive understanding of the MSAS and further stimulate the generation of new and high efficiency catalysts.
Enhancing Photoswitchable Wetting Properties of Hydrophobic Porous Spiropyran Copolymer Surfaces Through Surface Roughness Engineering
Authors: Nekoonam Niloofar , Dreher Franziska , Mayoussi Fadoua , Zhu Pang , Thomann Ralf , Montazeri Ramin , Bhagwat Sagar , Hambitzer Leonhard , Helmer Dorothea 
Published: September 2024

AbstractSurfaces with photoswitchable wettability are of great interest for various applications such as smart coatings or liquid condensation. The photochromic ring opening reaction of spiropyran (SP) to merocyanine (MC) implies a high dipole moment change, making it interesting for photo‐controlled wetting properties. In addition to the material chemistry, surface wettability is influenced by the surface topography. Porous SP copolymers with various micro‐/nanostructures, that is, different submicron roughness, are fabricated via polymerization‐induced phase separation. The influence of the surface topography on the photoswitchable wetting properties is studied. Surfaces with arithmetic mean roughness (Sa) below 150 nm exhibited a maximum static contact angle (SCA) photoswitch up to 16° from 124 ± 6° to 108 ± 4° upon UV exposure. While superhydrophobic surfaces with higher Sa (157 – 608 nm) showed an insignificant SCA switch. The latter surfaces have a SCA above 150° and low CA hysteresis indicating small and insufficient contact with SP/MC surface asperities for the switch. With the optimized surfaces, photo‐controlled water condensation is studied on microscale and showed that the condensate droplets merged faster, and formed larger droplets pinned to the original contact lines on surfaces switched to the less hydrophobic state.
Construction of Concentration Quenching‐Resistant Multi‐Resonance TADF Emitters via Positional Isomerization for OLEDs
Authors: Xiao Xiong , Hu Jia‐Jun , Huo Zhong‐Zhong , Liang Jia‐Qi , Yang Bo , Hong Xian‐Fang , Chen Zong‐Ju , Wang Yu , Li Cheng‐Hui , Zheng You‐Xuan 
Published: September 2024

AbstractMultiple resonance thermally activated delayed fluorescence (MR‐TADF) emitters are promising for high‐definition organic light‐emitting diodes (OLEDs) due to their high exciton utilization and color purity. However, strong interchromophore interactions cause most MR‐TADF emitters with planar structures to aggregate at high doping concentrations, leading to degraded efficiencies. Herein, using benzenesulfonyl‐functionalized dibenzothiophene sulfoximine with steric effects, three MR‐TADF emitters (2SBN, 3SBN, and 4SBN) are synthesized by coupling the classic DtBuCzB skeleton at different sites. Three emitters exhibit green or blue‐green emission with full width at half maximum (FWHM) values less than 29 nm and photoluminescence quantum yields exceeding 90%. OLEDs based on 2SBN, 3SBN, and 4SBN achieve high maximum external quantum efficiency (EQEmax) values of 30.1%, 27%, and 33.8%, respectively, at a 5 wt.% doping concentration. Notably, due to the distorted conformation of 4SBN and suppressed intermolecular interaction, the OLED remains high EQEmax of 28.9% at a doping concentration of 20 wt.%. These results demonstrate the feasibility of molecular design to modulate spatial conformations via positional isomerism to develop MR‐TADF emitters with reduced concentration quenching.
Brain‐Controlled Augmented Hearing for Spatially Moving Conversations in Multi‐Talker Environments
Authors: Choudhari Vishal , Han Cong , Bickel Stephan , Mehta Ashesh D. , Schevon Catherine , McKhann Guy M. , Mesgarani Nima 
Published: September 2024

AbstractFocusing on a specific conversation amidst multiple interfering talkers is challenging, especially for those with hearing loss. Brain‐controlled assistive hearing devices aim to alleviate this problem by enhancing the attended speech based on the listener's neural signals using auditory attention decoding (AAD). Departing from conventional AAD studies that relied on oversimplified scenarios with stationary talkers, a realistic AAD task that involves multiple talkers taking turns as they continuously move in space in background noise is presented. Invasive electroencephalography (iEEG) data are collected from three neurosurgical patients as they focused on one of the two moving conversations. An enhanced brain‐controlled assistive hearing system that combines AAD and a binaural speaker‐independent speech separation model is presented. The separation model unmixes talkers while preserving their spatial location and provides talker trajectories to the neural decoder to improve AAD accuracy. Subjective and objective evaluations show that the proposed system enhances speech intelligibility and facilitates conversation tracking while maintaining spatial cues and voice quality in challenging acoustic environments. This research demonstrates the potential of this approach in real‐world scenarios and marks a significant step toward developing assistive hearing technologies that adapt to the intricate dynamics of everyday auditory experiences.
A Few Charged Residues in Galectin‐3′s Folded and Disordered Regions Regulate Phase Separation
Authors: Sun Yung‐Chen , Hsieh Tsung‐Lun , Lin Chia‐I , Shao Wan‐Yu , Lin Yu‐Hao , Huang Jie‐rong 
Published: September 2024

AbstractProteins with intrinsically disordered regions (IDRs) often undergo phase separation to control their functions spatiotemporally. Changing the pH alters the protonation levels of charged sidechains, which in turn affects the attractive or repulsive force for phase separation. In a cell, the rupture of membrane‐bound compartments, such as lysosomes, creates an abrupt change in pH. However, how proteins’ phase separation reacts to different pH environments remains largely unexplored. Here, using extensive mutagenesis, NMR spectroscopy, and biophysical techniques, it is shown that the assembly of galectin‐3, a widely studied lysosomal damage marker, is driven by cation‐π interactions between positively charged residues in its folded domain with aromatic residues in the IDR in addition to π–π interaction between IDRs. It is also found that the sole two negatively charged residues in its IDR sense pH changes for tuning the condensation tendency. Also, these two residues may prevent this prion‐like IDR domain from forming rapid and extensive aggregates. These results demonstrate how cation‐π, π–π, and electrostatic interactions can regulate protein condensation between disordered and structured domains and highlight the importance of sparse negatively charged residues in prion‐like IDRs.
Making High Thermoelectric and Superior Mechanical Performance Nb0.88Hf0.12FeSb Half‐Heusler via Additive Manufacturing
Authors: Yao Zhifu , Qiu Wenbin , Chen Chen , Bao Xin , Luo Kaiyi , Deng Yong , Xue Wenhua , Li Xiaofang , Hu Qiujun , Guo Junbiao , Yang Lei , Hu Wenyu , Wang Xiaoyi , Liu Xingjun , Zhang Qian , Tanigaki Katsumi , Tang Jun 
Published: September 2024

AbstractThermoelectric generators held great promise through energy harvesting from waste heat. Their practical application, however, is greatly constrained by poor raw material utilization and tedious processing in fabricating desired shapes. Herein, a state‐of‐the‐art process is reported for 3D printing the half‐Heusler (Nb0.88Hf0.12FeSb) thermoelectric material using laser powder bed fusion (LPBF). The multi‐dimensional intra‐ and inter‐granular defects created by this process greatly suppress thermal conductivity by providing numerous phonon scattering centers. The resulting LPBF‐fabricated half‐Heusler exhibits a high figure of merit ≈1.2 at 923 K and a single‐leg maximum efficiency of ≈3.3% at a temperature difference (ΔT) of 371 K. Hafnium oxide nanoparticles generated during LPBF effectively prevent crack propagation, ensuring competent mechanical performance and reliable thermoelectric output. The findings highlight the significant potential of LPBF in driving the next industrial revolution of highly efficient and customizable thermoelectric materials.
Lateral Electronic Junction of a Single Ultrathin Silicon Induced by Interfacial Dipole of Self‐Assembled Monolayer
Authors: Han Junghyup , Lee Won Hyung , Park Junwoo , Jin Huding , Cho Yong Hyun , Yu Seungyeon , Li Lianghui , Lee Jaewon , Woo Gunhoo , Kim Taesung , Kim Youn Sang 
Published: September 2024

AbstractInterface engineering is pivotal for enhancing the performance and stability of devices with layered structures, including solar cells, electronic devices, and electrochemical systems. Incorporating the interfacial dipole between the bulk layers effectively modulates the energy level difference at the interface and does not significantly influence adjacent layers overall. However, interfaces can drastically affect adjoining layers in ultrathin devices, which are essential for next‐generation electronics with high integrity, excellent performance, and low power consumption. In particular, the interfacial effect is pronounced in ultrathin semiconductors, which have a weak electric field screening effect. Herein, the substantial interfacial impact on the ultrathin silicon is shown, the p‐ to n‐type inversion of the semiconductor solely through the deposition of a self‐assembled monolayer (SAM) without external bias. The effects of SAMs with different interfacial dipoles are investigated by using Hall measurement and surface analytic techniques, such as UPS, XPS, and KPFM. Furthermore, the lateral electronic junction of the ultrathin silicon is engineered by the regioselective deposition of SAMs with opposite dipoles, and the device exhibits rectification behavior. When the interfacial dipole of SAM is manipulated, the rectification ratio changes sensitively, and thus the fabricated diode shows potential to be developed as a sensing platform.
A Live‐Cell Epigenome Manipulation by Photo‐Stimuli‐Responsive Histone Methyltransferase Inhibitor
Authors: Wu Chuan‐Shuo , Sun Xin , Liu Li , Cheng Liang 
Published: September 2024

AbstractPost‐translational modifications on the histone H3 tail regulate chromatin structure, impact epigenetics, and hence the gene expressions. Current chemical modulation tools, such as unnatural amino acid incorporation, protein splicing, and sortase‐based editing, have allowed for the modification of histones with various PTMs in cellular contexts, but are not applicable for editing native chromatin. The use of small organic molecules to manipulate histone‐modifying enzymes alters endogenous histone PTMs but lacks precise temporal and spatial control. To date, there has been no achievement in modulating histone methylation in living cells with spatiotemporal resolution. In this study, a new method is presented for temporally manipulating histone dimethylation H3K9me2 using a photo‐responsive inhibitor that specifically targets the methyltransferase G9a on demand. The photo‐caged molecule is stable under physiological conditions and cellular environments, but rapidly activated upon exposure to light, releasing the bioactive component that can immediately inhibit the catalytic ability of the G9a in vitro. Besides, this masked compound could also efficiently reactivate the inhibition of methyltransferase activity in living cells, subsequently suppress H3K9me2, a mark that regulates various chromatin functions. Therefore, the chemical system will be a valuable tool for manipulating the epigenome for therapeutic purposes and furthering the understanding of epigenetic mechanisms.