bluuebunny/crossref_metadata_2025_split huggingface dataset:
Double‐Lattice Packing of Pentagonal Gold Bipyramids in Supercrystals with Triclinic Symmetry
Authors: Lyu Jieli , Chaâbani Wajdi , Modin Evgeny , Chuvilin Andrey , Bizien Thomas , Smallenburg Frank , Impéror‐Clerc Marianne , Constantin Doru , Hamon Cyrille 
Published: March 2022

AbstractPentagonal packing is a long‐standing issue and a rich mathematical topic, brought to the fore by recent progress in nanoparticle design. Gold pentagonal bipyramids combine fivefold symmetry and anisotropy and their section varies along the length. In this work, colloidal supercrystals of pentagonal gold bipyramids are obtained in a compact arrangement that generalizes the optimal packing of regular pentagons in the plane. Multimodal investigations reveal a two‐particle unit cell with triclinic symmetry, a lower symmetry than that of the building blocks. Monte Carlo computer simulations show that this lattice achieves the densest possible packing. Going beyond pentagons, further simulations show an odd–even effect of the number of sides on the packing: odd‐sided bipyramids are non‐centrosymmetric and require the double‐lattice arrangement to recover inversion symmetry. The supercrystals display a facet‐dependent optical response that is promising for sensing, metamaterials applications, and for fundamental studies of self‐assembly processes.
Negative Phototransistors with Ultrahigh Sensitivity and Weak‐Light Detection Based on 1D/2D Molecular Crystal p–n Heterojunctions and their Application in Light Encoders
Authors: Zhu Xiaoting , Yan Yujie , Sun Lingjie , Ren Yiwen , Zhang Yihan , Liu Yang , Zhang Xiaotao , Li Rongjin , Chen Huipeng , Wu Jishan , Yang Fangxu , Hu Wenping 
Published: March 2022

AbstractAnomalous negative phototransistors in which the channel current decreases under light illumination hold potential to generate novel and multifunctional optoelectronic applications. Although a variety of design strategies have been developed to construct such devices, NPTs still suffer from far lower device performance compared to well‐developed positive phototransistors (PPTs). In this work, a novel 1D/2D molecular crystal p–n heterojunction, in which p‐type 1D molecular crystal (1DMC) arrays are embedded into n‐type 2D molecular crystals (2DMCs), is developed to produce ultrasensitive NPTs. The p‐type 1DMC arrays act as light‐absorbing layers to induce p‐doping of n‐type 2DMCs through charge transfer under illumination, resulting in ineffective gate control and significant negative photoresponses. As a result, the NPTs show remarkable performances in photoresponsivity (P) (1.9 × 108) and detectivity (D*) (1.7 × 1017 Jones), greatly outperforming previously reported NPTs, which are one of the highest values among all organic phototransistors. Moreover, the device exhibits intriguing characteristics undiscovered in PPTs, including precise control of the threshold voltage by controlling light signals and ultrasensitive detection of weak light. As a proof‐of‐concept, the NTPs are demonstrated as light encoders that can encrypt electrical signals by light. These findings represent a milestone for negative phototransistors, and pave the way for the development of future novel optoelectronic applications.
A Novel Methodology of Using Nonsolvent in Achieving Ultraclean Transferred Monolayer MoS2
Authors: Bhuyan C. Abinash , Madapu Kishore K. , Prabakar K. , Das Arindam , Polaki S. R. , Sinha Shyam K. , Dhara Sandip 
Published: March 2022

AbstractThe transfer of monolayer molybdenum disulfide (1L‐MoS2) onto any target substrates is inevitable for the next generation of optoelectronic devices such as flexible electronics. However, the existing post‐transfer treatments are ineffective for the complete removal of poly(methyl methacrylate) (PMMA) polymer, which is usually used as carrier polymer in the wet‐transfer method. The presence of PMMA residues seriously degrades the intrinsic properties of any 2D materials. Several new cleaning methods such as annealing, ozone cleaning, and acetone treatment adopted in this report are found to be ineffective for the complete removal of PMMA residues on the transferred 1L‐MoS2 film. A new chemical route is developed and demonstrated with a PMMA nonsolvent, ethanol, and ultraclean transferred 1L‐MoS2 is obtained after 96 h hot ethanol treatment. An interfacial diffusion model is proposed for the mechanism of PMMA removal from the 1L‐MoS2 surface. To observe the effect of cleaning process on electrical properties, 1L‐MoS2 field‐effect transistor (FET) devices are fabricated. An enhancement of 80%–85% in the electron mobility is achieved for ultraclean 1L‐MoS2. One order improvement in the FET parameters such as ON/OFF ratio and the subthreshold slope is also observed. It is believed that this novel method can also be applicable for other 2D materials.
Multifunctional Molecule‐Modified SnO2–Perovskite Interface for Efficient Planar Perovskite Solar Cells
Authors: Xin Xu , Yang Jiabao , Pu Xingyu , Li Yuke , Wang Tong , Chen Hui , Cao Qi , Zhang Yixin , Tojiboyev Ilhom , Salari Hadi , Ye Fei , Li Xuanhua 
Published: March 2022

AbstractThe electron transport layer (ETL) is one of the determinants for the performance improvement of perovskite solar cells (PSCs). Here, a multifunctional molecule named 4‐fluoro‐phenylalanine (4‐F‐Phe) to modify the surface of tin oxide (SnO2) ETL is introduced as a novel interfacial layer for high‐efficiency PSCs. The modified SnO2 ETLs exhibit an elevated Fermi level, increasing the carrier extraction and suppressing the interfacial recombination. In addition, the various functional groups of the 4‐F‐Phe realize strong interfacial interactions with both the bottom SnO2 ETLs and the top perovskite, which reduces trap state density significantly to promote the interfacial charge transport. As a result, power conversion efficiency (PCE) for the 4‐F‐Phe optimized device reaches 21.91%. Most importantly, the 4‐F‐Phe optimized device without encapsulation maintains 91% of its initial PCE after 2000 h at 25 °C with a humidity of 50 ± 5%, and 90% of the initial PCE after 1000 h at 80 °C in N2. In addition, the encapsulated devices maintain 94% of their initial efficiency under continuous 1 sun illumination for 1000 h when tracking the maximum power point at 45 °C. This work provides a new strategy of modifying ETL to simultaneously improve the efficiency and stability of PSCs.
Synergistic Pd/Cu Catalyzed Allylation of Cyclic Ketimine Esters with Vinylethylene Carbonates: Enantioselective Construction of Trisubstituted Allylic 2H‐Pyrrole Derivatives
Authors: Ke Miaolin , Yu Yuyan , Zhang Ke , Zuo Sheng , Liu Zhigang , Xiao Xiao , Chen Fener 
Published: March 2022

AbstractAn asymmetric allylation of cyclic ketimine esters with vinylethylene carbonates was accomplished through a Pd/Cu dual catalysis system under a mild condition, providing a range of trisubstituted allylic 2H‐pyrrole analogues bearing a chiral quaternary stereogenic center in high yields (up to 92% yield) and with excellent regioselectivities and enantioselectivities (up to 96% ee). A gram‐scale operation was also conducted in high efficiency without erosion of enantioselectivity and stereoselectivity.magnified image
Metal‐Free Photochemical C−Se Cross‐Coupling of Aryl Halides with Diselenides
Authors: Wang Ruizhe , Wang Xinyu , Mao Shuai , Zhao Yahao , Yuan Bo , Yang Xue‐Yan , Li Jianjun , Chen Zhengkai 
Published: March 2022

AbstractA light‐mediated C−Se bond coupling reaction of aryl halides with diselenides under mild photocatalyst‐free conditions for preparing aryl selenoethers has been achieved. The transformation is charactered by readily available materials, mild conditions, broad substrate scope and high efficiency. A reasonable mechanism has been proposed based on the preliminary mechanistic investigation. The protocol is also suitable for forging C−S bond and C−Te bond by the use of disulfides and ditellurides.magnified image
Remote Giese Radical Addition by Photocatalytic Ring Opening of Activated Cycloalkanols
Authors: Salaverri Noelia , Carli Benedetta , Gratal Patricia B. , Marzo Leyre , Alemán José 
Published: March 2022

AbstractThe application of proton coupled electron transfer (PCET) processes in organic synthesis has opened the door to new radical intermediates for synthesis such as alkyl radicals in remote positions to a ketone. Herein, we present the addition of these remote alkyl radicals to electron deficient double bonds under photoorganocatalyzed and very mild conditions. The method is not only applicable to diactivated double bonds, but monoactivated ones are also accessible using more stabilized alkyl radicals, and alkyl chains of any length can be introduced. The final products can be easily converted into more complex structures via a one‐pot process, and the activating functional groups were transformed in the more versatile methyl esters. Mechanistic investigations support a mechanistic proposal based on a PCET process.magnified image
Revealing the Sole Impact of Acceptor's Molecular Conformation to Energy Loss and Device Performance of Organic Solar Cells through Positional Isomers
Authors: Cai Guilong , Chen Zeng , Li Mengyang , Li Yuhao , Xue Peiyao , Cao Qingbin , Chi Weijie , Liu Heng , Xia Xinxin , An Qiaoshi , Tang Zheng , Zhu Haiming , Zhan Xiaowei , Lu Xinhui 
Published: March 2022

AbstractTwo new fused‐ring electron acceptor (FREA) isomers with nonlinear and linear molecular conformation, m‐BAIDIC and p‐BAIDIC, are designed and synthesized. Despite the similar light absorption range and energy levels, the two isomers exhibit distinct electron reorganization energies and molecular packing motifs, which are directly related to the molecular conformation. Compared with the nonlinear acceptor, the linear p‐BAIDIC shows more ordered molecular packing and higher crystallinity. Furthermore, p‐BAIDIC‐based devices exhibit reduced nonradiative energy loss and improved charge transport mobilities. It is beneficial to enhance the open‐circuit voltage (VOC) and short‐current current density (JSC) of the devices. Therefore, the linear FREA, p‐BAIDIC yields a relatively higher efficiency of 7.71% in the binary device with PM6, in comparison with the nonlinear m‐BAIDIC. When p‐BAIDIC is incorporated into the binary PM6/BO‐4Cl system to form a ternary system, synergistic enhancements in VOC, JSC, fill factor (FF), and ultimately a high efficiency of 17.6% are achieved.
Single‐Cell RNA‐seq Reveals a Developmental Hierarchy Super‐Imposed Over Subclonal Evolution in the Cellular Ecosystem of Prostate Cancer
Authors: Ge Guangzhe , Han Yang , Zhang Jianye , Li Xinxin , Liu Xiaodan , Gong Yanqing , Lei Zhentao , Wang Jie , Zhu Weijie , Xu Yangyang , Peng Yiji , Deng Jianhua , Zhang Bao , Li Xuesong , Zhou Liqun , He Huiying , Ci Weimin 
Published: March 2022

AbstractProstate cancer (PCa) is a complex disease. An ongoing accumulation of mutations results in increased genetic diversity, with the tumor acquiring distinct subclones. However, non‐genetic intra‐tumoral heterogeneity, the cellular differentiation state and the interplay between subclonal evolution and transcriptional heterogeneity are poorly understood. Here, the authors perform single‐cell RNA sequencing from 14 untreated PCa patients. They create an extensive cell atlas of the PCa patients and mapped developmental states onto tumor subclonal evolution. They identify distinct subclones across PCa patients and then stratify tumor cells into four transcriptional subtypes, EMT‐like (subtype 0), luminal A‐like (subtype 1), luminal B/C‐like (subtype 2), and basal‐like (subtype 3). These subtypes are hierarchically organized into stem cell‐like and differentiated status. Strikingly, multiple subclones within a single primary tumor present with distinct combinations of preferential subtypes. In addition, subclones show different communication strengths with other cell types within the tumor ecosystem, which may modulate the distinct transcriptional subtypes of the subclones. Notably, by integrating TCGA data, they discover that both tumor cell transcriptional heterogeneity and cellular ecosystem diversity correlate with features of a poor prognosis. Collectively, their study provides the analysis of subclonal and transcriptional heterogeneity and its implication for patient prognosis.
Material‐Assisted Strategies for Osteochondral Defect Repair
Authors: Lesage Constance , Lafont Marianne , Guihard Pierre , Weiss Pierre , Guicheux Jérôme , Delplace Vianney 
Published: March 2022

AbstractThe osteochondral (OC) unit plays a pivotal role in joint lubrication and in the transmission of constraints to bones during movement. The OC unit does not spontaneously heal; therefore, OC defects are considered to be one of the major risk factors for developing long‐term degenerative joint diseases such as osteoarthritis. Yet, there is currently no curative treatment for OC defects, and OC regeneration remains an unmet medical challenge. In this context, a plethora of tissue engineering strategies have been envisioned over the last two decades, such as combining cells, biological molecules, and/or biomaterials, yet with little evidence of successful clinical transfer to date. This striking observation must be put into perspective with the difficulty in comparing studies to identify overall key elements for success. This systematic review aims to provide a deeper insight into the field of material‐assisted strategies for OC regeneration, with particular considerations for the therapeutic potential of the different approaches (with or without cells or biological molecules), and current OC regeneration evaluation methods. After a brief description of the biological complexity of the OC unit, the recent literature is thoroughly analyzed, and the major pitfalls, emerging key elements, and new paths to success are identified and discussed.
3D‐Laminated Graphene with Combined Laser Irradiation and Resin Infiltration toward Designable Macrostructure and Multifunction
Authors: Gao Yan , Zhai Yujiang , Wang Guantao , Liu Fu , Duan Haibin , Ding Xilun , Luo Sida 
Published: March 2022

AbstractMacroscopic 3D graphene has become a significant topic for satisfying the continuously upgraded smart structures and devices. Compared with liquid assembling and catalytic templating methods, laser‐induced graphene (LIG) is showing facile and scalable advantages but still faces limited sizes and geometries by using template induction or on‐site lay‐up strategies. In this work, a new LIG protocol is developed for facile stacking and shaping 3D LIG macrostructures by laminating layers of LIG papers (LIGPs) with combined resin infiltration and hot pressing. Specifically, the constructed 3D LIGP composites (LIGP‐C) are compatible with large area, high thickness, and customizable flat or curved shapes. Additionally, systematic research is explored for investigating critical processing parameters on tuning its multifunctional properties. As the laminated layers are stacked from 1 to 10, it is discovered that piezoresistivity (i.e., gauge factor) of LIGP‐C dramatically reflects an ≈3900% improvement from 0.39 to 15.7 while mechanical and electrical properties maintain simultaneously at the highest levels, attributed to the formation of densely packed fusion layers. Along with excellent durability for resisting multiple harsh environments, a sensor‐array system with 5 × 5 LIGP‐C elements is finally demonstrated on fiber‐reinforced polymeric composites for accurate strain mapping.
Through‐Space Conjugated Electron Transport Materials for Improving Efficiency and Lifetime of Organic Light‐Emitting Diodes
Authors: Shen Pingchuan , Liu Hao , Zhuang Zeyan , Zeng Jiajie , Zhao Zujin , Tang Ben Zhong 
Published: March 2022

AbstractThermally stable electron transport (ET) materials with high electron mobility and high triplet state energy level are highly desired for the fabrication of efficient and stable organic light‐emitting diodes (OLEDs). Herein, a new design strategy of constructing through‐space conjugated folded configuration is proposed to explore robust ET materials, opposite to the widely used planar configuration. By bonding two quinolines to the 9,10‐positions of phenanthrene, two novel folded molecules with high thermal and morphological stabilities and high triplet state energy levels (>2.7 eV) are created. These folded molecules possess excellent ET ability with electron mobilities of three orders of magnitude higher than those of linear and planar counterparts. Theoretical calculation and crystallography analysis demonstrate the through‐space conjugated folded configuration has not only reduced reorganization energy but also enlarged charge transfer integral at various dimensions, bringing about efficient multi‐dimensional ET, independent of molecular orientation. By adopting the folded molecule as ET layers, OLEDs with no matter delayed fluorescence or phosphorescence emitters can achieve high external quantum efficiencies and long operational lifetimes simultaneously. This work paves a new avenue towards robust ET materials to improve efficiency and stability of OLEDs.
Direkte Affinitätsreinigung lang wirksamer PASylierter Proteine mit therapeutischem Anwendungspotential unter Nutzung von L‐Prolinamid zur milden Elution
Authors: Schilz Jonas , Clement Charlotte , Greiner Franziska , Skerra Arne 
Published: March 2022

AbstractSowohl unzureichende Plasma‐Halbwertszeit (Zirkulation für nur wenige Stunden oder kürzer) als auch ein aufwendiger Reinigungsprozeß können Flaschenhals sein für die biologische Wirkstoffentwicklung. Wir berichten über eine neuartige Strategie zur effizienten und schonenden Afinitätsreinigung pharmakologisch relevanter Proteine, die durch PASylierung hinsichtlich verlängerter Aktivität in vivo modifiziert wurden. Zuvor hatten wir Antikörper mit Spezifität für Pro/Ala‐reiche Sequenzen (PAS) beschrieben, die ein Spektrum an Bindungseigenschaften abdecken. Unser Ansatz hier beruht auf einer Chromatographiematrix, die mit einem niedrigaffinen PAS‐spezifischen Fab‐Fragment zum Zweck der spezifischen Adsorption des PASylierten Proteins aus einer makromolekularen Mischung funktionalisiert ist. Aufgrund vollständiger Abwesenheit hydrophober/aromatischer oder ionischer Gruppen in dem PAS‐Sequenzepitop wird die Bindung allein durch Van‐der‐Waals‐Kontakte und charakteristische Wasserstoffbrückenbindungen vermittelt. Überraschenderweise kann die selektive kompetitive Elution durch Anwendung des hochlöslichen und biologisch inaktiven Iminosäurederivats L‐Prolinamid erreicht werden. Basierend auf der spezifischen, aber hochdynamischen biomolekularen Wechselwirkung gestattet unser Verfahren die direkte Einschrittreinigung PASylierter Proteine aus einem Zellextrakt oder Kulturüberstand, wobei grobe Elutionsbedingungen, wie sie häufig für die konventionelle Affinitätschromatographie erforderlich sind, vermieden werden.
Änderungen der elektronischen Struktur einer Amino‐Photosäure entlang des Förster Zyklus
Authors: Eckert Sebastian , Winghart Marc‐Oliver , Kleine Carlo , Banerjee Ambar , Ekimova Maria , Ludwig Jan , Harich Jessica , Fondell Mattis , Mitzner Rolf , Pines Ehud , Huse Nils , Wernet Philippe , Odelius Michael , Nibbering Erik T. J. 
Published: March 2022

AbstractPhotosäuren sind Moleküle, die einen starken Anstieg ihrer Acidität im ersten elektronisch angeregten Zustand aufweisen. Diese Eigenschaft ermöglicht Echtzeitstudien des Protonentransfers in Säure‐Base‐Reaktionen, des Protonentransports in Energiespeichern und biomolekularen Sensorproteinsystemen. Erklärungsansätze für die Ursachen der Photoacidität reichen von Variationen der freien Solvatationsenergie bis hin zu Veränderungen der elektronischen Struktur während der vier Phasen des Förster‐Zyklus. Wir berichten hier Veränderungen der elektronischen Struktur der Protonen‐Donor Gruppe in einer protonierten aromatischen Amino‐Photosäure in Lösung bei Photoanregung und anschließender Protonentransferdynamik mit Hilfe von Pikosekunden‐Stickstoff‐K‐Kanten‐Spektroskopie. Anhand der Orbitalspezifität von Rumpf‐Valenz‐Übergängen an der funktionellen Aminogruppe weisen wir deutlich ausgeprägte Veränderungen der elektronischen Struktur, des Dipolmoments und der Energiezustände auf der Seite der konjugierten Photobase nach. Diese Ergebnisse bilden die Grundlage für eine zukünftige detaillierte Charakterisierung des Phänomens der Photoacidität im Lichte der elektronischen Struktur.
In Situ Spectroscopic Characterization and Theoretical Calculations Identify Partially Reduced ZnO1−x/Cu Interfaces for Methanol Synthesis from CO2
Authors: Liu Xinyu , Luo Jie , Wang Hengwei , Huang Li , Wang Shasha , Li Shang , Sun Zhihu , Sun Fanfei , Jiang Zheng , Wei Shiqiang , Li Wei‐Xue , Lu Junling 
Published: March 2022

AbstractThe active site of the industrial Cu/ZnO/Al2O3 catalyst used in CO2 hydrogenation to methanol has been debated for decades. Grand challenges remain in the characterization of structure, composition, and chemical state, both microscopically and spectroscopically, and complete theoretical calculations are limited when it comes to describing the intrinsic activity of the catalyst over the diverse range of structures that emerge under realistic conditions. Here a series of inverse model catalysts of ZnO on copper hydroxide were prepared where the size of ZnO was precisely tuned from atomically dispersed species to nanoparticles using atomic layer deposition. ZnO decoration boosted methanol formation to a rate of 877 gMeOH kgcat−1 h−1 with ≈80 % selectivity at 493 K. High pressure in situ X‐ray absorption spectroscopy demonstrated that the atomically dispersed ZnO species are prone to aggregate at oxygen‐deficient ZnO ensembles instead of forming CuZn metal alloys. By modeling various potential active structures, density functional theory calculations and microkinetic simulations revealed that ZnO/Cu interfaces with oxygen vacancies, rather than stoichiometric interfaces, Cu and CuZn alloys were essential to catalytic activation.
Nitrate‐to‐Ammonia Conversion at an InSn‐Enriched Liquid‐Metal Electrode
Authors: Crawford Jessica , Yin Hanqing , Du Aijun , O'Mullane Anthony P. 
Published: March 2022

AbstractThe renewable energy driven electrochemical conversion of nitrates to ammonia is emerging as a viable route for the creation of this hydrogen carrier. However, the creation of highly efficient electrocatalysts that show prolonged stability is an ongoing challenge. Here we show that room temperature liquid metal Galinstan can be used as an efficient and stable electrocatalyst for nitrate conversion to ammonia achieving rates of up to 2335 μg h−1 cm−2 with a Faradaic efficiency of 100 %. Density functional theory (DFT) calculations and experimental observation indicated the activity is due to InSn alloy enrichment within the liquid metal that occurs during the electrocatalytic reaction. This high selectivity for NH3 is also due to additional suppression of the competing hydrogen evolution reaction at the identified In3Sn active site. This work adds to the increasing applicability of liquid metals based on Ga for clean energy technologies.