bluuebunny/crossref_metadata_2025_split huggingface dataset:
High‐Performing Acid‐Free PEDOT:PSS‐Based Organic Photodiodes for Cardiovascular Disease Diagnosis
Authors: Yang Zhao , Kim Byung Gi , Jang Woongsik , Park Jong Hyeok , Wang Dong Hwan 
Published: October 2023

AbstractPhotodetectors made from low‐toxicity organic materials are considered a promising alternative to conventional inorganic photodetectors. However, the performance of current organic photodetectors (OPD) needs to be further enhanced. This study aims to introduce acid‐free poly(3,4‐ethylenedioxythiophene)‐(polystyrene sulfonate) (PEDOT‐(PSS)) films in order to improve the performance of OPDs in practical applications. Utilization of heterocyclic 1,3‐diazole (HDZ) in PEDOT‐(PSS) improves the polymerization degree, carrier mobility, and other physicochemical properties. These enhanced properties also improve the comprehensive performance of OPD. In this flow, the enhanced noise suppression is also confirmed by elucidating the device's performance limitations. Consequently, the presented OPD‐based photoplethysmography sensor has the ability to diagnose blood circulation status and cardiovascular diseases. This accomplishment marks the first in single pixel‐based organic photodiode research.
Graphdiyne as an Electron Modifier for Boosting Electrochemical Production of Adipic Acid
Authors: Liu Fulai , Gao Xutao , Shi Rui , Xiong Jinfan , Guo Zhengxiao , Tse Edmund C. M. , Chen Yong 
Published: October 2023

AbstractAdipic acid (AA) is a crucial feedstock for nylon polymers, and is industrially produced by thermal oxidation of cyclohexanone/cyclohexanol mixture (KA oil). However, this process consumes large quantities of corrosive nitric acid as oxidants, while emits ozone‐depleting greenhouse gas N2O. Here, an electrocatalytic strategy for selective oxidation of KA oil to AA coupled with H2 evolution over a Co3O4/graphdiyne cooperative catalyst (Co3O4/GDY) is reported. The Co3O4/GDY displays high electrooxidation activity of KA oil to AA (100 mA cm−2 at ≈1.5 V vs RHE), outperforming all the reported findings. Detailed ex situ and in situ experimental studies, theoretical calculations, and molecular dynamic simulations reveal that GDY not only facilitates the enrichment of cyclohexanone on the catalyst surface in aqueous medium, but also upshifts the d‐band center of Co sites, strengthening the adsorption/activation of cyclohexanone. This study offers a green route for AA synthesis and proposes a GDY interface engineering strategy for efficient electrooxidation.
PCTS‐Controlled Synthesis of L10/L12‐Typed Pt‐Mn Intermetallics for Electrocatalytic Oxygen Reduction
Authors: Yan Wei , Wang Xuan , Liu Manman , Ma Kaiyue , Wang Liqi , Liu Qicheng , Wang Caikang , Jiang Xian , Li Hao , Tang Yawen , Fu Gengtao 
Published: October 2023

AbstractPt‐based intermetallics are recognized as effective catalysts for oxygen reduction reaction (ORR) in fuel cells. However, the synthesis of intermetallics often requires prolonged annealing and the effect of different crystal structures on ORR still need to be investigated. Herein, L12‐Pt3Mn and L10‐PtMn intermetallics with Pt‐skin are rapidly synthesized through an emerging periodic carbothermal shock method to investigate their ORR‐activity difference. The formation of L12‐Pt3Mn and L10‐PtMn can be well‐controlled by the Pt/Mn feeding ratio, pulse cycles, and temperature. Electrocatalytic investigations show that L12‐Pt3Mn presents a more positive half‐wave potential (0.91 V vs RHE) and onset potential (1.02 V vs RHE) than those of L10‐PtMn. The mass activity and specific activity of L12‐Pt3Mn are respectively fourfold and threefold greater than those of L10‐PtMn. Theoretical calculations indicate that the L12‐Pt3Mn has a more substantial work function than L10‐PtMn, thereby conferring L12‐Pt3Mn with an increased electron density allocation for catalytic involvement. This electron confinement imparts L12‐Pt3Mn with a Pt d‐band center lower than that of L10‐PtMn, consequently attenuating the adsorption of strongly bonded *O intermediates during the rate‐determining step. This study not only employs a straightforward method for intermetallic preparation but also elucidates the discrepancies in ORR activity across intermetallics with distinct structures.
Thiomolybdate Clusters: From Homogeneous Catalysis to Heterogenization and Active Sites
Authors: Batool Samar , Langer Marcel , Myakala Stephen Nagaraju , Heiland Magdalena , Eder Dominik , Streb Carsten , Cherevan Alexey 
Published: October 2023

AbstractThiomolybdates are molecular molybdenum‐sulfide clusters formed from Mo centers and sulfur‐based ligands. For decades, they have attracted the interest of synthetic chemists due to their unique structures and their relevance in biological systems, e.g., as reactive sites in enzymes. More recently, thiomolybdates are explored from the catalytic point of view and applied as homogeneous and molecular mimics of heterogeneous molybdenum sulfide catalysts. This review summarizes prominent examples of thiomolybdate‐based electro‐ and photocatalysis and provides a comprehensive analysis of their reactivities under homogeneous and heterogenized conditions. Active sites of thiomolybdates relevant for the hydrogen evolution reaction are examined, aiming to shed light on the link between cluster structure and performance. The shift from solution‐phase to surface‐supported thiomolybdates is discussed with a focus on applications in electrocatalysis and photocatalysis. The outlook highlights current trends and emerging areas of thiomolybdate research, ending with a summary of challenges and key takeaway messages based on the state‐of‐the‐art research.
Pseudopolymorphic Phase Engineering for Improved Thermoelectric Performance in Copper Sulfides
Authors: Yang Tian‐Yu , Gu Shi‐Wei , Zhang Yi‐Xin , Zheng Fengshan , Kong Deli , Dunin‐Borkowski Rafal E. , Wu Di , Ge Zhen‐Hua , Feng Jing , Jin Lei 
Published: October 2023

AbstractPolymorphism (and its extended form – pseudopolymorphism) in solids is ubiquitous in mineralogy, crystallography, chemistry/biochemistry, materials science, and the pharmaceutical industries. Despite the difficulty of controlling (pseudo‐)polymorphism, the realization of specific (pseudo‐)polymorphic phases and associated boundary structures is an efficient route to enhance material performance for energy conversion and electromechanical applications. Here, this work applies the pseudopolymorphic phase (PP) concept to a thermoelectric copper sulfide, Cu2‐xS (x ≤ 0.25), via CuBr2 doping. A peak ZT value of 1.25 is obtained at 773 K in Cu1.8S + 3 wt% CuBr2, which is 2.3 times higher than that of a pristine Cu1.8S sample. Atomic‐resolution scanning transmission electron microscopy confirms the transformation of pristine Cu1.8S low digenite into PP‐engineered high digenite, as well as the formation of (semi‐)coherent interfaces between different PPs, which is expected to enhance phonon scattering. The results demonstrate that PP engineering is an effective approach for achieving improved thermoelectric performance in Cu‐S compounds. It is also expected to be useful in other materials.
Enhanced CO2 Electrolysis Through Mn Substitution Coupled with Ni Exsolution in Lanthanum Calcium Titanate Electrodes
Authors: Zhang Nuoxi , Naden Aaron , Zhang Lihong , Yang Xiaoxia , Connor Paul , Irvine John 
Published: October 2023

AbstractIn this study, perovskite oxides La0.3Ca0.6Ni0.05MnxTi0.95−xO3−γ (x = 0, 0.05, 0.10) are investigated as potential solid oxide electrolysis cell cathode materials. The catalytic activity of these cathodes toward CO2 reduction reaction is significantly enhanced through the exsolution of highly active Ni nanoparticles, driven by applying a current of 1.2 A in 97% CO2 – 3% H2O. The performance of La0.3Ca0.6Ni0.05Ti0.95O3−γ is notably improved by co‐doping with Mn. Mn dopants enhance the reducibility of Ni, a crucial factor in promoting the in situ exsolution of metallic nanocatalysts in perovskite (ABO3) structures. This improvement is attributed to Mn dopants enabling more flexible coordination, resulting in higher oxygen vacancy concentration, and facilitating oxygen ion migration. Consequently, a higher density of Ni nanoparticles is formed. These oxygen vacancies also improve the adsorption, desorption, and dissociation of CO2 molecules. The dual doping strategy provides enhanced performance without degradation observed after 133 h of high‐temperature operation, suggesting a reliable cathode material for CO2 electrolysis.
Molecular Masking of Synthetic Immunomodulator Evokes Antitumor Immunity With Reduced Immune Tolerance and Systemic Toxicity by Temporal Activity Recovery and Sustained Stimulation
Authors: Shin Hong Sik , Kim Sohyun , Jin Seung Mo , Yoo Yeon Jeong , Heo Jang Hun , Lim Yong Taik 
Published: October 2023

AbstractActivation of the innate immune system counteracts tumor‐induced immunosuppression. Hence, small molecule‐based toll‐like receptor 7/8 agonists (TLR7/8a), which can modulate immunosuppression in the tumor microenvironment along with the activation of innate immunity, are emerging as essential components of cancer immunotherapy. However, the clinical application of synthetic TLR7/8a therapies is limited by systemic immune‐associated toxicity and immune tolerance induced by uncontrolled stimulatory activities and repeated treatments. To address these limitations, a dynamic immunomodulation strategy incorporating masking and temporal recovery of the activity of TLR7/8a through prodrug‐like TLR7/8a (pro‐TLR7/8a) at the molecular level and a sustained and controlled release of active TLR7/8a from nanoliposome (pro‐TLR7/8a) (NL(pro‐TLR7/8)) in a macroscale depot are designed. Immunization with cationic NL(pro‐TLR7/8) and anionic antigens triggers robust activation of innate immune cells as well as antigen‐specific T cell responses, eliciting reprogramming of immunosuppressive cells into tumor‐suppressive cells, with decreased systemic adverse effects and immune tolerance. Combination treatment with NL(pro‐TLR7/8a) and immune checkpoint inhibitors (anti‐CTLA‐4 plus anti‐PD‐L1) or nanoliposomes (Doxorubicin) has synergistic effects on antitumor immunity in various tumor models. The concept of pro‐TLR7/8a suggested herein may facilitate the advancement of small‐molecule‐based immunomodulators for clinical translation and safe and effective cancer immunotherapy.
Polymer‐Entangled Spontaneous Pseudo‐Planar Heterojunction for Constructing Efficient Flexible Organic Solar Cells
Authors: Zhang Jiayou , Mao Houdong , Zhou Kangkang , Zhang Lifu , Luo Dou , Wang Pei , Ye Long , Chen Yiwang 
Published: October 2023

AbstractFlexible organic solar cells (FOSCs) have attracted considerable attention from researchers as promising portable power sources for wearable electronic devices. However, insufficient power conversion efficiency (PCE), intrinsic stretchability, and mechanical stability of FOSCs remain severe obstacles to their application. Herein, an entangled strategy is proposed for the synergistic optimization of PCE and mechanical properties of FOSCs through green sequential printing combined with polymer‐induced spontaneous gradient heterojunction phase separation morphology. Impressively, the toughened‐pseudo‐planar heterojunction (Toughened‐PPHJ) film exhibits excellent tensile properties with a crack onset strain (COS) of 11.0%, twice that of the reference bulk heterojunction (BHJ) film (5.5%), which is among the highest values reported for the state‐of‐the‐art polymer/small molecule‐based systems. Finite element simulation of stress distribution during film bending confirms that Toughened‐PPHJ film can release residual stress well. Therefore, this optimal device shows a high PCE (18.16%) with enhanced (short‐circuit current density) JSC and suppressed energy loss, which is a significant improvement over the conventional BHJ device (16.99%). Finally, the 1 cm2 flexible Toughened‐PPHJ device retains more than 92% of its initial PCE (13.3%) after 1000 bending cycles. This work provides a feasible guiding idea for future flexible portable power supplies.
Optical Read‐Out of the Electrical Switching of Cobalt‐Terpyridine‐BODIPY Molecules Immobilized as Single Layer on ITO
Authors: Magra Kévin , Audibert Jean‐Frédéric , Dragoe Diana , Mallah Talal , Miomandre Fabien , Boillot Marie‐Laure 
Published: October 2023

AbstractA single layer of a dyad made of a cobalt(II) bis‐terpyridine complex functionalized with a Boron‐dipyrromethene (BODIPY) fluorophore on transparent Indium Tin Oxide (ITO) electrode is prepared. A modulation of the photoluminescence intensity of the fluorophore upon the application of an electric stimulus on the ITO electrode that supports 10 picomoles of molecules is demonstrated. The intensity of the fluorescence intensity decreases when the cobalt is at the oxidation state +III, due to CoIII oxidative quenching of BODIPY emission that has a higher driving force than the CoII reductive quenching initially responsible for the low fluorescence intensity of the chemisorbed dyad.
Improving Performance of Organic Photodetectors by Using TCNQ Doped Copper Thiocyanate as the Anode Interfacial Layer
Authors: Luo Xuanang , Huang Zhenqiang , Zhong Zhiming , Quan Huilei , Peng Feng , An Kang , Li Ning , Ying Lei 
Published: October 2023

AbstractThe responsivity and specific detectivity are critical figures of merits for organic photodetectors; however, it remains challenging to simultaneously enhance two such parameters, since enhancing external quantum efficiency corresponding to responsivities will inevitably increase leakage current and noises, resulting in decreased specific detectivity. To address such a trade‐off, an effective anode interfacial layer of 7,7,8,8‐tetracyanoquinodimethane (TCNQ) doped copper thiocyanate (CuSCN) is developed herein, which can enhance shunt resistance, increase depletion width, enhance hole extraction efficiency, as well as reduce trap density of states of organic photodetectors. The organic photodetectors based on doped CuSCN present a very low dark current density of 4.4 × 10−11 A cm−2 and an impressively high specific detectivity of 1.1 × 1014 Jones. As evidenced by X‐ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy measurements, the energy levels of the doped CuSCN:TCNQ film are deepened, associated with the occurrence of dopant bonding and charge transfer. In addition, it is found that increasing the delay time can suppress the hysteresis effects of current density–voltage characteristics of organic photodetectors and make the minimum dark current density obtainable at 0 V. These findings demonstrate the great potential of using molecular doping to adjust the anode interfacial layer for developing high‐performance organic photodetectors.
Low rates of sugarcane bagasse‐derived biochar have limited effects on soil properties and sugarcane crop yield
Authors: White Paul M. , Ellsworth Patrick Z. , Lima Isabel 
Published: October 2023

AbstractSugarcane (Saccharumspp.) represents the most valuable row crop in Louisiana. High levels of biomass production and extensive tillage have degraded portions of the state's alluvial soils used to grow sugarcane. In addition to sucrose, processing the crop generates excess bagasse each year, which can represent a disposal problem for sugar factories. However, converting the bagasse to biochar at nearby pyrolysis facilities may prove to be an economical means of improving degraded soils. The objective was to determine the impacts of low rates of biochar (<3.2 mt ha−1) on soil physical, chemical, and biological properties. Plant available nutrient levels were marginally impacted by biochar additions as the biochar exhibited a relatively low surface area and neutral pH. Bagasse‐derived biochar did not affect soil nitrate retention or leaching, and overall recovery was >86%. Biochar did not increase soil CO2evolution, indicating its stability as a soil carbon amendment. However, adding biochar with mineral nitrogen decreased CO2evolution, compared to biochar alone, indicating a negative priming effect. Soil moisture retention was minimally impacted by biochar. Cane yield, sucrose content, and sucrose yield were not statistically affected by applying biochar with or without starter fertilizer at planting. Overall, the results indicate that lower levels of bagasse‐derived biochar minimally impacted soil properties and crop yield; however, the biochar was stable in soil and may find utility as a carbon‐rich amendment should carbon credits prove to be an additional source of grower or land‐owner revenue.
Synthesis of Heptagon‐Containing Polyarenes by Catalytic C−H Activation
Authors: Yamada Keigo E. , Stepek Iain A. , Matsuoka Wataru , Ito Hideto , Itami Kenichiro 
Published: October 2023

AbstractNanocarbons incorporating non‐hexagonal aromatic rings ‐ such as five‐, seven‐, and eight‐membered rings ‐ have various intriguing physical properties such as curved structures, unique one‐dimensional packing, and promising magnetic, optical, and conductivity properties. Herein, we report an efficient synthetic approach to polycyclic aromatics containing seven‐membered rings via a palladium‐catalyzed intramolecular Ar−H/Ar−Br coupling. In addition to all‐hydrocarbon scaffolds, heteroatom‐embedded heptagon‐containing polyarenes can be efficiently constructed with this method. Rhodium‐ and palladium‐catalyzed sequential six‐ and seven‐membered ring formations also afford complex heptagon‐containing molecular nanocarbons from readily available arylacetylenes and biphenyl boronic acids. Detailed mechanistic analysis by DFT calculations showed the feasibility of seven‐membered ring formation by a concerted metalation‐deprotonation mechanism. This reaction can serve as a template for the synthesis of a wide range of seven‐membered ring‐containing molecular nanocarbons.
Neutral and Anionic Square Planar Palladium(0) Complexes Stabilized by a Silicon Z‐Type Ligand
Authors: Ansmann Nils , Münch Joshua , Schorpp Marcel , Greb Lutz 
Published: October 2023

AbstractAnionic [Pd(0)−X]− ate complex were proposed as key intermediates in Pd‐catalyzed cross‐coupling for decades, but their isolation remained elusive. Herein, a chelating Lewis acidic bis(amidophenolato)silane is introduced as a strong Z‐type ligand which enables the characterization of the first anionic [Pd(0)−X]− ate complex. Intriguingly, these compounds and the neutral L−Pd(0) analogs exhibit a square planar coordination that is highly unusual for a d10 metal. Theoretical methods scrutinize the interaction between the Lewis acidic Si(IV) center and the late transition metal, while reactivity studies shed light on the potential role of anionic additives in oxidative addition reactions.
Non‐Interacting Ni and Fe Dual‐Atom Pair Sites in N‐Doped Carbon Catalysts for Efficient Concentrating Solar‐Driven Photothermal CO2 Reduction
Authors: Mo Shengpeng , Zhao Xinya , Li Shuangde , Huang Lili , Zhao Xin , Ren Quanming , Zhang Mingyuan , Peng Ruosi , Zhang Yanan , Zhou Xiaobin , Fan Yinming , Xie Qinglin , Guo Yanbing , Ye Daiqi , Chen Yunfa 
Published: October 2023

AbstractSolar‐to‐chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO2 reduction. Herein, a new concentrated solar‐driven photothermal system coupling a dual‐metal single‐atom catalyst (DSAC) with adjacent Ni−N4 and Fe−N4 pair sites is designed for boosting gas‐solid CO2 reduction with H2O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)−N−C DSAC exhibits a superior photothermal catalytic performance for CO2 reduction to CO (86.16 μmol g−1 h−1), CH4 (135.35 μmol g−1 h−1) and CH3OH (59.81 μmol g−1 h−1), which are equivalent to 1.70‐fold, 1.27‐fold and 1.23‐fold higher than those of the Fe−N−C catalyst, respectively. Based on theoretical simulations, the Fermi level and d‐band center of Fe atom is efficiently regulated in non‐interacting Ni and Fe dual‐atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)−N−C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni−N−N−Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO3 dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO3 pathways) for solar‐driven photothermal CO2 reduction to initial CO production.
Photoenzymatic Enantioselective Synthesis of Oxygen‐Containing Benzo‐Fused Heterocycles
Authors: Zhu Changtong , Yuan Zhenbo , Deng Zhiwei , Yin Dejing , Zhang Yan , Zhou Jingwen , Rao Yijian 
Published: October 2023

AbstractNew‐to‐nature biocatalysis in organic synthesis has recently emerged as a green and powerful strategy for the preparation of valuable chiral products, among which chiral oxygen‐containing benzo‐fused heterocycles are important structural motifs in pharmaceutical industry. However, the asymmetric synthesis of these compounds through radical‐mediated methods is challenging. Herein, a novel asymmetric radical‐mediated photoenzymatic synthesis strategy is developed to realize the efficient enantioselective synthesis of oxygen‐containing benzo‐fused heterocycles through structure‐guided engineering of a flavin‐dependent ‘ene’‐reductase GluER. It shows that variant GluER‐W100H could efficiently produce various benzoxepinones, chromanone and indanone with different benzo‐fused rings in high yields with great stereoselectivities under visible light. Moreover, these results are well supported by mechanistic experiments, revealing that this photoenzymatic process involves electron donor‐acceptor complex formation, single electron transfer and hydrogen atom transfer. Therefore, we provide an alternative green approach for efficient chemoenzymatic synthesis of important chiral skeletons of bioactive pharmaceuticals.
High‐Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All‐Solid‐State Batteries
Authors: Li Shenghao , Lin Jing , Schaller Mareen , Indris Sylvio , Zhang Xin , Brezesinski Torsten , Nan Ce‐Wen , Wang Shuo , Strauss Florian 
Published: October 2023

AbstractSuperionic solid electrolytes (SEs) are essential for bulk‐type solid‐state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge‐transport properties, however a thorough understanding of how configurational entropy (ΔSconf) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen‐rich lithium argyrodites with the general formula Li5.5PS4.5ClxBr1.5‐x (0≤x≤1.5). Using neutron powder diffraction and 31P magic‐angle spinning nuclear magnetic resonance spectroscopy, the S2−/Cl−/Br− occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li‐ion dynamics, leading to a room‐temperature ionic conductivity of 22.7 mS cm−1 (9.6 mS cm−1 in cold‐pressed state) for Li5.5PS4.5Cl0.8Br0.7 (ΔSconf=1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li5.5PS4.5Cl0.8Br0.7 SE allowed for stable cycling of single‐crystal LiNi0.9Co0.06Mn0.04O2 (s‐NCM90) composite cathodes in SSB cells, emphasizing that dual‐substituted lithium argyrodites hold great promise in enabling high‐performance electrochemical energy storage.