bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bifidobacterium pseudolongum‐Derived Bile Acid from Dietary Carvacrol and Thymol Supplementation Attenuates Colitis via cGMP‐PKG‐mTORC1 Pathway
Authors: Zhang Ke , Xu Yangbin , Zheng Yining , Zhang Ting , Wu Yujiang , Yan Yiting , Lei Yu , Cao Xi , Wang Xiaolong , Yan Frances , Lei Zhaomin , Brugger Daniel , Chen Yulin , Deng Lu , Yang Yuxin 
Published: September 2024

AbstractCarvacrol and thymol (CAT) have been widely recognized for their antimicrobial and anti‐inflammatory properties, yet their specific effects on colitis and the mechanisms involved remain insufficiently understood. This study establishes a causative link between CAT administration and colitis mitigation, primarily through the enhancement of Bifidobacterium pseudolongum abundance in the colon. This increase promotes the production of secondary bile acids, particularly hyodeoxycholic acid (HDCA) and 12‐ketodeoxycholic acid (12‐KCAC), which exert anti‐inflammatory effects. Notably, CAT does not alleviate colitis symptoms in germ‐free mice, indicating the necessity of gut microbiota. This research uncovers a novel regulatory mechanism where HDCA and 12‐KCAC inhibit colonic inflammation by reducing the expression of transmembrane guanylate cyclase 1A in the colonic epithelium. This downregulation elevates intracellular Ca2+ and cGMP levels, activating protein kinase G (PKG). Activated PKG subsequently suppresses the mTOR signaling pathway, thereby ameliorating dextran sulfate sodium (DSS)‐induced colonic damage. These findings highlight potential metabolites and therapeutic targets for preventing and treating colitis. Bifidobacterium pseudolongum, HDCA, and 12‐KCAC emerge as promising candidates for therapeutic interventions in colitis and related disorders characterized by impaired tight junction function.
Operando Decoding Ion‐Conductive Switch in Stimuli‐Responsive Hydrogel by Nanodiamond‐Based Quantum Sensing
Authors: Dou Ruqiang , Li Zan , Zhu Guoli , Lin Chao , Liu Frank X. , Wang Biao 
Published: September 2024

AbstractThermal‐responsive hydrogels are developed as ion‐conductive switchs for energy storage devices, however, the molecule mechanism of switch on/off remains unclear. Here, poly(N‐isopropylacrylamide‐co‐acrylamide) hydrogel is synthesized as a model material and nanodiamond (ND) based quantum sensing for phase change study is developed. First, micro‐scale phase separation with cross‐linked mesh structure after sol‐gel transition is visualized in situ and water molecules are trapped by polymer chains and on a chemically “frozen” state. Then, the nano‐scale inhomogeneous distributions of viscosity, thermal conductivity and ionic mobility in hydrogel at high temperature are observed by measuring the rotation, translation and zero‐field splitting of NDs. Besides, the ionic mobility of hydrogel is found to be dependent not only on temperature but also on polymer concentration. These observations suggested that the physical “wall” induced by inhomogeneous phase separation at microscopic scale blocked the ion conduction pathways, providing a potential intrinsic explanation for ion migration shut‐down of ionic hydrogels at high temperature.
Advances and Applications of Oxidized van der Waals Transition Metal Dichalcogenides
Authors: Kim Brian S. Y. , Ngo Tien Dat , Hassan Yasir , Chae Sang Hoon , Yoon Soon‐Gil , Choi Min Sup 
Published: September 2024

AbstractThe surface oxidation of 2D transition metal dichalcogenides (TMDs) has recently gained tremendous technological and fundamental interest owing to the multi‐functional properties that the surface oxidized layer opens up. In particular, when integrated into other 2D materials in the form of van der Waals heterostructures, oxidized TMDs enable designer properties, including novel electronic states, engineered light‐matter interactions, and exceptional‐point singularities, among many others. Here, the evolving landscapes of the state‐of‐the‐art surface engineering technologies that enable controlled oxidation of TMDs down to the monolayer‐by‐monolayer limit are reviewed. Next, the use of oxidized TMDs in van der Waals heterostructures for different electronic and photonic device platforms, materials growth processes, engineering concepts, and synthesizing new condensed matter phenomena is discussed. Finally, challenges and outlook for future impact of oxidized TMDs in driving rapid advancements across various application fronts is discussed.
Thermosensitive Hydrogel with Programmable, Self‐Regulated HIF‐1α Stabilizer Release for Myocardial Infarction Treatment
Authors: Deng Kaicheng , Hua Yuyan , Gao Ying , Zheng Houwei , Jiang Yangzi , Wang Yaping , Gao Changyou , Ren Tanchen , Zhu Yang 
Published: September 2024

AbstractHIF‐1α (hypoxia induced factor‐1α), a vital protective signal against hypoxia, has a short lifetime after myocardial infarction (MI). Increasing HIF‐1α stability by inhibiting its hydroxylation with prolyl hydroxylases inhibitors such as DPCA (1,4‐dihydrophenonthrolin‐4‐one‐3‐carboxylic acid) presents positive results. However, the optimal inhibitor administration profile for MI treatment is still unexplored. Here, injectable, thermosensitive hydrogels with programmable DPCA release are designed and synthesized. Hydrogel degradation and slow DPCA release are coupled to form a feedback loop by attaching pendant DPCA to polymer backbone, which serve as additional crosslinking points through π–π and hydrophobic interactions. Pendant carboxyl groups are added to the copolymer to accelerate DPCA release. Burst release in the acute phase for myocardial protection and extended near zero‐order release across the inflammatory and fibrotic phases with different rates are achieved. All DPCA‐releasing hydrogels upregulate HIF‐1α, decrease apoptosis, promote angiogenesis, and stimulate cardiomyocyte proliferation, leading to preserved cardiac function and ventricular geometry. Faster hydrogel degradation induced by faster DPCA release results in a HIF‐1α expression eight times of healthy control and better therapeutic effect in MI treatment. This research demonstrates the value of precise regulation of HIF‐1α expression in treating MI and other relevant diseases and provides an implantable device‐based modulation strategy.
Scaling Behavior in the Spectral and Power Density Dependent Photovoltaic Response of Hot Polaronic Heterojunctions
Authors: Kressdorf Birte , Hoffmann Jörg , Dehning Annika , Blöchl Peter E. , Seibt Michael , Jooss Christian 
Published: September 2024

AbstractStrongly correlated manganites can be considered as model systems for the study of photovoltaic harvesting of hot polarons that can be excited from the electronically ordered ground state. In order to gain basic understanding of hot polaron harvesting, the deviations of the photovoltaic response of a heterojunction with polaronic absorber from a conventional semiconductor are analyzed. Specifically, the spectral and photon power density dependence of the open circuit voltage Uoc and the short circuit current density Jsc in heterojunctions consisting of orbital ordered Pr1‐xCaxMnO3 (x = 0.1, PCMO) thin films epitaxially grown on single crystalline (100) SrTiO3 (STO) and Nb‐doped (100) SrTiO3 (STNO) substrates are investigated. The observed behavior is fundamentally different from conventional solar cells, in which Uoc is limited by fast carrier relaxation to the band edges. Whereas the spectral and photon power dependence of Uoc of conventional semiconductor junctions is well described by the Shockley‐Queisser (SQ) theory, the hot polaron junctions surprisingly show a scaling law behavior of Uoc. Such scaling laws otherwise apply to equilibrium order parameters in second‐order phase transitions. It is concluded that its physical origin is the unique dependence of the quasi‐Fermi level splitting on temperature, photon energy, and power density in a hot polaron system.
Intensity‐Modulated Photocurrent and Photovoltage Spectroscopy for Characterizing Charge Dynamics in Solar Cells
Authors: Wang Yanlong , Zheng Haofeng , Xiao Jin , Liu Yanan , Liu Qi , Ma Xuyu , Hu Jing , Zou Dechun , Hou Shaocong 
Published: September 2024

AbstractIntensity‐modulated photocurrent and photovoltage spectroscopy (IMPS/IMVS) are powerful tools in optoelectronics such as photoelectrochemistry and photovoltaics, as they demonstrate distinct charge dynamic processes at different frequencies. Unlike the material characterization techniques, IMPS/IMVS offer an approach for investigating the dynamic behavior of charge carriers and ions from the device perspective. This review examines IMPS/IMVS from both theories and experiments to understand the intricate charge dynamics in solar cells with various materials and structures. To accommodate different types of cells, four primary theoretical models including the rate constant model, drift‐diffusion model, equivalent circuit model, and distribution of relaxation times, are evaluated in detail. In the future, the incorporation of IMPS/IMVS with other time‐domain and frequency‐domain methods, along with imaging techniques, can significantly facilitate the characterization of charge dynamics with enhanced convenience, spatial dimensions, and accuracy.
Anti‐Swelling Supramolecule‐Crosslinked Hydrogel Interphase for Stable Zn Metal Anodes
Authors: Luo Xuan , Nian Qingshun , Dong Qi , Ruan Digen , Cui Zhuangzhuang , Wang Zihong , Xiong Bing‐Qing , Ren Xiaodi 
Published: September 2024

AbstractAqueous Zn metal batteries show promise for large‐scale energy storage but face challenges including dendrite formation, volume changes, and side reactions. This study introduces a novel anti‐swelling supramolecule‐crosslinked hydrogel (SCH) interphase to stabilize Zn metal anodes. The SCH, composed of cyclodextrin molecules crosslinked with polyvinyl alcohol, offers a multifaceted approach to enhance anode stability. It homogenizes ion flux and suppresses Zn dendrite growth by creating well‐defined pathways for Zn2+ movement. The supramolecular structure selectively traps SO42− ions, effectively desolvating Zn2+ and enabling fast ion transportation. Additionally, by disrupting water cluster hydrogen bonds, SCH reduces free water activity, mitigating corrosion at the Zn surface. Electrochemical tests demonstrate the excellent performance of SCH‐Zn, with symmetric cells achieve lifespans of 1800 h at 4 mA cm−2/2 mAh cm−2 and 1100 h at 10 mA cm−2/5 mAh cm−2. Zn||Cu half‐cells maintain 99.7% Coulombic efficiency over 500 cycles, while full cells with polyaniline cathodes exhibit stable cycling for 1500 cycles at 5 A g−1 with no apparent capacity decay. These results highlight the effectiveness of the SCH in stabilizing Zn anodes. This study provides a new interfacial engineering strategy for high‐performance aqueous Zn batteries, potentially accelerating their practical implementation in large‐scale energy storage.
Room‐Temperature Single‐Molecule Infrared Imaging and Spectroscopy through Bond‐Selective Fluorescence
Authors: Wang Haomin , Kocheril Philip A. , Yang Ziguang , Lee Dongkwan , Naji Noor , Du Jiajun , Lin Li‐En , Wei Lu 
Published: September 2024

AbstractInfrared (IR) spectroscopy stands as a workhorse for exploring bond vibrations, offering a wealth of chemical insights across diverse frontiers. With increasing focus on the regime of single molecules, obtaining IR‐sensitive information from individual molecules at room temperature would provide essential information about unknown molecular properties. Here, we leverage bond‐selective fluorescence microscopy, facilitated by narrowband picosecond mid‐IR and near‐IR double‐resonance excitation, for high‐throughput mid‐IR structural probing of single molecules. We robustly capture single‐molecule images and analyze the combined polarization dependence, vibrational peaks, linewidths, and lifetimes of probe molecules with representative scaffolds. From bulk to single molecules, we find that vibrational lifetimes remain consistent, while linewidths are narrowed by approximately twofold and anisotropy becomes more pronounced. Additionally, unexpected peak shifts from single molecules were observed, attributed to the generation of new modes due to previously unexplored dimerization, supported by quantum chemistry calculations. These findings underscore the importance of infrared analysis on individual single molecules in ambient environments, offering molecular information crucial for functional imaging and the investigation of the fundamental properties and utilities of luminescent molecules.
Small‐Molecule Mixed Ionic‐Electronic Conductors for Efficient N‐Type Electrochemical Transistors: Structure‐Function Correlations
Authors: Cho Yongjoon , Gao Lin , Yao Yao , Kim Jaehyun , Zhang Dayong , Forti Giacomo , Duplessis Isaiah , Wang Yuyang , Pankow Robert M. , Ji Xudong , Rivnay Jonathan , Marks Tobin J. , Facchetti Antonio 
Published: September 2024

AbstractThe fundamental challenge in electron‐transporting organic mixed ionic‐electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6‐type/U‐shaped non‐fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1 g to 3 g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Yn series: a U‐shaped/planar core, close π–π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion‐electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high transconductance of 16.5 mS, an on/off current ratio of ~106, and a turn‐on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY‐based OECT performance in terms of denser ngY OEG content, increased crystallite dimensions with decreased long‐range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small‐molecule‐based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small‐molecule OMIECs.
Tailoring the Properties of Chemically Recyclable Polyethylene‐Like Multiblock Polymers by Modulating the Branch Structure
Authors: Zhao Yucheng , Rettner Emma M. , Battson Megan E. , Hu Zhitao , Miscall Joel , Rorrer Nicholas A. , Miyake Garret M. 
Published: September 2024

AbstractDeveloping plastics that fill the need of polyolefins yet are more easily recyclable is a critical need to address the plastic waste crisis. However, most efforts in this vein have focused on high‐density polyethylene (PE), while many different types of PE exist. To create broadly sustainable PE with modular properties, we present the synthesis, characterization, and demonstration of materials applications for chemically recyclable PE‐like multiblock polymers prepared from distinct hard and soft blocks using ruthenium‐catalyzed dehydrogenative polymerization. By altering the branching pattern within the soft blocks, a series of PE‐like multiblock polymers were synthesized with tunable glass transition temperatures (Tg) while maintaining consistent high melting temperatures (Tm). A clear U‐shape trend between Tg and mechanical properties was found, showcasing their potential as sustainable materials with tailored properties spanning commercial linear low‐density polyethylene (LLDPE) and low‐density polyethylene (LDPE). These materials offer adjustable adhesive strength to metal and demonstrate chemical recyclability and selective depolymerization in mixed plastic streams, promoting circularity and separation.
Constructing Unsaturated Ru Atom Arrays Confined in Mn Oxides to Boost Neutral Water Reduction
Authors: Hu Qi , Cao Jianyong , Qi Shuai , Meng Na , Zhao Jingwen , Huang Tianchi , You Jiao , Liang Taiyu , Shang Chunyan , Yu Jiaying , Yang Hengpan , He Chuanxin 
Published: September 2024

AbstractRecently, Ru single atoms supported on carbon nanomaterials have demonstrated ultrahigh activity for acid hydrogen evolution reaction (HER), however their neutral HER activity remains low due to the sluggish kinetics for both the water dissociation step to generate H* intermediates and subsequent H* recombination in neutral electrolytes. Here, we synthesize ordered low‐coordinated Ru atom arrays confined in Mn oxides (i.e., Li4Mn5O12) for concurrently boosting the water dissociation and H* recombination, thus achieving a 6‐fold HER activity enhancement than commercial Pt/C in neutral media. Control experiments indicate that low‐coordinated Ru atoms with strong affinity to oxygen atoms of water molecules facilitate the water dissociation to rapidly generate H*. More importantly, both electrochemical and theoretic results uncover that the array‐like structure allows the activation of two water molecules on two adjacent Ru atoms for enabling direct H*−H* recombination via the Tafel step, while isolated Ru atoms can only activate water one by one for recombining H* via the sluggish Heyrovsky step. Clearly, this work paves new avenues to boosting the electrocatalytic activity by constructing ordered metal atoms assembles with controllable coordination environments.
Controlling the Redox Chemistry of Cobalt Radiopharmaceuticals
Authors: Lin Wilson , Śmiłowicz Dariusz , Joaqui‐Joaqui M. Andrey , Bera Abhijit , Zhong Zhuoran , Aluicio‐Sarduy Eduardo , Mixdorf Jason C. , Barnhart Todd E. , Engle Jonathan W. , Boros Eszter 
Published: September 2024

AbstractThe elementally matched 55Co2+/3+ (t1/2=17.53 h, Iβ+=77 %)/58mCo2+/3+ (t1/2=9.10 h, internal conversion=100 %) radioisotope pair is of interest for development of paired diagnostic/therapeutic radiopharmaceuticals. Due to the accessibility of the nat/55Co2+/3+ redox couple, the redox state can be readily modulated. Here, we show that macroscopic and radiochemical redox reactions can be closely monitored and controlled using spectroscopic and radiochemical methods. We employ model systems to inform how to selectively synthesize thermodynamically favored oxidation state coordination complexes. In addition to exogenous oxidants, our data indicates that 55Co‐induced radiolysis of water efficiently and directly drives selective oxidation to the 55Co3+ species under no‐carrier added (n.c.a.) conditions. Our synthetic strategies subsequently stabilize the respective 55Co2+ or 55Co3+ species for targeted positron emission tomography imaging in a mouse tumor model.
Intermolecular 1,2‐Aminoboration of Alkynes and the Critical Role of Electron‐Rich Alkynes
Authors: Dotzauer Simon , Jayaraman Arumugam , Reinhart David , Braunschweig Holger 
Published: September 2024

AbstractThe intramolecular 1,2‐aminoboration of alkynes by aminoboranes is rare and invariably requires a catalyst to proceed, while the intermolecular aminoboration of alkynes is yet entirely unknown. Through an exploration of the significance of electronics in alkynes for activating the B−N σ‐bond of aminoboranes, we demonstrate in this work the first intermolecular 1,2‐aminoboration of alkynes. These reactions employ a series of (amino)dihaloboranes and aminoboronic esters, mild reaction conditions, and no catalysts, yielding syn‐addition alkene products with the incorporation of two crucial functionalities: amino and boryl. While highly electron‐rich examples can afford the aminoborated products (Z)‐2‐borylethenamines, other alkynes, including unactivated and less electron‐rich examples, do not lead to the corresponding aminoborated products due to the fundamental impediment that the reactions are significantly endergonic.
Pairing Oxygen Reduction and Water Oxidation for Dual‐Pathway H2O2 Production
Authors: Sun Xin , Yang Jindi , Zeng Xiangkang , Guo Lijun , Bie Chuanbiao , Wang Zhuyuan , Sun Kaige , Sahu Aloka Kumar , Tebyetekerwa Mike , Rufford Thomas E. , Zhang Xiwang 
Published: September 2024

AbstractHydrogen peroxide (H2O2) is a crucial chemical applied in various industry sectors. However, the current industrial anthraquinone process for H2O2 synthesis is carbon‐intensive. With sunlight and renewable electricity as energy inputs, photocatalysis and electrocatalysis have great potential for green H2O2 production from oxygen (O2) and water (H2O). Herein, we review the advances in pairing two‐electron O2 reduction and two‐electron H2O oxidation reactions for dual‐pathway H2O2 synthesis. The basic principles, paired redox reactions, and catalytic device configurations are introduced initially. Aligning with the energy input, the latest photocatalysts, electrocatalysts, and photo‐electrocatalysts for dual‐pathway H2O2 production are discussed afterward. Finally, we outlook the research opportunities in the future. This minireview aims to provide insights and guidelines for the broad community who are interested in catalyst design and innovative technology for on‐site H2O2 synthesis.
Enhanced chitosan and carboxymethylcellulose scaffolds with natural fiber reinforcement for hernia repair meshes
Authors: Rodríguez Guadalupe de Jesús , Patiño‐Herrera Rosalba , Zavala‐Alonso Verónica , Armendáriz‐Alonso Edgar F. , Cruz‐Guerrero Rosario , Pérez Elias 
Published: September 2024

AbstractChitosan (Chi) and carboxymethylcellulose (CMC) scaffolds, with and without reinforcement by Luffa cylindrica (Lc) or Asclepias curassavica (Ac), were synthesized to evaluate their potential application as hernia repair meshes. These meshes are crucial as they provide structural support to weakened tissues, reducing the risk of hernia recurrence and promoting faster recovery. They improve patient outcomes by enhancing the durability and effectiveness of hernia repairs. Chi scaffolds exhibited lower porosity compared to CMC scaffolds, with fiber inclusion enhancing porosity. The CMC4‐Ac scaffold demonstrated the highest porosity at 67.2%, which is crucial for supporting cell growth and tissue regeneration. All scaffolds exhibited exceptional hydration levels, which is vital for cell growth. Scanning electron microscope (SEM) images revealed open pores in the CMC4 scaffolds, which enhances tissue formation. Tensile strength tests indicated that all scaffolds surpassed the minimum requirements, with CMC4‐Ac standing out for its exceptional properties. CMC scaffolds showed greater degradation, which was mitigated by fiber reinforcement. Chi scaffolds absorbed more Croton draco extract (Cdext) but exhibited lower release rates compared to CMC scaffolds. No hemolytic and non‐cytotoxicity effects were observed. CMC4‐Ac emerged as the most promising scaffold due to its superior properties, making it suitable for hernia repair meshes.
Syntheses of Novel Spirobenzazepinoindole Derivatives via Lewis‐Acid Catalyzed Pictet‐Spengler Cyclization
Authors: Bansal Diksha , Nataraj Gokulprasanth , Sivaganesan Pooja , Das Mrinal Kanti , Chaudhuri Saikat 
Published: September 2024

AbstractThe syntheses of novel spirobenzazepinoindole derivatives has been achieved through a highly efficient and synthetic route. The approach involves a two‐step reaction, utilizing indole derivatives, 2‐amino benzyl alcohol, and ninhydrin as key starting materials under mild reaction conditions. The reaction proceeds via a sequential cascade process involving cyclization, condensation and spiro‐annulation, leading to the formation of the spirobenzazepinoindole core structure in good to excellent yields. The method offers broad substrate scope, high atom economy, and operational simplicity. The synthesized spirobenzazepinoindoles were fully characterized by spectroscopic techniques, including NMR (1H & 13C), IR and mass spectrometry. The methodology provides a valuable tool for the rapid generation of structurally complex spirobenzazepinoindoles, which could serve as scaffolds for the development of new therapeutic agents.