bluuebunny/crossref_metadata_2025_split huggingface dataset:
Achieving Ultrabright NIR‐II Nanofluorophore for In Vivo Imaging by Inhibiting H‐Aggregates Formation
Authors: Tang Xialian , Xiong Jiabao , Chen Liying , Zhang Xunwen , Ma Dalong , Li Wen , Shen Yaowei , Liu Jie , Alifu Nuernisha 
Published: December 2024

AbstractSmall molecules with an acceptor–donor–acceptor (A−D−A) structure, featuring a fused‐ring core as the donor and two electron‐withdrawing end groups as acceptor units, represent a potential option for NIR‐II fluorophores, benefiting from their narrow bandgaps, superior light‐harvesting capabilities, and exceptional photostabilities. However, their planar conformations predispose them to forming H‐aggregates during self‐assembly, leading to significantly reduced fluorescence quantum yield (QY) of the resulting nanofluorophores. Herein, we report a small molecule, PF8CN, with a terminal unit‐A−D−A‐terminal unit structure. The terminal units of 3,5‐bis(octyloxy)phenyl group result in a twisted conformation for PF8CN, preventing face‐to‐face stacking and thereby inhibiting the formation of H‐aggregates. Consequently, the NIR‐II fluorescence QY of PF8CN NPs is 3.8 times that of the model nanofluorophore (F8CN NPs), which contains a substantial amount of H‐aggregates. The NIR‐II brightness of PF8CN NPs is 5.3‐ and 14.9‐times that of F8CN NPs and ICG/FBS, respectively, at an equal molar concentration. Such ultrahigh NIR‐II brightness of PF8CN NPs allows us to perform long‐term and real‐time NIR‐II fluorescence imaging of cerebral and hindlimb vessels, as well as the thrombolytic process. This work provides an effective method for producing nanofluorophores with ultrahigh NIR‐II brightness, positioning PF8CN NPs as a strong contender in the field of NIR‐II nanofluorophores.
Sheets Copper‐Cobalt Graphitic Carbon Nitride Dual Single‐Atom Catalysts for the Epoxidation of Styrene
Authors: Fu Yufang , Zhu Ziqian , Chen Yunhong , Liu Chuang , Wang Ganping , Rong Youqi , Liang Kun , Mei Bingbao , Fang Jian , Zhao Jihua 
Published: December 2024

AbstractDual single‐atom catalysts have attracted considerable research interest due to their higher metal atom loading and more flexible active sites compared to single‐atom catalysts (SACs). We pioneered the one‐step synthesis of sheets copper‐cobalt graphitic carbon nitride dual single‐atom (S−Cu/Co‐g‐C3N4) using folding fan‐shaped aluminum foil as a template, and used them as catalysts in the epoxidation of styrene respectively. Through XAFS (X‐ray Absorption Fine Structure) and other characterizations, it is found that Cu and Co single atoms are stabilized separately on g‐C3N4 via coordination with nitrogen (N), hindered the ordered growth of sheets, and formed more pore structures, which not only increased more catalytically active sites, but also effectively prevented the flakes re‐aggregate during the catalytic process. And the synergistic effect between Cu and Co changes the energy band structure of the material and facilitates electron transfer during catalysis, hence an excellent catalytic effect of 89 % styrene conversion and 85 % styrene oxide selectivity was achieved when S−Cu/Co‐g‐C3N4‐1 : 1 was applied in the epoxidation of styrene. Furthermore, the mechanisms of the epoxidation of styrene with S−Cu/Co‐g‐C3N4‐1 : 1 was probed by the density functional theory (DFT) based on the slab model.
A Multifunctional Ru‐Re Complex for Photodynamic Therapy and CO‐Mediated Therapeutics in Alzheimer's Disease
Authors: Hau Gan Chun , Chen Hsin‐Jou , Yu‐Syun Fan Ricky , Pan Siao‐Cian , Voon Kong Kien 
Published: December 2024

AbstractThe development of multifunctional therapeutic agents is crucial for addressing complex diseases such as Alzheimer's disease. Herein, we report a ruthenium‐rhenium (Ru−Re) complex that combines photodynamic therapy (PDT) and carbon monoxide (CO) generation capabilities. The Ru−Re complex shows promising photophysical property and significant therapeutic potential. Our studies reveal the complex's ability to generate singlet oxygen (1O2), CO, inhibit tau aggregation, and enhance mitochondrial respiration. These multifunctional properties position the Ru−Re complex as a versatile tool for therapeutic applications in Alzheimer's disease.
Addition and Oxidation Reactivity of a Pentacoordinate Nickelacyclobutane
Authors: Sansores‐Paredes María L. G. , Lutz Martin , Moret Marc‐Etienne 
Published: December 2024

AbstractNickelacyclobutanes are reactive intermediates in catalytic cycles including cyclopropanation and insertion reactions. The stoichiometric study of these intermediates has shown that their reactivity is highly influenced by the coordination environment of the nickel center. A pentacoordinated nickelacyclobutane embedded in a diphosphine pincer ligand has been shown to selectively undergo various reactions with exogenous ligands, including [2+2] cycloreversion and carbene transfer to an isocyanide. Herein, we investigate the reactivity of the pentacoordinated nickelacyclobutane towards addition and oxidation reactions. Addition reactions lead to ring‐opening to form stable square planar Ni(II) compounds, while metal oxidation enhances [2+2] cycloreversion. DFT calculations are used to shed light on the different mechanisms.
One‐Pot Synthesis of Multicentric DIL@PDIL Catalyst for Mild CO2 Conversion to Cyclic Carbonates
Authors: Wang Yeying , Zeng Yanbin , Tang Zhenzhu , Qiu Jiaxiang , Wang Xiaoxia , Xie Guanqun , Wang Xiufang 
Published: December 2024

AbstractAmong the various studies on CO2 utilization, the sustainable and cost‐effective fixation of CO2 into cyclic carbonates remains one of the most intriguing subjects. To this end, a novel type of composite dicationic ionic liquid material, DIL@PDIL, was developed. This composite consists of a dicationic ionic liquid (DIL), DMAP[TMGH]Br, supported on a polymeric dicationic ionic liquid (PDIL), P‐DVB/Im[TMGH]Br. The multicentric high‐ion‐density material was prepared with exceptional efficiency from five readily available starting materials in one pot through simultaneous quaternization, neutralization and polymerization. The structure was characterized using FT‐IR, XPS, SEM, TGA, ICP‐MS and BET, as well as through stepwise synthesis verification. Evaluation of the catalytic performance revealed the ionic liquid composite delivered chloropropylene carbonate (CPC) in excellent yield and selectivity from either pure CO2 or simulated flue gas at 60 °C and relatively lower pressure. Additionally, the DIL@PDIL catalyst exhibited good recyclability and were applicable to a range of epoxide substrates. The high activity of the the catalyst could be attributed to the abundant [TMGH]+ hydrogen bonding donors and Br− anions, which synergistically catalyze the epoxide ring‐opening, as well as the abundant ‐COO− groups and imidazole cations, which facilitate the adsorption and activation of CO2.
Unveiling the Potential of Thiophene‐Functionalized Porous Organic Polymers for Bromine Adsorption and Selective Separation from Iodine
Authors: Mondal Bikram , Bishal Kashyap Akash , Das Gopal 
Published: December 2024

AbstractBromine is a significant environmental threat due to its corrosive nature and contribution to ozone layer depletion. It often coexists with iodine and forms interhalogen complexes (IBr), which require an effective and selective bromine adsorption strategy. Leveraging the electrophilic nature of bromine, we designed an electron‐rich thiophene‐based porous organic polymer (POF‐2). This material exhibits exceptional efficiency for bromine adsorption (2.86 g g−1) and rapid uptake kinetic from aqueous solutions, driven by noncovalent charge transfer interactions. POF‐2 also demonstrates selective capture of bromine from a bromine‐iodine mixture in cyclohexane. The material's electron‐rich sites exhibit a stronger orbital interaction with the σ* orbital of bromine compared to iodine, leading to the observed selectivity in cyclohexane.
Achieving Precise Control Over the Molecular Periphery of Dibenzoixenes Through Modular Synthesis
Authors: Shin Seongrok , Kim Hwon , Ha Jee Ho , Eun Kyung Yeon , Kim Jiyeon , Kim Yeram , Choe Wonyoung , Kang Seok Ju , Min Seung Kyu , Bielawski Christopher W. , Park Young S. 
Published: December 2024

AbstractNanographenes and polycyclic aromatic hydrocarbons, both finite forms of graphene, are promising organic semiconducting materials because their optoelectronic and magnetic properties can be modulated through precise control of their molecular peripheries. Several atomically precise edge structures have been prepared by bottom‐up synthesis; however, no systematic elucidation of these edge topologies at the molecular level has been reported. Herein, we describe rationally designed modular syntheses of isomeric dibenzoixenes with diverse molecular peripheries, including cove, zigzag, bay, fjord, and gulf structured. The single‐crystal structures of dibenzo[a,p]ixene and dibenzo[j,y]ixene reveal enantiomeric pairs with helically twisted cove edges and packing structures. The molecular edge structures are identified from the C−H bonds of the dibenzoixenes using Fourier transform infrared spectroscopy with different vibrational modes, which were further explained using density functional theory calculations. Electron spin resonance spectroscopy indicates that the zigzag‐edged molecular periphery significantly affects the magnetic properties of the material. Furthermore, the electrochemical characteristics, examined using dibenzoixenes as anode materials in Li‐ion batteries, reveal that the dibenzo[a,p]ixene exhibits promising Li intercalation behaviors with a specific capacity of ~120 mAh g−1. The findings of this study could facilitate the synthesis of larger
‐extended systems with engineered molecular peripheries and potential application in organic electronics.
Light‐Driven Adaptive Molecular Crystals Activated by [2+2] and [4+4] Cycloadditions
Authors: Yu Chunjiao , Wang Zhengcheng , Zhu Xiaotong , Gao Lin , Li Liang , Naumov Panče , Yu Qi , Wang Guoming 
Published: December 2024

AbstractPhotomechanical crystals act as light‐driven material‐machines that can convert the energy carried by photons into kinetic energy via shape deformation or displacement, and this capability holds a paramount significance for the development of photoactuated devices. This transformation is usually attributed to anisotropic expansion or contraction of the unit cell engendered by light‐induced structural modifications that lead to accumulation and release of stress that generates a momentum, resulting in readily observable mechanical effects. Among the available photochemical processes, the photoinduced [2+2] and [4+4] reactions are known for their robustness, predictability, amenability to control with molecular and supramolecular engineering approaches, and efficiency that has already been elevated to a proof‐of‐concept smart devices based on organic crystals. This review article presents a summary of the recent research progress on photomechanical properties of organic and metal‐organic crystals where the mechanical effects are based on [2+2] and [4+4] cycloaddition reactions. It consolidates the current understating of the chemical strategies and structure–property correlations, and highlights the advantages and drawbacks of this class of adaptive crystals within the broader field of crystal adaptronics.
Thiazole‐Based IL‐17 Inhibitors Discovered by Scaffold Morphing
Authors: Velcicky Juraj , Ngo Estelle , Bauer Matthias R. , Meyer Arndt , Schlapbach Achim , Racine Sophie , Orain David , Pflieger Daniel , Teixeira‐Fouchard Sylvie , Dubois Celine , Goetz Alban , Steiner Roland , Palmieri Marco , Bussenault Alex , Stringer Rowan , Larger Patrice , Riek Simone , Schmutz Patrick , Lehmann Sylvie , Scheufler Clemens , Rondeau Jean‐Michel , Burkhart Christoph , Knoepfel Thomas , Gommermann Nina 
Published: December 2024

AbstractThe pro‐inflammatory cytokine interleukin‐17A (IL‐17) plays an important role in the body's defense against bacterial and fungal infections. However, overexpression of IL‐17 has been associated with several diseases, including rheumatoid arthritis, asthma, psoriasis, and even cancer. The role of IL‐17 in psoriasis has been confirmed by clinical use of IL‐17 antibodies, e. g. secukinumab (Cosentyx®). Ongoing research is focused on discovering low molecular weight IL‐17 inhibitors. In this publication, we present thiazole‐based IL‐17 inhibitors discovered through a scaffold‐morphing strategy. This strategy involved ring‐opening of a known scaffold and utilization of a chalcogen interaction between thiazole‐sulfur and central amide‐oxygen to maintain the coplanar conformation found in the parent compound. The new scaffold enabled the generation of highly potent compounds with good overall profile. The optimized compounds 11 and 15 demonstrated good exposure in rats after oral dosing. Importantly, compound 11 exhibited no adverse effects in a rat tolerability study after a four‐day administration of up to 300 mg/kg/day.
Hierarchical Pore Engineering of Slope‐Type Hard Carbon for Enhanced Sodium‐Ion Storage
Authors: Liu Yongqi , Zhang Yun , Hu Zhaowei , Zhang Wenjie , Wang Chuan , Lian Jiabiao 
Published: December 2024

AbstractDesigning hierarchical porous structures is widely recognized as an effective strategy to improve ion transport and create active sites for disordered carbon anodes of sodium‐ion batteries (SIBs). Herein, hierarchical porous hard carbon (hp‐HC) is synthesized using zinc acetate as a templating agent. The hierarchical porous structure facilitates effective Na+ ion storage with a high reversible capacity of 327 mA h g−1 at a current density of 0.1 A g−1. Notably, the sodium storage behavior is capacitance‐dominated, with the capacity primarily characterized by slope capacity. Additionally, the hp‐HC retains 94.5 % of its capacity after 6000 cycles at 1.0 A g−1. This work provides a convenient route for manipulating pore types, which is of great significance for developing high‐capacity hard carbon electrodes for enhanced sodium‐ion storage.
The Electronic Spin State of Diradicals Obtained from the Nuclear Perspective: The Strange Case of Chichibabin Radicals
Authors: Moise Gabriel , Fernández Saleta , Joll Kit , Vaganov Mikhail V. , García Fátima , Timmel Christiane R. , Peña Diego , Ardavan Arzhang 
Published: December 2024

AbstractWith a view towards the development of molecular spintronics, non‐linear optics, and qubits, a great amount of research effort aims to establish the factors which govern the spin classification of diradicals. Electron spin resonance (ESR) is an indispensable tool for such research. However, in some cases, the mere presence of an ESR spectrum is insufficient to ascertain that the presumed diradical is indeed a triplet state. In a comparative case study of a Chichibabin diradical and a monoradical analogue, we show how the signals from different spin states present in liquid solutions of these species may be disentangled. Ultimately, the correct spin classification depends on ESR techniques which probe the spin quantum number directly. In this work, electron nuclear double resonance experiments reveal that the nuclei provide a clear experimental probe of the electronic spin configuration.
Solvation Structure and Dynamics of the Thiocyanate Anion in mixed N,N‐Dimethylformamide‐Water Solvents: A Molecular Dynamics Approach
Authors: Skarmoutsos Ioannis , Karvounis Ilias G. 
Published: December 2024

AbstractThe solvation structure and dynamics of the thiocyanate anion at infinite dilution in mixed N, N‐Dimethylformamide (DMF)‐water liquid solvents was studied using classical molecular dynamics simulation techniques. The results obtained have indicated a preferential solvation of the thiocyanate anions by the water molecules, due to strong hydrogen bonding interactions between the anion and water molecules. A first hydration shell at short intermolecular distances is formed around the SCN− anion consisting mainly by water molecules, followed by a second shell consisting by both DMF and water molecules. The strong interactions between the thiocyanate anion and water molecules are further reflected upon the calculated intermittent residence lifetimes of water and DMF in the first and second solvation shells. The dependence of the reorientational relaxation times of the thiocyanate anion upon the mole fraction of DMF in the mixtures has been found to be in good agreement with experiment, revealing strong concentration effects upon these relaxation phenomena. An appreciable solvent composition effect upon the low frequency intermolecular vibrations, due to the anion‐water interactions, has also been revealed by calculating the atomic velocity correlation functions and corresponding spectral densities of the anion.
Synthesis and Characterization of N‐Doped Carbon Quantum Dots and its Application for Efficient Delivery of Curcumin in Live Cell
Authors: Upadhyaya Arun K. , Agarwala Pratibha , Sharma Chanchal , Sasmal Dibyendu K. 
Published: December 2024

AbstractTo improve bioavailability, enhance the solubility and stability of the hydrophobic drug curcumin, nanoparticles such as carbon quantum dots (CQDs) are unique choices. In this study, we present a simple, cost‐effective, and eco‐friendly method for synthesizing nitrogen‐doped carbon quantum dots (N‐CQDs) and their application in the efficient delivery of hydrophobic drugs curcumin into live cancer cells. The N‐CQDs produced in this study exhibit excellent water solubility, remarkable stability, and high biocompatibility. To synthesize the N‐CQD, we use a carbon source found naturally (lemon juice) and for doping, we use N‐rich doping agents such as ethylene diamine and urea by using eco‐friendly chemical oxidation methods. The resulting N‐CQDs, with particle sizes under 10 nm, exhibit a good quantum yield, reinforcing their utility for biomedical applications. N‐CQDs and drug‐loaded particles are evaluated using various techniques like UV‐Vis, Fluorescence Spectroscopy, Dynamic Light Scattering (DLS), and Atomic Force Microscopy (AFM) as well. Additionally, we report a remarkable method to use N‐CQDs as carriers for the anticancer drug curcumin, significantly enhancing the solubility in live cells. Our research also delved into the application of N‐CQDs in in vivo bioimaging and drug release studies within live cancer cells, with a particular focus on their pH‐dependence behavior.
Going from Pt to PGM‐free Catalysts: Effects of Ink Compositions on PEM Water Electrolysis
Authors: Wierper Janna , Hiltrop Jannick , Pellumbi Kevinjeorjios , Jökel Julia , Sanden Sebastian , Kożusznik Miłosz , Mikuła Andrzej , Apfel Ulf‐Peter 
Published: December 2024

AbstractThe commercialisation of PEM water electrolysis is still hindered by the necessity of using noble metals that are rare, expensive and therefore unsustainable. To replace the benchmark HER catalyst Pt with more abundant materials, promising non‐noble catalysts need to be identified and optimal electrode preparation and electrolysis conditions need to be transferred between catalyst materials to reveal their full potential under industrially relevant conditions. This study investigates the optimal ink composition for spray‐coating the cathode regarding the effects on electrode structure, performance and catalyst layer composition. The ratio of catalyst to binder and carbon support was varied as well as the specific carbon material and the resulting electrodes were analysed via polarisation curves, electrochemical impedance spectroscopy, X‐ray photoelectron spectroscopy and scanning electron microscopy for three different catalysts. These results show that ink compositions with a catalyst : carbon : binder ratio of 3 : 1 : 1 using Carbon Vulcan give the highest performance. Interestingly, resulting trends concerning electrochemical behaviour and electrode structure observed with different characterisation techniques can be transferred between Pt catalysts and non‐noble transition metal chalcogenide materials. Boosting the performance via ink optimisation is much more pronounced for the non‐noble catalysts, narrowing the gap to competing with noble standard Pt materials.
Employment of a Newly Defined In Vitro Fertilization Protocol to Determine the Cytoskeletal Machinery, DNA Damage, and Subsequent DNA Repair Resulting from Endocrine Disruption by Hexavalent Chromium in Rat Metaphase II Oocytes
Authors: Wuri Liga , Zarutskie Paul W. , Arosh Joe A. , Banu Sakhila K. 
Published: December 2024

AbstractThese protocols describe a detailed method to determine the DNA damage and F‐actin and microtubule defects of metaphase II oocytes caused by hexavalent chromium, Cr(VI), an endocrine disrupting chemical (EDC). The protocol provides systematic steps to determine protein expression encoded by pluripotency proteins such as Oct4, Nanog, and Cdx2 during early embryonic development. Occupational or environmental exposure to EDCs has significantly increased infertility in both men and women. The urinary concentration of the EDC bisphenol A in patients undergoing in vitro fertilization (IVF) is directly related to decreased implantation rates and the number of metaphase II oocytes recovered. This protocol outlines crucial steps in assessing the structure of F‐actin and microtubules, DNA damage, and repair mechanisms in metaphase II oocytes as well as pluripotency protein markers of early‐stage embryos. IVF techniques to achieve fertility goals in both humans and animals are of paramount importance. The interplay between F‐actin and microtubules is crucial for bipolar spindle assembly and correct partitioning of the nuclear genome in mammalian oocyte meiosis. EDCs induce DNA damage and impair DNA repair mechanisms, compromising oocyte quality. In human IVF, this results in failure to implant, early miscarriage, and live births with congenital disorders, thus decreasing success rates and increasing poor outcomes. The application of IVF protocols in rats to understand EDC‐mediated defects in the cytoskeletal network of metaphase II oocytes is not well established. We present a newly defined rat IVF protocol and demonstrate outcomes using these protocols to determine the adverse effects of Cr(VI) on metaphase II oocytes. Basic Protocol 1 includes steps to superovulate rats, dissect ampullae, retrieve oocytes/eggs, perform immunofluorescence staining of cytoskeletal machinery (microtubules and F‐actin), and assess expression of the DNA double‐strand break marker γ‐H2AX and the DNA repair protein RAD51 in control and Cr(VI)‐exposed rats. Basic Protocol 2 describes methods for detecting the pluripotency proteins Oct4, Nanog, and Cdx2 during early embryonic development in control rats. © 2024 Wiley Periodicals LLC.Basic Protocol 1: In vivo EDC treatment of rats and immunostaining of treated oocytesBasic Protocol 2: In vitro fertilization and immunostaining of early‐stage embryos