bluuebunny/crossref_metadata_2025_split huggingface dataset:
Intracellular Gold Nanocluster/Organic Semiconductor Heterostructure for Enhancing Photosynthesis
Authors: Cong Yujie , Wang Xiaoyu , Bai Haotian , Yao Chuang , Liu Jiaren , Wei Yi , Kang Yuetong , Wang Shu , Li Lidong 
Published: August 2024

AbstractPhotosynthetic microorganisms, which rely on light‐driven electron transfer, store solar energy in self‐energy carriers and convert it into bioenergy. Although these microorganisms can operate light‐induced charge separation with nearly 100 % quantum efficiency, their practical applications are inherently limited by the photosynthetic energy conversion efficiency. Artificial semiconductors can induce an electronic response to photoexcitation, providing additional excited electrons for natural photosynthesis to improve solar conversion efficiency. However, challenges remain in importing exogenous electrons across cell membranes. In this work, we have developed an engineered gold nanocluster/organic semiconductor heterostructure (AuNCs@OFTF) to couple the intracellular electron transport chain of living cyanobacteria. AuNCs@OFTF exhibits a prolonged excited state lifetime and effective charge separation. The internalized AuNCs@OFTF permits its photogenerated electrons to participate in the downstream of photosystem II and construct an oriented electronic highway, which enables a five‐fold increase in photocurrent in living cyanobacteria. Moreover, the binding events of AuNCs@OFTF established an abiotic‐biotic electronic interface at the thylakoid membrane to enhance electron flux and finally furnished nicotinamide adenine dinucleotide phosphate. Thus, AuNCs@OFTF can be exploited to spatiotemporally manipulate and enhance the solar conversion of living cyanobacteria in cells, providing an extended nanotechnology for re‐engineering photosynthetic pathways.
Azobenzene‐Bridged Covalent Organic Frameworks Boosting Photocatalytic Hydrogen Peroxide Production from Alkaline Water: One Atom Makes a Significant Improvement
Authors: Sun Hui‐Hui , Zhou Zhi‐Bei , Fu Yubin , Qi Qiao‐Yan , Wang Zhen‐Xue , Xu Shunqi , Zhao Xin 
Published: August 2024

AbstractCovalent organic frameworks (COFs) have been demonstrated as promising photocatalysts for hydrogen peroxide (H2O2) production. However, the construction of COFs with new active sites, high photoactivity, and wide‐range light absorption for efficient H2O2 production remains challenging. Herein, we present the synthesis of a novel azobenzene‐bridged 2D COF (COF‐TPT‐Azo) with excellent performance on photocatalytic H2O2 production under alkaline conditions. Notably, although COF‐TPT‐Azo differs by only one atom (−N=N− vs. −C=N−) from its corresponding imine‐linked counterpart (COF‐TPT‐TPA), COF‐TPT‐Azo exhibits a significantly narrower band gap, enhanced charge transport, and prompted photoactivity. Remarkably, when employed as a metal‐free photocatalyst, COF‐TPT‐Azo achieves a high photocatalytic H2O2 production rate up to 1498 μmol g−1 h−1 at pH = 11, which is 7.9 times higher than that of COF‐TPT‐TPA. Further density functional theory (DFT) calculations reveal that the −N=N− linkages are the active sites for photocatalysis. This work provides new prospects for developing high‐performance COF‐based photocatalysts.
Stereodivergency in Copper‐Catalyzed Borylative Difunctionalizations: The Impact of Boron Coordination
Authors: Mirabi Bijan , Li Shangyu , Ching Justin , Lenz Madina , Popovic Simon M. , Lautens Mark 
Published: August 2024

AbstractA reagent‐controlled diastereodivergent copper‐catalyzed borylative difunctionalization is reported. The formation of Lewis adducts that guide selectivity is commonly invoked in organic reaction mechanisms. Using density functional theory calculations, we identified BpinBdan as a sterically similar and less Lewis acidic alternative to B2pin2. Using a newly developed borylative aldol domino reaction as the proof‐of‐concept, we demonstrate a change in stereochemical outcome by a simple change of borylating reagent—B2pin2 affords the diastereomer associated with coordination control while BpinBdan overturns this mode of binding. We show that this strategy can be generalized to other scaffolds and, more importantly, that BpinBdan does not alter the diastereomeric outcome of the reaction when coordination is not involved. BpinBdan can be viewed as a mechanistic probe for coordination in future copper‐catalyzed borylation reactions.
Novel Dissymmetric Formal Quinoidal Molecules End‐Capped by Dicyanomethylene and Triphenylphosphonium
Authors: Shang Wansong , Meng Wei , Chen Lingfang , Shangguan Zhichun , Huang Yanyan , Zhang Xi‐Sha , Li Cheng , Bai Shuming , Zhang Guanxin , Zhang Deqing 
Published: August 2024

AbstractA number of quinoidal molecules with symmetric end‐capping groups, particularly dicyanomethylene units, have been synthesized for organic optoelectronic materials. In comparison, dissymmetric quinoidal molecules, characterized by end‐capping with different groups, are less explored. In this paper, we present the unexpected formation of new formal quinoidal molecules, which are end‐capped with both dicyanomethylene and triphenylphosphonium moieties. The structures of these dissymmetric quinoidal molecules were firmly verified by single crystal structural analyses. On the basis of the control experiments and DFT calculations, we proposed the reaction mechanism for the formation of these dissymmetric quinoidal molecules. The respective zwitterionic forms should make contributions to the ground state structures of these quinoidal molecules based on the analysis of their bond lengths and aromaticity and Mayer Bond Orbital (MBO) calculation. This agrees well with the fact that negative solvatochromism was observed for these quinoidal molecules. Although these new quinoidal molecules are non‐emissive both in solutions and crystalline states, they become emissive with quantum yields up to 51.4 % after elevating the solvent viscosity or dispersing them in a PMMA matrix. Interestingly, their emissions can also be switched on upon binding with certain proteins, in particular with human serum albumin.
Novel Ni(II) Complexes as Minor Groove Binders: Crystal Structures, Biomolecular Interactions, Molecular Docking, and Biological Activities
Authors: Özbağcı Duygu İnci 
Published: August 2024

ABSTRACTA novel ternary Ni(II) complexes, [Ni(5Clsal‐phe)(phen)(H2O)] (1) and [Ni(5Clsal‐phe)(bpy)(H2O)]CH3OH (2), (Schiff base derived from the condensation of L‐phenylalanine and 5‐chlorosalicylaldehyde, phen: 1,10‐phenanthroline, bpy: 2,2′‐bipyridine) has been synthesized. The structure of the complexes was clarified by CHN analysis, FTIR, electronic absorption spectroscopy, ESI‐MS, and X‐ray single crystal diffraction methods. In biological activity studies, the interactions of the complexes with calf thymus DNA (CT‐DNA) were examined using fluorescence spectroscopy. The results show that the complexes could bind to CT‐DNA via a minor groove mode. The interactions of the complexes with bovine serum albumin (BSA) were investigated using electronic absorption and fluorescence spectroscopy techniques, and the BSA quenching mechanism was found. The radical scavenging activity of the complexes was investigated in comparison with hederacolchiside, taxifoline, hederasaponin, arachidonoyl dopamine, and silychristin used as standard. Molecular docking simulations were employed to investigate the interactions between the complexes and biomolecules such as DNA and BSA. The results revealed that the complexes insert into DNA via the minor groove and bind to BSA at subdomains I and IIA. These interactions are facilitated by conventional hydrogen bonds, van der Waals forces, alkyl, and π‐alkyl interactions.
Self‐healable Mn‐doped PVA‐borax hydrogel electrodes for supercapacitor applications
Authors: Kockar Aysegul , Demirel Serkan , Kerimli Genber 
Published: August 2024

AbstractThis study aims to investigate the effect of Mn doping on the performance of polyvinyl alcohol/borax‐structured (PMB) supercapacitor electrodes for high‐capacity, flexible, and self‐healing supercapacitor electrodes. The PMB electrodes were characterized by x‐ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM). Electrochemical characterization was conducted using cyclic voltammetry (CV), which revealed that redox reactions, which are evident at low scan rates, enhance capacitive performance. However, high scan rates introduce limitations owing to the increased vibrations of the PVA chains and incomplete electrolyte polarization. The PMB electrodes exhibited remarkable electrochemical properties and capacitive performances, which were significantly affected by the MnO₂ structure. The electrodes exhibited self‐healing properties and demonstrated flexibility to stretch by up to 40%. In addition, the results indicate that the electrode capacity of the PVA/borax system increased by 2.03 times after 1000 cycles with manganese doping. The solid electrolyte interface (SEI) layer formed on the electrode surface plays a critical role in stabilizing the capacity loss during prolonged charge–discharge cycles. The study concluded that PMB supercapacitors offer higher capacitance in 0‐2 V applications compared to other PVA/borax combination hydrogels. Moreover, the incorporation of metal‐based additives, particularly manganese, enhanced the capacitive performance, and operating voltage levels.
AIE‐Based & Organic Luminescent Materials: Nanoarchitectonics and Advanced Applications
Authors: Gawade Vilas K. , Jadhav Ratan W. , Bhosale Sheshanath V. 
Published: August 2024

AbstractOrganic luminescence materials makes the molecule more enthusiastic in wide variety of applications. The luminescent organic materials are in a attraction of the researchers, and the Aggregation‐Induced Emission (AIE) is attributed to the occurrence that particular chromophores (typically fluorophores) display very low or nearly no emission in the monomolecular soluble state but become highly emissive when forming aggregates in solution or in solid state. This phenomenon is relatively abnormal when compared with many other traditional fluorophores. AIE research suppresses aggregation‐caused quenching (ACQ). Nevertheless, the carbon dots (CDs) and quantum dots have shown to have tyical florescence properties, therefore, recent years many researchers have also attracted for their developments. The CDs, luminescent, and AIE materials are not only used in biomedical applications and organic light‐emitting diodes but also in sensing, self‐assembly, and other areas. One should introduce promising material to a designed framework that exhibits AIE characteristics to ensure moral results in AIE. Amongest, AIE‐active tetraphenylethylene (TPE) is attractive fluorophores due to its easy synthesis strategy. This review article discusses the synthesis properties of TPE, CDs, and luminescent materials with a broad range of applications. We have outlined linear, branched‐shaped supramolecular, and hybrid macromolecules due to its potential in the future.
Ammonium Zincates as Catalysts for the Microwave‐Enhanced Synthesis of Symmetric Piperazines by Regioselective Opening of Aziridines
Authors: Alberti Matteo , Dariol Andrea , Panza Nicola , Abbiati Giorgio , Caselli Alessandro 
Published: August 2024

Abstract2,5‐disubstituted N,N’‐alkylpiperazines represent an interesting target in organic synthesis both for pharmaceutical or agrochemical applications and as a promising class of ligands in coordination chemistry. We report here a microwave‐enhanced synthesis of these compounds starting from non‐activated N‐alkyl aziridines in the presence of catalytic amounts of simple ammonium metallates. A remarkable TOF of 2787.9 h−1 has been observed in the case of [TBA]2[ZnI4] as the catalyst (catalyst loading 0.1 mol %) and with an almost complete selectivity (up to 97 %) in favor of both diastereoisomers (meso and chiral form) of the target 2,5‐disubstituted piperazines, obtained in 1 : 1 ratio. The two isomers are easily separated, because the meso form precipitates in pure from the reaction crude. A stereochemical investigation and the unprecedented isolation of 2,6‐disubstituted N,N’‐alkylpiperazines allowed us to shed light on the reaction mechanism.
Electrochemical Charge Transfer Kinetics of Ferrocene in the Light of Different Working Electrodes
Authors: Kaur Rajwinder , Ghoshal Abhik , Galav Prachi , Mondal Prakash Chandra 
Published: August 2024

AbstractFerrocene is an accidentally discovered organometallic compound that serves as a crucial redox probe in investigating electrochemical charge transfer dynamics. Besides solution phase studies, ferrocene derivatives are well‐explored in molecular thin films, including self‐assembled monolayers on various electrodes for understanding on‐surface redox behavior, molecular electronics, and charge storage applications. Heterogeneous charge transfer is an imperative parameter for efficient charge transport in spin‐dependent electrochemistry, photoelectrochemistry, and molecular electronic devices. In this work, we aim to study the electrochemical charge transfer of ferrocene on various electrodes such as commercially obtained glassy carbon, graphite rod, indium tin oxide (ITO), and as‐prepared gold, and nickel to determine the impact of the nature of the working electrode on the electron transfer rate, diffusion coefficient, and reversibility of the redox process. Both the direct current and alternating current‐based electrochemical experiments are performed, followed by digitization of the experimental results. The kinetics of electron transfer and electrochemical reversibility reveal a strong dependence on the nature of the working electrode, as the electrochemically driven oxidation and reduction of the material of interest are directly related to the Fermi energy and electronic structure of the working electrode.
Polymerizable Ionic Liquid‐Derived N, S co‐Doped sp3/sp2 Carbon as Electrocatalyst for H2O2 Generation
Authors: Gao Jian , Meng Lingxin , Gui Jianzhou , Wang Hong , Ma Na , Yin Zhen , Tan Xiaoyao , Li Yuan 
Published: August 2024

AbstractThe H2O2 generation via the green electrochemical process is of high interest. For the H2O2 electrochemical generation, the oxygen reduction reaction (ORR) is important. Unfortunately, the ORR is kinetically sluggish and catalysts are needed. However, noble metal ORR catalysts are pricy and scarcely applicable in applications. Therefore, non‐precious metal catalysts are desired. Heteroatom‐doped carbons show promise as metal‐free ORR catalysts. The ORR catalytic activity will be enhanced by the carbon's sp2 and/or sp3 engineering. For N, S co‐Cdoped and sp2/sp3 modulated carbon, a polymerizable ionic liquid of hydrolyzed vinyl imidazolium was studied. The carbon is studied as a metal‐free catalyst for the ORR via the 2e− process. It is possible to get an onset potential of 0.88 V vs. RHE with approximately 50 % selectivity for the H2O2. The current study offers a simple technique for synthesizing heteroatom‐doped sp2/sp3 designed carbon as catalysts for the electroreduction of O2 to produce H2O2, and a new way of tunning the sp3/sp2 carbon catalytic activity by modulating the ionic liquid.
Development and validation of an ultra‐performance liquid chromatography–tandem mass spectrometry method to quantify the small molecule inhibitors adagrasib, alectinib, brigatinib, capmatinib, crizotinib, lorlatinib, selpercatinib, and sotorasib in human plasma
Authors: Hollander Esther M. , Zimmerman Nachel M. C. , Piet Berber , van den Heuvel Michel M. , Burger David M. , te Brake Lindsey H. M. , ter Heine Rob 
Published: August 2024

AbstractSmall molecule inhibitors (SMIs) are increasingly being used in the treatment of non‐small cell lung cancer. To support pharmacokinetic research and clinical treatment monitoring, our aim was to develop and validate an ultra‐performance liquid chromatography–mass spectrometry (UPLC‐MS/MS) assay for quantification of eight SMIs: adagrasib, alectinib, brigatinib, capmatinib, crizotinib, lorlatinib, selpercatinib, and sotorasib. Development of the UPLC‐MS/MS assay was done by trying different columns and eluents to optimize peak shape. The assay was validated based on guidelines of the European Medicines Agency. Chromatographic separation was performed with a gradient elution using ammonium formate in water and methanol. Detection was performed using a triple quadrupole tandem mass spectrometer with electrospray ionization. Validation was performed in a range of 10–2500 μg/L for lorlatinib, 25–6250 μg/L for alectinib and crizotinib, 25–10,000 μg/L for capmatinib and selpercatinib, 50–12,500 μg/L for brigatinib, and 100–25,000 μg/L for adagrasib and sotorasib. Imprecision was <8.88% and inaccuracy was <12.5% for all compounds. Seven out of eight compounds were stable for 96 h at room temperature. Sotorasib was stable for 8 h at room temperature. A sensitive and reliable method has been developed to quantify eight SMIs with a single assay, enhancing efficacy and safety of targeted therapies.
LncRNA ILF3‐AS1 mediates oxidative stress and inflammation through miR‐504‐3p/HMGB1 axis in a cellular model of temporal lobe epilepsy
Authors: Gao Peipei , Wu Ying , Yan Zhixin 
Published: August 2024

AbstractBackgroundTemporal lobe epilepsy (TLE), a prevalent neurological disorder, is associated with hippocampal oxidative stress and inflammation. A recent study reveals that the long noncoding RNA ILF3 divergent transcript (ILF3‐AS1) level is elevated in the hippocampus of TLE patients; however, the functional roles of ILF3‐AS1 in TLE and underlying mechanisms deserve further investigation. Hence, this study aimed to elucidate whether ILF3‐AS1 is involved in the pathogenesis of TLE by regulating oxidative stress and inflammation and to explore its underlying mechanism in vitro.MethodsHuman hippocampal neurons were subjected to a magnesium‐free (Mg2+‐free) solution to establish an in vitro model of TLE. The potential binding sites between ILF3‐AS1 and miRNA were predicted by TargetScan/Starbase and confirmed by dual luciferase reporter assay. Cell viability and damage were assessed by cell counting kit‐8 and lactate dehydrogenase assay kits, respectively. Levels of reactive oxygen species, malondialdehyde, and superoxide dismutase were determined by commercial kits. Levels of Interleukin‐6 (IL‐6), IL‐1β, and tumor necrosis factor‐alpha were quantified by enzyme‐linked immunosorbent assay. The expressions of gene and protein were determined by quantitative real‐time polymerase chain reaction and Western blot analysis.ResultsIn Mg2+‐free‐treated hippocampal neurons, both ILF3‐AS1 and HMGB1 were highly up‐regulated, whereas miR‐504‐3p was down‐regulated. ILF3‐AS1 knockdown ameliorated Mg2+‐free‐induced cellular damage, oxidative stress, and inflammatory response. Bioinformatics analysis revealed that miR‐504‐3p was a target of ILF3‐AS1 and was negatively regulated by ILF3‐AS1. MiR‐504‐3p inhibitor blocked the protection of ILF3‐AS1 knockdown against Mg2+‐free‐induced neuronal injury. Further analysis presented that ILF3‐AS1 regulated HMGB1 expression by sponging miR‐504‐3p. Moreover, HMGB1 overexpression reversed the protective functions of ILF3‐AS1 knockdown.ConclusionOur findings indicate that ILF3‐AS1 contributes to Mg2+‐free‐induced hippocampal neuron injuries, oxidative stress, and inflammation by targeting the miR‐504‐3p/HMGB1 axis. These results provide a novel mechanistic understanding of ILF3‐AS1 in TLE and suggest potential therapeutic targets for the treatment of epilepsy.
Neuromyelitis optica spectrum disorder: Exploring the diverse clinical manifestations and the need for further exploration
Authors: Noori Hamid , Marsool Mohammed Dheyaa Marsool , Gohil Krutika Mahendra , Idrees Muhammad , Subash Tushar , Alazzeh Zainab , Prajjwal Priyadarshi , Jain Hritvik , Amir Omniat 
Published: August 2024

AbstractBackgroundNeuromyelitis optica spectrum disorder (NMOSD) is an autoimmune disorder characterized by inflammatory assaults on the central nervous system (CNS), particularly on the optic nerves and spinal cord. In recent years, a wider range of clinical manifestations of this complex disease have been observed, emphasizing the importance of gaining a more profound understanding beyond optic neuritis (ON) and transverse myelitis (TM).Current knowledgeThis study explores the many clinical symptoms of NMOSD, including common and uncommon presentations. Distinctive aspects of ON, TM, and diencephalic/brainstem syndromes are examined, highlighting their unique characteristics in contrast to conditions such as multiple sclerosis. We also discuss extra‐CNS involvement, such as unusual signs, including muscle involvement, retinal injury, auditory impairment, and rhinological symptoms.Aims and objectivesOur study intends to highlight the wide range and complexity of NMOSD presentations, emphasizing the significance of identifying unusual symptoms for precise diagnosis and prompt management. The specific processes that contribute to the varied clinical presentation of NMOSD are not well understood despite existing information. This emphasizes the necessity for more study to clarify the mechanisms that cause different symptoms and discover new treatment targets for this complex autoimmune disorder.ConclusionIt is essential to acknowledge the complex and varied clinical manifestations of NMOSD to enhance diagnosis, treatment, and patient results. By enhancing our comprehension of the fundamental processes and investigating innovative therapeutic approaches, we may aim to enhance the quality of life for persons impacted by this illness.
Alterations of contralesional hippocampal subfield volumes and relations to cognitive functions in patients with unilateral stroke
Authors: Lu Juan‐Juan , Xing Xiang‐Xin , Qu Jiao , Wu Jia‐Jia , Zheng Mou‐Xiong , Hua Xu‐Yun , Xu Jian‐Guang 
Published: August 2024

AbstractBackgroundThe volumes of the hippocampal subfields are related to poststroke cognitive dysfunctions. However, it remains unclear whether contralesional hippocampal subfield volume contributes to cognitive impairment. This study aimed to investigate the volumetric differences in the contralesional hippocampal subfields between patients with left and right hemisphere strokes (LHS/RHS). Additionally, correlations between contralesional hippocampal subfield volumes and clinical outcomes were explored.MethodsFourteen LHS (13 males, 52.57 ± 7.10 years), 13 RHS (11 males, 51.23 ± 15.23 years), and 18 healthy controls (11 males, 46.94 ± 12.74 years) were enrolled. Contralesional global and regional hippocampal volumes were obtained with T1‐weighted images. Correlations between contralesional hippocampal subfield volumes and clinical outcomes, including the Montreal Cognitive Assessment (MoCA) and Mini‐Mental State Examination (MMSE), were analyzed. Bonferroni correction was applied for multiple comparisons.ResultsSignificant reductions were found in contralesional hippocampal as a whole (adjusted p = .011) and its subfield volumes, including the hippocampal tail (adjusted p = .005), cornu ammonis 1 (CA1) (adjusted p = .002), molecular layer (ML) (adjusted p = .004), granule cell and ML of the dentate gyrus (GC‐ML‐DG) (adjusted p = .015), CA3 (adjusted p = .009), and CA4 (adjusted p = .014) in the RHS group compared to the LHS group. MoCA and MMSE had positive correlations with volumes of contralesional hippocampal tail (p = .015, r = .771; p = .017, r = .763) and fimbria (p = .020, r = .750; p = .019, r = .753) in the LHS group, and CA3 (p = .007, r = .857; p = .009, r = .838) in the RHS group, respectively.ConclusionUnilateral stroke caused volumetric differences in different hippocampal subfields contralesionally, which correlated to cognitive impairment. RHS leads to greater volumetric reduction in the whole contralesional hippocampus and specific subfields (hippocampal tail, CA1, ML, GC‐ML‐DG, CA3, and CA4) compared to LHS. These changes are correlated with cognitive impairments, potentially due to disrupted neural pathways and interhemispheric communication.