bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical Profiling by High‐Performance Liquid Chromatography With Diode Array Detection and Gas Chromatography‐Mass Spectrometry Analysis and Antimicrobial Potential of Achillea santolina Plant Extracts against Extended‐Spectrum Beta‐Lactamase‐producing Escherichia coli and Fungal Pathogens
Authors: Renda Chahna , Nina Sadou , Amina Bouzana , Amina Bougouizi , Imane Haouame , Khellaf Rebbas , Garzoli Stefania , Bendif Hamdi
Published: December 2024

The study examines the chemical composition and antimicrobial properties of petroleum ether and hydro‐methanolic extracts of Achillea santolina from Algeria. Chemical profiling was performed using high‐performance liquid chromatography with diode array detection for the hydro‐methanolic extract and gas chromatography‐mass spectrometry for the petroleum ether extract. Antibacterial and antifungal activities were evaluated using the disc diffusion method and broth dilution technique. Epicatechin (24.54 mg/g extract), and camphor (19.18%) were identified as main compounds in the hydro‐methanolic and petroleum ether extracts, respectively. Both extracts showed significant antibacterial effects against extended‐spectrum beta‐lactamase‐producing Escherichia coli strains, with inhibition diameters ranging from 10 to 13 mm, and minimum inhibitory concentration (MIC) values between 0.78 and 3.5 mg/mL. Anti‐fungal activity was also notable, particularly against Candida albicans, with an inhibition diameter of 14 mm, and MIC values between 0.39 and 1.56 mg/mL. The hydro‐methanolic extract showed up to 90% of growth inhibition against Aspergillus niger. These findings suggest that A. santolina could serve as a promising source of antimicrobial compounds to combat resistant pathogens.
Quantifying the Impact of High‐Pressure Processing on the Phenolic Profile, Antioxidant Activity, and Pollen Morphology in Honey
Authors: Scepankova Hana , Majtan Juraj , Pospiech Matej , Moreira Manuela M. , Pinto Carlos A. , Dias Luís G. , Estevinho Leticia M. , Delerue‐Matos Cristina , Saraiva Jorge A.
Published: December 2024

Honey can benefit from non‐thermal processing techniques such as high‐pressure processing (HPP) to improve its quality and bioactivity. This study investigated the impact of HPP (600 MPa for 5, 10, and 15 min) on honey's quality, including the levels of hydroxymethylfurfural (HMF), antioxidant activity, total phenolic content (TPC), and phenolic profile. HPP treatment did not significantly affect HMF or TPC levels but led to selective changes in the phenolic profile. Despite a reduction in certain phenolic compound content, HPP for 5 and 15 min caused a significant increase in the antioxidant activity (2,2‐diphenyl‐1‐picrylhydrazyl [DPPH]) of honey from the mean value of 41.8% to values of 45.4% and 49.6%, respectively. On the other hand, HPP for 10 min did not change the antioxidant activity of tested honey. A 27.5% reduction in the equatorial diameter of pollen grains was observed after HPP combined with temperature at 75°C, suggesting an improved release of bioactive compounds. The content of specific phenolic compounds, including caffeic acid, p‐coumaric acid, sinapic acid, naringin, kaempferol, and the TPC, significantly affected the DPPH activity. The increment in the antioxidant activity of HPP honey may be attributed to selective changes in the content of certain phenolic compounds and improved their extraction from pollen grains.
Characterisation of the Cytochrome P450 Monooxygenase CYP116B46 from Tepidiphilus thermophilus as a Homogentisic Acid Generating Enzyme and its Conversion to a Peroxygenase
Authors: Akter Jina , Lee Joel H. Z. , Whelan Fiona , De Voss James J. , Bell Stephen G.
Published: December 2024

The heme enzymes of the cytochrome P450 superfamily (CYPs) catalyse the selective hydroxylation of unactivated C−H bonds in organic molecules. There is great interest in applying these enzymes as biocatalysts with a focus on self‐sufficient CYP ‘fusion’ enzymes, comprising a single polypeptide chain with the electron transfer components joined to the heme domain. Here we elucidate the function of the self‐sufficient CYP116B46 fusion enzyme, from the thermophilic bacterium Tepidiphilus thermophilus. We demonstrate that it efficiently hydroxylates aromatic organic acids, exemplified by oxidation of 2‐hydroxyphenylacetic acid to homogentisic acid (2,5‐dihydroxyphenylacetic acid), an important metabolite in bacterial catabolism. In line with the thermophilic nature of the source bacterium, activity increased at higher temperatures, (50 °C), with a catalytic preference for NADPH over NADH. While self‐sufficient fusion enzymes simplify biocatalysis; engineered peroxygenase activity is also a key advance in the application of these enzymes as biocatalysts as it eliminates the need for electron transfer partner proteins and nicotinamide cofactors. We demonstrate that a T278E mutation in the heme domain of CYP116B46, confers peroxygenase activity. This engineered peroxygenase enzyme is stable to elevated temperatures and catalytic concentrations of hydrogen peroxide, with an observed optimal activity resulting in a total turnover number of ~650.
The Biarylitides: Understanding the Structure and Biosynthesis of a Fascinating Class of Cytochrome P450 Modified RiPP Natural Products
Authors: Padva Leo , Gullick Jemma , Coe Laura J. , Hansen Mathias H. , De Voss James J. , Crüsemann Max , Cryle Max J.
Published: December 2024

The biarylitides are a recently discovered class of RiPP natural products that are fascinating both from the small size of the core peptides as well as the diversity of peptide crosslinking exhibited by the cytochrome P450 enzymes found in these systems. In this review, we address the discovery and biosynthetic diversity of these systems and discuss the methods and challenges of analysing the structures of these constrained cyclic peptides. We also discuss the structures of the P450 enzymes involved in these pathways and address the potential for alternate catalytic outcomes and activities as seen most recently with the inclusion of biarylitide related enzymes within rufomycin biosynthesis.
Riboflavin with H2‐Driven or Electrochemical Recycling: A Cheap Cofactor System for Supporting Biocatalytic Alkene Reduction
Authors: Browne Lucy B. F. , Hancox Charlotte C. , Helin Sofia M. , Todd Peter M. T. , Vincent Kylie A.
Published: December 2024

This study shows that the organic cofactor riboflavin provides a cheap and atom‐efficient source of reducing equivalents to sustain biocatalytic alkene reductions by ene‐reductase enzymes, when coupled with a H2‐driven or electrochemical recycling system. We employ the robust NiFe hydrogenase, Escherichia coli Hyd1, for H2‐driven riboflavin reduction and show the feasibility of unmediated electrochemical recycling of reduced riboflavin at a simple carbon electrode. We show that H2‐driven reduction of riboflavin can be extended to continuous flow with a packed bed reactor comprising of Hyd1 immobilized on a carbon support. These findings demonstrate that there is scope for replacing the expensive nicotinamide cofactors—NADH or NADPH with riboflavin, for applications of ene‐reductases in biotechnology in either batch or continuous flow and in electrosynthesis.
Molecularly Defined Lubricant Hydrocarbons from Olefin Metathesis
Authors: Berkson Zachariah J. , Björgvinsdóttir Snædís , Barnes Alexander B. , Riek Roland , Schowner Roman , Buchmeiser Michael R. , Gibson Stephen , Price Gregory A. , Sunley Glenn J. , Copéret Christophe
Published: December 2024

Hydrocarbon‐based lubricants are ubiquitous in industrial applications but typically consist of complex mixtures of branched molecules that are challenging to characterize and to relate to their macroscopic properties. Consequently, lubricants are typically optimized empirically for specific applications by blending base oils with organic or inorganic additives. In this study, we report the synthesis and characterization of molecularly defined lubricants via metathesis of branched terminal olefins, followed by hydrogenation. The resulting saturated hydrocarbons are characterized by ultrahigh‐field (28.2 T) 1H and 13C NMR spectroscopies to establish their molecular structures and resolve different stereoisomers, showing the utility of state‐of‐the‐art spectroscopic tools for analyzing structures of branched alkanes. Furthermore, the molecular‐level diffusion and bulk viscosity properties compare favorably to classical synthetic lubricants based on hydrogenated polyalphaolefin (PAO) blends, establishing olefin metathesis as a selective and scalable route to high‐performance lubricant oils with defined molecular structures.
PtNi Nanorods Catalysts Prepared by Magnetron Sputtering for Alkaline Hydrogen Evolution Reaction
Authors: Tian Jinsen , Qin Junhao , Zhang Hao , Tang Mingwei , Shen Jun
Published: December 2024

The development of cost‐effective and highly efficient catalysts for the hydrogen evolution reaction (HER), particularly in alkaline environments, is a critical challenge for hydrogen applications. One promising approach involves the alloying of noble metals with transition metals. This study presents the synthesis of PtNi nanorod catalysts, characterized by a thickness of 500 nm, which were fabricated via magnetron sputtering onto nickel foam. When evaluated in a 1 M KOH electrolyte, the Pt–Ni alloy demonstrates superior HER performance compared with both Ni and Pt, exhibiting an overpotential of 35 mV at 10 mA/cm2 and a Tafel slope of 29 mV/dec. The enhanced catalytic activity is attributed to several factors, including a high electrochemically active surface area, increased mass activity, elevated turnover frequency, and reduced electrochemical impedance. Furthermore, the Pt–Ni catalyst maintains remarkable stability at a current density of 10 mA/cm2 over a duration of 100 h. The improved HER performance is ascribed to the nanorod architecture, which features a high density of grain boundaries, as well as the synergistic interactions between Ni and Pt.
Oxygen‐Vacancy Rich Co3O4/CeO2 Interface for Enhanced Oxygen Reduction and Evolution Reactions
Authors: Patowary Suranjana , Watson Amber , Chetry Rashmi , Sudarsanam Putla , Russell Andrea E. , Bharali Pankaj
Published: December 2024

Oxygen reduction and evolution reactions (ORR and OER, respectively) are the two most extensively studied reactions in electrochemistry. Herein, we report the synthesis of Co3O4/CeO2/GNP (GNP = graphene nanoplatelet) electrocatalyst for ORR and OER that exhibits an early onset potential (0.85 V) and half‐wave potential (E1/2) of 0.69 V for ORR. The reported catalyst is highly durable with 87.6% retention of its initial current after a 6 h chronoamperometry test compared to 72.5% by Pt/C. It exhibits a negligible shift of E1/2 after 10,000 potential cycles for ORR. Heterogeneous oxide/oxide interfaces, oxygen vacancies and semicrystalline nature are inferenced to play a dominant role in altering the collective catalytic efficiency of Co3O4/CeO2/GNP. High concentration of oxygen vacancy defects (68%) in Co3O4/CeO2/GNP is presumed to play a dominant role here. The catalyst is bifunctional for ORR and OER with a bifunctionality index of 0.98 V and operates at an overpotential of ƞ10 = 440 mV for OER. Ex situ X‐ray absorption studies indicate an increased average oxidation state of Co by 15% in Co3O4/CeO2/GNP compared to Co3O4/GNP, aiding in preserving its inherent catalytic nature of spinel Co3O4.
Development of Bifunctional Catalysts for CO2 Capture and Conversion at Low Temperatures Under an Electric Field
Authors: Tomozawa Keidai , Tsunoji Nao , Suwa Rin , Sadakane Masahiro , Ueda Tadaharu , Ogo Shuhei
Published: December 2024

Systems for direct conversion of captured CO2 into CO (i.e., CO2 capture and reduction: CCR) via bifunctional catalysts have attracted attention as technologies for achieving carbon neutrality. However, the reported systems require additional heating above 623 K, which is still an issue from an ecological perspective. The present work realized selective CO production through CCR under isothermal conditions at 423 K by the application of a direct current electric field and a Pt‐Na/TiO2 catalyst. The application of an electric field to the catalyst is needed for CO2 conversion at low temperature, and the loading of both Pt and Na is required for CO2 capture and its selective reduction to CO. The obtained results open the door for greener CCR technologies that effectively utilize waste heat from power plants and industry.
A One‐Pot Biocatalytic Cascade to Access Diverse l‐Phenylalanine Derivatives from Aldehydes or Carboxylic Acids
Authors: Anderson Shelby R. , Gopal Madan R. , Spangler Abigail P. , Jones Michaela A. , Wyllis D'Jana R. , Kunjapur Aditya M.
Published: December 2024

Nonstandard amino acids (nsAAs) that are l‐phenylalanine derivatives with aryl ring functionalization have long been harnessed in natural product synthesis, therapeutic peptide synthesis, and diverse applications of genetic code expansion. Yet, to date, these chiral molecules have often been the products of poorly enantioselective and environmentally harsh organic synthesis routes. Here, we reveal the broad specificity of multiple natural pyridoxal 5′‐phosphate (PLP)‐dependent enzymes, specifically an l‐threonine transaldolase, a phenylserine dehydratase, and an aminotransferase, toward substrates that contain aryl side chains with diverse substitutions. We exploit this tolerance to construct a one‐pot biocatalytic cascade that achieves high‐yield synthesis of 18 diverse l‐phenylalanine derivatives from aldehydes under mild aqueous reaction conditions. We demonstrate the addition of a carboxylic acid reductase module to this cascade to enable the biosynthesis of l‐phenylalanine derivatives from carboxylic acids that may be less expensive or less reactive than the corresponding aldehydes. Finally, we investigate the scalability of the cascade by developing a lysate‐based route for preparative‐scale synthesis of 4‐formyl‐l‐phenylalanine, a nsAA with a bio‐orthogonal handle that is not readily market‐accessible. Overall, this work offers an efficient, versatile, and scalable route with the potential to lower manufacturing costs and democratize synthesis for many valuable nsAAs.
BiVO4‐Based Photoelectrochemical Water Splitting
Authors: Yi Qinghua , Wang Hao , Lee Jong‐Min
Published: December 2024

Photoelectrochemical water splitting is one of the most promising and appealing strategies for converting sunlight into sustainable hydrogen energy and has received increasing attention. Among the potential photocatalysts, BiVO4 has attracted particular attention as a photoanode material because of its appropriate bandgap (2.4 eV) and favorable band‐edge position. Moreover, its carrier mobility and hole‐diffusion length are modest, and the photocurrent density is below the theoretical expectation (7.5 mA cm−2). Recently, diverse strategies have been developed to improve the performance of BiVO4‐based photoanodes with rapid progress. In this article, engineering strategies including facet tailoring, intrinsic and extrinsic doping, surface modification, are summarized, and remaining challenges and perspective for the future research are provided.
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

Small 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

Dual 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

The 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

Nickelacyclobutanes 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

Among 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

Bromine 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

Nanographenes 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

Photomechanical 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

The 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

Designing 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

With 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

The 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

To 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

The 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

These 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 oocytes

Basic Protocol 2: In vitro fertilization and immunostaining of early‐stage embryos
Using Vesicular Stomatitis Virus as a Platform for Directed Protease Evolution
Authors: Costacurta Francesco , Rauch Stefanie , von Laer Dorothee , Heilmann Emmanuel
Published: December 2024

Antiviral drugs are essential medications to save the lives of infected people. However, they are under constant threat to become ineffective as viruses evolve quickly. Studying the development of resistance is therefore paramount to understand the impact of mutations on pharmacological treatment and to make informed decisions. Yet, such studies are open to scrutiny, as they are considered gain‐of‐function research, which is especially problematic with viruses of pandemic potential. In this article, we present a protocol that allows for the selection of antiviral resistance mutations safely, without using the actual virus (e.g., SARS‐CoV‐2, MERS‐CoV). Instead, we use vesicular stomatitis virus (VSV) that serves as a surrogate virus; like other RNA viruses, it is prone to mutations due to its polymerase lacking proofreading. By replacing parts of the VSV genome with transgenes from other viruses, VSV becomes dependent on their function. Thus, we can mount a selection pressure with antivirals targeting the transgenes to subsequently sequence selected resistance mutations. This article provides a protocol for this process as well as a sequencing pipeline that we used to collect mutations. © 2024 The Author(s). Current Protocols published by Wiley Periodicals LLC.

Basic Protocol: Using VSV as a platform for directed protease evolution

Alternate Protocol: Dose response assay with TCID50 readout

Support Protocol 1: A pipeline for high‐throughput VSV sequencing

Support Protocol 2: Rescue of VSV
Magnetic Effects in Electrocatalysis Studied with Electrochemical Impedance Spectroscopy: The Cases of Oxygen Reduction and Evolution Reactions on Cobalt Ferrite Electrodes
Authors: Giner‐Requena Alfredo , Gracia Jose , Lana‐Villarreal Teresa , Gómez Roberto
Published: December 2024

Recent years have witnessed an intense effort to unravel magnetic field effects in electrocatalysis, as they can enhance the performance of common electrocatalysts. Both experimental and theoretical studies have shown that magnetic fields may affect, among others, the macroscopic spin‐orbital ordering, charge transport, bubble release, and electron transfer kinetics. This paper highlights Electrochemical Impedance Spectroscopy (EIS) as a tool to analyze and separate the effects of magnetic field on both the oxygen reduction and evolution reactions at cobalt iron oxide electrodes. The unequivocal existence of magnetic field effects is demonstrated through EIS, which provides additional information useful to individuate the magnetic field effects. In the almost superparamagnetic nanoparticles studied here, while the magnetic field impact is positive for oxygen reduction, it turns out to be negligible in the case of oxygen evolution. In addition, this study reveals new significant insights, including the exceptionally slow relaxation kinetics of the magnetic effects and the significance of magnetic‐induced surface modifications. The fact that the effects virtually disappear in the presence of electrolyte cesium ions points to the key role of electrode surface states. This study showcases the potential of EIS to probe the effects of permanent magnetic fields in electrocatalysis.
Structural Regulating of Cu‐Based Metallic Electrocatalysts for CO2 to C2+ Products Conversion
Authors: Dai Jiawei , Zhu Jiannan , Xu You , Liu Xiaoling , Zhu Deyu , Xu Guichan , Liu Hongfang , Li Guangfang
Published: December 2024

Electrochemical carbon dioxide reduction reaction (CO2RR) to highly value‐added multi‐carbon (C2+) fuels or chemicals is a promising pathway to address environment issues and energy crisis. In the periodic table, Cu as only the candidate can convert CO2 to C2+ products such as C2H4 and C2H5OH due to the suitable absorption energy to reaction intermediate. However, application of Cu is limited for its low activity and poor selectivity. The tandem catalytic strategy can effectively solve the problems caused by single copper catalyst. In tandem catalysis, how to promote the formation, transport, adsorption and coupling of the important intermediate CO is the key issue to improve the selectivity of C2+ products. Regulating the structure of Cu‐based bimetallic can effectively promote these processes to Electrochemical CO2RR on account of its synergistic effect, electronic effect and interfacial interaction. In this review, we systematically summarized the relationship between structure of Cu‐based bimetallic catalysts with performance of electrochemical CO2RR. More importantly, we reveal that different Cu‐based bimetallic structures enhance the activity and selectivity of the catalysts by regulating the processes such as the transport and adsorption of the reaction intermediate CO. Then, we proposed well‐effective strategies to rationally design Cu‐based metallic catalysts. Finally, we put forward some challenges and opportunities that Cu‐based bimetallic catalysts would face in the development of electrochemical CO2RR technology in the future.
Co3O4‐RuO2/Ti3C2Tx MXene Electrocatalysts for Oxygen Evolution Reaction in Acidic and Alkaline Media
Authors: Cam Tran Thi My , Anh Quang The , Gnanasekaran Lalitha , Aminabhavi Tejraj M. , Vasseghian Yasser , Joo Sang‐Woo
Published: December 2024

MXene 2D materials and non‐noble transition metal oxide nanoparticles have been proposed as novel pH‐universal platforms for oxygen evolution reaction (OER), owing to the enhancement of active site exposures and conductivity. Herein, Co3O4‐RuO2 /Ti3C2Tx/carbon cloths (CRMC) were assembled in a facile way as an efficient OER platform through a hydrothermal process. The Co3O4‐RuO2/Ti3C2Tx demonstrated prominent OER catalytic performance under acidic and alkaline conditions, which showed overpotential values of 195 and 247 mV at 10 mA cm−2 with Tafel slopes of 93 and 97 mVdec−1, respectively. The experimental results demonstrated that the electron transfer from Co3O4‐RuO2 to Ti3C2Tx/carbon cloth played a remarkable role in promoting OER catalytic activity. Further OER characterization indicated that the enhanced multi‐electron reaction kinetics are attributed to Co and Ru acting as the primary active places for O2 adsorption and activation, which facilitated the generation of *OOH intermediate.
Induction Heating for the Electrification of Catalytic Processes
Authors: Truong‐Phuoc Lai , Duong‐Viet Cuong , Nhut Jean‐Mario , Pappa Anastasia , Zafeiratos Spyridon , Pham‐Huu Cuong
Published: December 2024

The increasing availability of electrical energy generated from clean, low‐carbon, renewable sources like solar and wind power is paving the way for a more sustainable future. This has resulted in a growing trend in the chemical industry to increase the share of electricity use in chemical processes, particularly catalytic ones. This shift towards electrifying catalytic processes offers significant environmental benefits. Current practices rely heavily on fossil fuel‐based burners, primarily using natural gas, which contribute significantly to greenhouse gas emissions. Therefore, replacing fossil fuels with electricity can significantly reduce the carbon footprint associated with chemical production. Additionally, the energy‐intensive production of metal catalysts used in these processes further exacerbates the environmental impact. This review focuses on the electrification of chemical processes, particularly using induction heating (IH), as a method to reduce the environmental impact of both catalyst production and operation. IH shows promise compared to conventional heating methods, since it offers a cleaner, more efficient, and precise way to heat catalysts in chemical processes by directly generating heat within the catalyst itself. It can potentially even enhance the reaction performance through its influence on the reaction mechanism. By exploring recent advancements in IH‐driven catalytic processes, the review delves into how this method is revolutionizing catalysis by enhancing performance, selectivity, and sustainability. It highlights recent breakthroughs and discusses perspectives for further exploration in this rapidly developing field.
Trophic Change and Community Decline in Acrobat Ants After Rainforest Conversion to Cash Crops
Authors: Ehlers Jessica , Hartke Tamara R. , Janotta Noah , Mawan Amanda , Nazarreta Rizky , Desriana Rizky , Hidayat Purnama , Buchori Damayanti , Scheu Stefan , Pollierer Melanie M. , Drescher Jochen
Published: December 2024

The conversion of tropical rainforests to agriculture causes population declines and biodiversity loss across taxa. This impacts ants (Formicidae), a crucial tropical group for ecosystem functioning. While biodiversity loss among ants is well documented, the responses of individual ant taxa and their adjustments in trophic strategies to land‐use change are little studied. Here, we investigated a collection of > 12,000 acrobat ants (Crematogaster) from 14 species collected by canopy fogging in four land‐use systems in Jambi Province, Sumatra, including (1) lowland rainforest, (2) jungle rubber (low impact rubber agroforestry), and monocultures of (3) rubber and (4) oil palm. Abundance‐weighted trophic positions as indicated by stable isotopes of carbon and nitrogen were significantly different between land uses: Lower average, maximum, minimum and range of δ13C values in monocultures than in rainforest and jungle rubber indicate a shift of Crematogaster towards more plant‐based resources, but may be driven substantially by the “canopy effect” of differential carbon assimilation of leaves between lower and higher canopy. Similar Δ15N average, maximum and minimum among the land uses, but a significantly reduced range of Δ15N in monocultures, suggest lowered trophic diversity and increased stochasticity of trophic niches in monocultures. In contrast, community decline in Crematogaster was very pronounced, with density, richness and rarity in monocultures of rubber and oil palm at a fraction of that in rainforest and jungle rubber. Crematogaster communities in oil palm formed a subset of those in rubber, which were a subset of those in jungle rubber, which were a subset of those in rainforest. A notable exception was Crematogaster ferarii, which was exclusively found in oil palm. In conclusion, tropical land‐use change induces slight shifts in the trophic structure of Crematogaster communities, but massive declines in its density and diversity. This likely affects Crematogaster‐driven ecosystem functions in agricultural systems in Southeast Asia.