bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Hybrid Redox‐Mediated Zinc‐Air Fuel Cell for Scalable and Sustained Power Generation
Authors: Song Yuxi , Xia Lingchao , Salla Manohar , Xi Shibo , Fu Weiyin , Wang Wanwan , Gao Mengqi , Huang Songpeng , Huang Shiqiang , Wang Xun , Yu Xingzi , Niu Tong , Zhang Yuqi , Wang Shijie , Han Ming , Ni Meng , Wang Qing , Zhang Hang 
Published: February 2024

AbstractZinc‐air batteries (ZABs) have attracted considerable attention for their high energy density, safety, low noise, and eco‐friendliness. However, the capacity of mechanically rechargeable ZABs was limited by the cumbersome procedure for replacing the zinc anode, while electrically rechargeable ZABs suffer from issues including low depth of discharge, zinc dendrite and dead zinc formation, and sluggish oxygen evolution reaction, etc. To address these issues, we report a hybrid redox‐mediated zinc‐air fuel cell (HRM‐ZAFC) utilizing 7,8‐dihydroxyphenazine‐2‐sulfonic acid (DHPS) as the anolyte redox mediator, which shifts the zinc oxidation reaction from the electrode surface to a separate fuel tank. This approach decouples fuel feeding and electricity generation, providing greater operation flexibility and scalability for large‐scale power generation applications. The DHPS‐mediated ZAFC exhibited a superior peak power density of 0.51 W/cm2 and a continuous discharge capacity of 48.82 Ah with ZnO as the discharge product in the tank, highlighting its potential for power generation.
Anion‐modulated Ion Conductor with Chain Conformational Transformation for stabilizing Interfacial Phase of High‐Voltage Lithium Metal Batteries
Authors: Wang Chao , Zhao Xiaoxue , Li Dabing , Yan Chong , Zhang Qiang , Fan Li‐Zhen 
Published: February 2024

AbstractIn solid‐state lithium metal batteries (SSLMBs), the inhomogeneous electrolyte‐electrode interphase layer aggravates the interfacial stability, leading to discontinuous interfacial ion/charge transport and continuous degradation of the electrolyte. Herein, we constructed an anion‐modulated ionic conductor (AMIC) that enables in situ construction of electrolyte/electrode interphases for high‐voltage SSLMBs by exploiting conformational transitions under multiple interactions between polymer and lithium salt anions. Anions modulate the decomposition behavior of supramolecular poly (vinylene carbonate) (PVC) at the electrode interface by changing the spatial conformation of the polymer chains, which further enhances ion transport and stabilizes the interfacial morphology. In addition, the AMIC weakens the “Li+‐solvation” and increases Li+ vehicle sites, thereby enhancing the lithium‐ion transport number (tLi+=~0.67). Consequently, Li || LiNi0.8Co0.1Mn0.1O2 cell maintains about 85 % capacity retention and Coulombic efficiency >99.8 % in 200 cycles at a charge cut‐off voltage of 4.5 V. This study provides a new understanding of lithium salt anions regulating polymer chain segment behavior in the solid‐state polymer electrolyte (SPE) and highlights the importance of the ion environment in the construction of interfacial phases and ionic conduction.
Darstellung der chemischen Diversität bioaktiver Meroterpenoide, die vom größten Organismus der Erde produziert werden
Authors: Pfütze Sebastian , Charria‐Girón Esteban , Schulzke Esther , Toshe Rita , Khonsanit Artit , Franke Raimo , Surup Frank , Brönstrup Mark , Stadler Marc 
Published: February 2024

AbstractIn dieser Forschungsarbeit untersuchten wir die Diversität von Melleolid‐Meroterpenoiden, die von Armillaria ostoyae, einem der größten und ältesten Organismen der Erde, produziert werden. Dazu verwendeten wir Extrakte aus flüssiger und fester Kulturführung. Die Studie führte zur Isolierung und Identifikation von drei neuartigen dimeren Bismelleoliden (1–3) und drei neuen fettsäuresubstituierten Kongeneren (4–6) sowie 11 neuen (7–17) und 21 bekannten (18–38) Derivaten. Die Strukturaufklärung erfolgte durch 1D‐ und 2D NMR‐Spektroskopie, HRESI‐MS‐Daten und Analyse der ROESY‐Spektren für relative Konfigurationen. Absolute Konfigurationen wurden durch den Vergleich von Kristallstrukturen und ECD‐Spektren bestimmt. Eine Substanzbibliothek von Melleolid‐Meroterpenoiden ermöglichte eine Metabolomik‐Studie und zeigte Produktionsmuster unter verschiedenen Kulturbedingungen auf. Unter Verwendung dieser Substanzbibliothek wurden die antimikrobiellen und zytotoxischen Aktivitäten der hierin beschriebenen Substanzen untersucht und gezeigt, dass eine Δ2,4‐Doppelbindung nicht entscheidend für die antimykotische Aktivität ist. Die Zytotoxizität war hingegen an das Vorhandensein eines Aldehyds an C‐1 gebunden, ging jedoch durch eine Hydroxylierung an C‐13 verloren. Chemoinformatische Untersuchungen zeigten das komplexe Zusammenspiel zwischen chemischen Modifikationen und biologischen Eigenschaften. Diese Studie stellt die erste systematische Untersuchung der Vielfalt von Meroterpenoiden aus Armillaria spp. mittels MS‐basierter, nicht‐gezielter Metabolomik dar und bietet Einblicke in die Struktur‐Aktivitäts‐Beziehungen dieser Substanzklasse durch innovative Chemoinformatische Ansätze.
Ring Expansion toward Disila‐carbocycles via Highly Selective C−Si/C−Si Bond Cross‐Exchange
Authors: Liu Min , Yan Nuo , Tian Haowen , Li Bo , Zhao Dongbing 
Published: February 2024

AbstractHerein, we successfully inhibited the preferential homodimerization and C−Si/Si−H bond cross‐exchange of benzosilacyclobutenes and monohydro‐silacyclobutanes and achieved the first highly selective C−Si/C−Si bond cross‐exchange reaction by deliberately tuning the Ni‐catalytic system, which constitutes a powerful and atom‐economical ring expansion method for preparing medium‐sized cyclic compounds bearing two silicon atoms at the ring junction, which are otherwise inaccessible. The DFT calculation explicitly elucidated the pivotal role of Si−H bond at silacyclobutanes and the high ring strain of two substrates in realizing the two C−Si bonds cleavage and reformation in the catalytic cycle.
Water‐Tolerant Superbase Polyoxometalate [H2(Nb6O19)]6− for Homogeneous Catalysis
Authors: Kikkawa Soichi , Fujiki Yu , Chudatemiya Vorakit , Nagakari Hiroki , Shibusawa Kazuki , Hirayama Jun , Nakatani Naoki , Yamazoe Seiji 
Published: February 2024

AbstractHere, doubly protonated Lindqvist‐type niobium oxide cluster [H2(Nb6O19)]6–, fabricated by microwave‐assisted hydrothermal synthesis, exhibited superbase catalysis for Knoevenagel and crossed aldol condensation reactions accompanied by activating C−H bond with pKa >26 and proton abstraction from a base indicator with pKa=26.5. Surprisingly, [H2(Nb6O19)]6− exhibited water‐tolerant superbase properties for Knoevenagel and crossed aldol condensation reactions in the presence of water, although it is well known that the strong basicity of metal oxides and organic superbase is typically lost by the adsorption of water. Density functional theory calculation revealed that the basic surface oxygens that share the corner of NbO6 units in [H2(Nb6O19)]8− maintained the negative charges even after proton adsorption. This proton capacity and the presence of un‐protonated basic sites led to the water tolerance of the superbase catalysis.
Innovation and Team Spirit: The Magic of Science Competitions Seen through the Lens of the Compound Challenge
Authors: Seipp Charles A. , Monks Brendan Michael , Karnysh Iuliia , Betz Ulrich A. K. 
Published: February 2024

AbstractFor five years now, Merck KGaA, Darmstadt, Germany has hosted The Compound Challenge—a global retrosynthesis competition. When the event kicked off in 2018 on the occasion of the 350th anniversary of the company, no one could have predicted the path it would take—from a novel competition to a pivotal event within the synthetic chemistry community. But what makes the Compound Challenge tick and what drives its popularity? And, more importantly, what lessons can be taken from the Compound Challenge and applied to other challenges in scientific education and outreach? In this Viewpoint Article we will tell the story of the Compound Challenge, from its inception to its current status. Through examining feedback following each of its iterations, we begin to define what makes an open innovation challenge so compelling. It is our hope that educators, leaders, and innovators will be able to learn from our successes as well as our mistakes and apply these lessons to their future outreach activities.
Depicting the Chemical Diversity of Bioactive Meroterpenoids Produced by the Largest Organism on Earth
Authors: Pfütze Sebastian , Charria‐Girón Esteban , Schulzke Esther , Toshe Rita , Khonsanit Artit , Franke Raimo , Surup Frank , Brönstrup Mark , Stadler Marc 
Published: February 2024

AbstractIn this investigation, we explored the diversity of melleolide‐type meroterpenoids produced by Armillaria ostoyae, one of the largest and oldest organisms on Earth, using extracts from liquid and solid fermentation media. The study unveiled three unprecedented dimeric bismelleolides and three novel fatty‐acid‐substituted congeners, along with 11 new and 21 known derivatives. The structures were elucidated by 1D and 2D NMR spectroscopy and HRESI‐MS, and ROESY spectral analysis for relative configurations. Absolute configurations were determined from crystal structures and through ECD spectra comparison. A compound library of melleolide‐type meroterpenoids facilitated metabolomics‐wide associations, revealing production patterns under different culture conditions. The library enabled assessments of antimicrobial and cytotoxic activities, revealing that the Δ2,4 double bond is not crucial for antifungal activity. Cytotoxicity was linked to the presence of an aldehyde at C1, but lost with hydroxylation at C13. Chemoinformatic analyses demonstrated the intricate interplay of chemical modifications on biological properties. This study marks the first systematic exploration of Armillaria spp. meroterpenoid diversity by MS‐based untargeted metabolomics, offering insight into structure–activity relationships through innovative chemoinformatics.
Total Synthesis of Principinol B
Authors: Du Qiang , Fan Zhibo , Yang Ming 
Published: February 2024

AbstractWe have accomplished the first and asymmetric total synthesis of principinol B, a grayanoid possessing an oxabicyclo[3.2.1] architecture. A functionalized 5/7/6/5 tetracyclic intermediate was assembled in a convergent manner by a diastereoselective intermolecular aldol reaction and subsequent carbonyl–olefin metathesis of two enantiomerically enriched fragments. The oxabicyclo[3.2.1] architecture containing a 6,10‐ether bridge was constructed by the Williamson ether synthesis.
Topology Controlled All‐(Meth)acrylic Thermoplastic Elastomers by Multi‐Functional Lewis Pairs‐Mediated Polymerization
Authors: Li Chengkai , Zhao Wuchao , He Jianghua , Zhang Yuetao 
Published: February 2024

AbstractIt remains challenging to synthesize all‐(meth)acrylic triblock thermoplastic elastomers (TPEs), due to the drastically different reactivities between the acrylates and methacrylates and inevitable occurrence of side reactions during polymerization of acrylates. By taking advantage of the easy structural modulation features of N‐heterocyclic olefins (NHOs), we design and synthesize strong nucleophilic tetraphenylethylene‐based NHOs varying in the number (i.e. mono‐, dual‐ and tetra−) of initiating functional groups. Its combination with bulky organoaluminum [iBuAl(BHT)2] (BHT=bis(2,6‐di‐tBu‐4‐methylphenoxy)) constructs Lewis pair (LP) to realize the living polymerization of both acrylates and methacrylates, furnishing polyacrylates with ultrahigh molecular weight (Mn up to 2174 kg ⋅ mol−1) within 4 min. Moreover, these NHO‐based LPs enable us to not only realize the control over the polymers’ topology (i.e. linear and star), but also achieve triblock star copolymers in one‐step manner. Mechanical studies reveal that the star triblock TPEs exhibit better mechanical properties (elongation at break up to 1863 % and tensile strength up to 19.1 MPa) in comparison with the linear analogs. Moreover, the presence of tetraphenylethylene group in the NHOs entitled the triblock TPEs with excellent AIE properties in both solution and solid state.
Topologically Tunable Conjugated Metal–Organic Frameworks for Modulating Conductivity and Chemiresistive Properties for NH3 Sensing
Authors: Shan Zhen , Xiao Jian‐Ze , Wu Miaomiao , Wang Jinjian , Su Jian , Yao Ming‐Shui , Lu Ming , Wang Rui , Zhang Gen 
Published: February 2024

AbstractElectrically conductive metal–organic frameworks (cMOFs) have garnered significant attention in materials science due to their potential applications in modern electrical devices. However, achieving effective modulation of their conductivity has proven to be a major challenge. In this study, we have successfully prepared cMOFs with high conductivity by incorporating electron‐donating fused thiophen rings in the frameworks and extending their π‐conjugated systems through ring‐closing reactions. The conductivity of cMOFs can be precisely modulated ranging from 10−3 to 102 S m−1 by regulating their dimensions and topologies. Furthermore, leveraging the inherent tunable electrical properties based on topology, we successfully demonstrated the potential of these materials as chemiresistive gas sensors with an outstanding response toward 100 ppm NH3 at room temperature. This work not only provides valuable insights into the design of functional cMOFs with different topologies but also enriches the cMOF family with exceptional conductivity properties.
A Fluorous Peptide Amphiphile with Potent Antimicrobial Activity for the Treatment of MRSA‐induced Sepsis and Chronic Wound Infection
Authors: Hu Jingjing , Liu Nan , Fan Qianqian , Gu Yunqing , Chen Sijia , Zhu Fang , Cheng Yiyun 
Published: February 2024

AbstractThe rising prevalence of global antibiotic resistance evokes the urgent need for novel antimicrobial candidates. Cationic lipopeptides have attracted much attention due to their strong antimicrobial activity, broad‐spectrum and low resistance tendency. Herein, a library of fluoro‐lipopeptide amphiphiles was synthesized by tagging a series of cationic oligopeptides with a fluoroalkyl tail via a disulfide spacer. Among the lipopeptide candidates, R6F bearing six arginine moieties and a fluorous tag shows the highest antibacterial activity, and it exhibits an interesting fluorine effect as compared to the non‐fluorinated lipopeptides. The high antibacterial activity of R6F is attributed to its excellent bacterial membrane permeability, which further disrupts the respiratory chain redox stress and cell wall biosynthesis of the bacteria. By co‐assembling with lipid nanoparticles, R6F showed high therapeutic efficacy and minimal adverse effects in the treatment of MRSA‐induced sepsis and chronic wound infection. This work provides a novel strategy to design highly potent antibacterial peptide amphiphiles for the treatment of drug‐resistant bacterial infections.
Gold(I) N‐heterocyclic carbene (NHC) complexes containing 6‐mercaptopurine derivatives and their in vitro anticancer and anti‐inflammatory effects
Authors: Trávníček Zdeněk , Vančo Ján , Čajan Michal , Belza Jan , Popa Igor , Hošek Jan , Lenobel René , Dvořák Zdeněk 
Published: February 2024

A series of eight N‐heterocyclic carbenes (NHC) gold(I) complexes, involving 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (iPr) ligand in combination with 6‐mercaptopurine derivatives (HL1–8), has been prepared and thoroughly characterized, including elemental analysis, mass spectrometry, infrared and multinuclear NMR spectroscopy, and single crystal X‐ray analysis. The complexes, showing general composition of [Au (iPr)(Ln)] 1–8, were evaluated for their in vitro cytotoxicity against four human cancer cell lines including A2780 (ovarian) and A2780R (ovarian Cisplatin resistant), PC3 (prostate) and MCF‐7 (breast), and normal human MRC‐5 cells (lung fibroblasts). The complexes revealed significant cytotoxicity, with the best IC50 values ≈ 3.4–6.4 μM against A2780 and reasonable selectivity. Cellular effects of the selected complexes on the A2780 cells were evaluated using various flow cytometry assays. Complexes 1, 3, and 4 showed a strong pro‐apoptotic effect and a strong effect on the loss of mitochondrial membrane potential. These findings indicate that their major mechanism of action is based on the collapse of the mitochondrial metabolism and activation of the intrinsic signaling pathway of apoptosis, consequently resulting in cell death. The complexes 1–8 revealed only negligible effect on the production of inflammatory‐related cytokine (TNF‐α), as well as the activation of nuclear factor kappa‐light‐chain‐enhancer of activated B cells (NF‐κB) or peroxisome proliferator‐activated receptor gamma (PPARγ). Moreover, the shotgun proteomic analysis was performed, and the obtained results suggest that the mechanism of action of complexes 1, 3, and 4 differs somewhat from that of Auranofin.
Enhanced hydrolytic stability and photocatalytic performance of a uranium‐based organic framework by hybrid carbon nanotubes
Authors: Gu Dongxu , Qin Xudong , Che Guang , Chen Lu , Yang Weiting 
Published: February 2024

Owing to their highly predictable porous structures, facile synthesis, and the presence of functional open metal sites, metal–organic frameworks (MOFs) are extensively employed in various fields, including energy storage, catalysis, adsorption, and separation. Nevertheless, the limited hydrolytic stability exhibited by numerous MOFs poses a significant challenge to their practical application. In the present study, we present the synthesis and characterization of a uranyl organic framework (TCPP‐U1) with a highly porous structure, which is constructed by assembling cobalt, uranyl, and the porphyrin ligand 5,10,15,20‐tetra(4‐carboxyphenyl)porphyrin (TCPP). However, TCPP‐U1 demonstrates poor hydrolytic stability when exposed to water (the structure can be destroyed even after 2 min of exposure to water), greatly impeding its potential applications that would benefit from its high surface area. To address this limitation, we developed a hybrid composite by incorporating acid‐treated multi‐walled carbon nanotubes (CNTs) into the TCPP‐U1 framework via a solvothermal method designated as CNTs@TCPP‐U1. Remarkably, the obtained CNTs@TCPP‐U1 composite possesses an identical crystal structure and morphology to the original TCPP‐U1 yet exhibits significant enhancements in hydrolytic stability (the structure remains stable even after 3 days of immersion in water). Furthermore, CNTs@TCPP‐U1 demonstrates a significant photocatalytic effect on the degradation of tetracycline hydrochloride in aqueous solutions. The reaction rate constant (k) for the pseudo‐first‐order kinetic model is 0.0059 min−1. Our findings present a novel perspective for enhancing the stability and expanding the performance of MOFs materials.
Monitoring the movement, habitat use and mortality of captive‐bred reintroduced gharials in the Mahanadi River, India
Authors: Rath Laxmi Prasad , Dash Suraj Kumar , Khan Ashaharraza , Mohapatra Rajesh Kumar , Kumar Sanjeet , Nair Manoj V. , Paul Shashi , Maharana Sudarsan 
Published: February 2024

Abstract

Gharials (Gavialis gangeticus) are endemic to the Indian subcontinent and meet IUCN Red List criteria for critically endangered.
The Mahanadi River, located in the southernmost part of the gharial range, currently has a few individuals survived although historically had many more.
Between 2019 and 2021, the movement, habitat use and survival rate of 13 captive‐bred (juvenile = 6, subadult = 5, adult = 2) reintroduced gharials were monitored using very high frequency (VHF) radio transmitters tracked manually from the river banks. Kernel density estimates and generalized linear model (GLM) were used to investigate the home range and habitat use of individuals.
Tagged gharials travelled throughout the river system, with the highest movement during summer and the least in winter. Females moved further and established larger linear home ranges than males. Kernel home ranges were established in and around the Satkosia Gorge wildlife sanctuary, which has favourable ecological conditions for gharials, namely, deep water, sandbars, abundant fish and low human disturbance.
Gharial mortality was detected during the study, and post‐mortem examination indicated anthropogenic causes. The use of explosives for fishing, entanglement in fishing nets and a lack of ecological awareness within local communities were identified as key factors that need to be addressed if gharials are to survive the Mahanadi River.
Intact shallow and mesophotic assemblages of large carnivorous reef fishes underscore the importance of large and remote protected areas in the Coral Triangle
Authors: Salvador Mikaela L. , Utzurrum Jean Asuncion T. , Murray Ryan , Delijero Kymry , Conales Segundo F. , Bird Christopher E. , Gauthier David T. , Abesamis Rene A. 
Published: February 2024

Abstract
Overfishing remains a threat to coral reef fishes worldwide, with large carnivores often disproportionately vulnerable. Marine protected areas (MPAs) can restore fish populations and biodiversity, but their effect has been understudied in mesophotic coral ecosystems (MCEs), particularly in the Coral Triangle.
Videos were analysed from baited remote underwater video systems deployed in 2016 to investigate the assemblage structure of large carnivorous fishes at shallow (4–12 m) and mesophotic (45–96 m) depths in two of the largest and most isolated MPAs in the Philippines: an uninhabited, fully no‐take MPA enacted in 1988 (Tubbataha Reefs Natural Park) and an archipelagic municipality surrounded by an extensive but not fully no‐take MPA declared in 2016 (Cagayancillo). Taxa focused on were groupers (Serranidae), snappers (Lutjanidae), emperors (Lethrinidae), jacks (Carangidae) and the endangered Cheilinus undulatus (Labridae).
Mean abundance and species richness were not greater in TRNP than in Cagayancillo regardless of depth despite long‐term protection in the former. Limited impacts of fishing in Cagayancillo may explain this result. Differentiation of fish assemblages was evident between TRNP and Cagayancillo but more obvious between depths at each location, probably due more to habitat than MPA effects. In Cagayancillo, overall carnivorous reef fish, grouper and jack mean abundance were 2, 2 and 10 times higher, respectively, at mesophotic depths, suggesting that MCEs can serve as deep refugia from fishing.
These findings of differentiation between depths and higher abundance of certain taxa in mesophotic depths emphasize that MCEs are distinct from shallow reefs, serve as important habitat for species susceptible to overfishing and, thus, must be explicitly included in the design of MPAs. This study also highlights the value of maintaining strict protection of MPAs like TRNP for the Coral Triangle and an opportunity to safeguard intact fish assemblages in Cagayancillo by expanding its no‐take zones.