bluuebunny/crossref_metadata_2025_split huggingface dataset:
DRD4 Interacts with TGF‐β Receptors to Drive Colorectal Cancer Metastasis Independently of Dopamine Signaling Pathway
Authors: Zhou Yuan , Tang Jinlong , Weng Menghan , Zhang Honghe , Lai Maode 
Published: December 2024

AbstractThe functional and pharmacological significance of dopamine receptor D4 (DRD4) in psychiatric and neurological disorders is well elucidated. However, the roles of DRD4 in colorectal cancer (CRC) remain unclear. This study observes a significant upregulation of DRD4 expression in clinical samples, which is negatively correlated with patient prognosis. In vitro, overexpression of DRD4 causes a constitutive activation of β‐Arrestin2/PP2A/AKT independent of dopamine. Interestingly, this classical signaling pathway is not associated with the phenotype of DRD4‐promoted migration and invasion in CRC cells. Instead, DRD4 interacts with transforming growth factor beta receptors (TGFBR1 and TGFBR2) to activate Smad2 phosphorylation and promote Smad2/Smad4 complex nucleus translocation. Then, SNAI1 and JAG1 are transcriptionally activated to induce epithelial‐mesenchymal transition and enhance the metastatic potential of CRC. Notably, the COOH‐terminal domain is identified as the key intracellular region for the pro‐metastatic roles of DRD4. Furthermore, treatment with a TGFBR1 inhibitor combined with a BMP inhibitor effectively counteracts the pro‐metastatic effects induced by DRD4 both in vitro and in vivo. In conclusion, these findings uncover an unconventional role for DRD4 beyond its classic function as a neurotransmitter receptor. The intracellular signaling of DRD4 interacting with TGFBR1 can be targeted pharmacologically for CRC therapy.
Photocatalytic Cascade Alkylation/Cyclization of N‐Arylacrylamides with Simple Alkanes: A Convenient Approach to Quaternary C3 Alkylated Oxindoles
Authors: Ye Liang , Xu Haibin , Yu Jiong , Yan Han , Wang Min , Li Pinhua 
Published: December 2024

AbstractA convenient and efficient protocol for the synthesis of 3,3‐dialkylated oxindoles through photocatalytic aerobic radical‐cascade alkylation/cyclization of N‐arylacrylamides with the alkyl radicals generated from simple alkanes is described. This method features a broad substrate scope, inexpensive alkyl radical precursors, simple conditions and good yields.
Program‐Modulated Kinetics of Perovskite‐Film Growth by Molecular “Thruster” for High‐Efficiency and Stable Perovskite Solar Cells
Authors: Han Chuanshuai , Wu Yeyong , Xu Guiying , Wu Xiaoxiao , Xu Jiacheng , Xu Tingting , Huang Shihao , Shen Yunxiu , Cao Zhiyun , Chen Weijie , Xu Xiaoping , Li Yaowen 
Published: December 2024

AbstractThe rapid reaction between lead iodide (PbI2) and formamidinium iodide (FAI) complicates the fabrication of high‐quality formamidinium lead iodide (FAPbI3) films. Conventional methods, such as using nonvolatile small molecular additives to slow the reaction, often result in buried interfacial voids and molecule diffusion, compromising the devices’ operational stability. In this study, we introduced a molecular “thruster”—a hypervalent iodine (III) compound with three carbonyl groups and a C−−I+ bond—that possesses coordination and dissociation abilities, enabling programed modulation of perovskite‐film growth kinetics. Initially, the three carbonyl groups coordinate with PbI2 to slow the reaction between FAI and PbI2, preventing δ‐phase formation. As temperature rises, the C−−I+ bond dissociates, promoting perovskite growth and the dissociated product iodobenzene will promote solvent volatilization, thus avoiding buried interfacial voids. Another product, a carbene compound with eight lone pair electrons sufficiently passivate the undercoordinated Pb2+ defects and anchors at grain boundaries without diffusion. Consequently, the resultant FAPbI3 film displays high‐quality with enhanced phase purity, compact morphology, and reduced defects. Evidently, 0.062‐ and 1.004‐cm2 pero‐SCs achieve power conversion efficiencies (PCEs) of up to 26.06 % (25.79 % certified) and 24.65 %, respectively. This approach also controls perovskite‐film growth on plastic substrates, resulting in flexible pero‐SCs with an impressive PCE of 25.12 %.
Erzeugung von HO−Zn−N2‐aktiven Zentren in Zeolithischen‐Imidazolat‐Gerüsten für Verbesserte (Foto−)elektrokatalytische Wasserstoffentwicklung
Authors: Huang Zheao , Wang Zhouzhou , Zhou Qiancheng , Rabl Hannah , Naghdi Shaghayegh , Yang Ze , Eder Dominik 
Published: December 2024

AbstractErzeugung und Charakterisierung wohldefinierter aktiver Zentren in zeolithischen Imidazolat‐basierten Gerüststrukturen (engl. zeolitic imidazolate frameworks ZIFs) ist zetral um ein grundlegendes Verständnis hinsichtlich der mechanistischen Details der (foto‐)elektrokatalytischen Wasserstoffentwicklungsreaktion (engl. hydrogen evolution reaction, HER) in diesen Hybridmaterialien zu erhalten. In dieser Arbeit erzeugen wirungesättigte, offene Metallzentren (engl. open metal sites) in ZIFs durch eine selektive Ligandenentfernungsstrategie (engl. selective ligand removal SeLiRe), charakterisieren diese umfassend hinsichtlich deren strukturelle und elektronische Eigenschaften und untersuchen deren Auswirkungen auf die HER Aktivität. In situ‐elektrochemische Analysen und Röntgenabsorptionsspektroskopie zeigen die Bildung von HO−Zn−N2 Zentren mit hoher Wertigkeit durch die Bindung von Zn−N2 mit Hydroxidionen des Elektrolyten. Das optimale OMS‐ZIF weist eine niedrige Überspannung von 0,41 V auf, um eine Stromdichte von 1,0 A cm−2 mit einer Stabilität von 120 Stunden zu erreichen. Theoretische Simulationen zeigen, dass diese aktiven Zentren die Aktivierungskinetik von Wassermolekülen beschleunigen und somit die Effizienz des Volmer‐Schrittes verbessern. Diese Arbeit zeigt eine vielseitige Strategie zur Einführung katalytisch aktiver Zentren in ZIFs und liefert neue Erkenntnisse über den elektrokatalytischen Mechanismus in alkalischen Medien.
Anionic Doping in Layered Transition Metal Chalcogenides for Robust Lithium‐Sulfur Batteries
Authors: Huang Chen , Yu Jing , Yue Zhang Chao , Cui Zhibiao , He Ren , Yang Linlin , Nan Bingfei , Li Canhuang , Qi Xuede , Qi Xueqiang , Li Junshan , Yuan Zhou Jin , Usoltsev Oleg , Simonelli Laura , Arbiol Jordi , Lei Yao‐Jie , Sun Qing , Wang Guoxiu , Cabot Andreu 
Published: December 2024

AbstractLithium‐sulfur batteries (LSBs) are among the most promising next‐generation energy storage technologies. However, a slow Li−S reaction kinetics at the LSB cathode limit their energy and power densities. To address these challenges, this study introduces an anionic‐doped transition metal chalcogenide as an effective catalyst to accelerate the Li−S reaction. Specifically, a tellurium‐doped, carbon‐supported bismuth selenide with Se vacancies (Te−Bi2Se3–x@C) is prepared and tested as a sulfur host in LSB cathodes. X‐ray absorption and in situ X‐ray diffraction analyses reveal that Te doping induces lattice distortions and modulates the local coordination environment and electronic structure of Bi atoms to promote the catalytic activity toward the conversion of polysulfides. Additionally, the generated Se vacancies alter the electronic structure around atomic defect sites, increase the carrier concentration, and activate unpaired cations to effectively trap polysulfides. As a result, LSBs based on Te−Bi2Se3–x@C/S cathodes demonstrate outstanding specific capacities of 1508 mAh ⋅ g−1 at 0.1 C, excellent rate performance with 655 mAh ⋅ g−1 at 5 C, and near‐integral cycle stability over 1000 cycles. Furthermore, under high sulfur loading of 6.4 mg ⋅ cm−2, a cathode capacity exceeding 8 mAh ⋅ cm−2 is sustained at 0.1 C current rate, with 6.4 mAh ⋅ cm−2 retained after 300 cycles under lean electrolyte conditions (6.8 μL ⋅ mg−1).
High‐Valent Cobalt‐Difluoride in Oxidative Fluorination of Saturated Hydrocarbons
Authors: Das Agnideep , Twamley Brendan , Kelly Oscar R. , Panda Chakadola , Richardson Paul , McDonald Aidan R. 
Published: December 2024

AbstractThe heme paradigm where Fe=O acts as the C−H oxidant and Fe−OH rebounds with the formed carbon‐centered radical guides the design of the prototypical synthetic hydroxylation catalyst. We are exploring methods to evolve beyond the metal‐oxo oxidant and hydroxide rebound, to incorporate a wider array of functional group. We have demonstrated the application of CoII(OTf)2 (10 mol% catalyst; OTf=trimfluoromethanesulfonate) in combination with polydentate N‐donor ligands (e. g. BPMEN=N,N′‐dimethyl‐N,N′‐bis(pyrid‐2‐ylmethyl)ethane‐1,2‐diamine) and Selectfluor in the oxidative fluorination of saturated hydrocarbons in high yields. The addition of CsF to the reaction mixture induced near‐quantitative yields of fluorinated saturated hydrocarbons (>90 % yield of fluorinated product). For 1‐hydroxy, 1‐acetyl, 1‐carboxy‐, and 1‐acetamido‐adamantane, we demonstrated selective fluorination at the 3‐position. We propose two mechanisms for the CoII‐catalyzed reaction: either (i) an N‐radical, derived from Selectfluor, acted as the C−H oxidant followed by radical rebound with CoIII−F; or (ii) a CoIV−(F)2 species was the C−H oxidant followed by radical rebound with CoIII−F. Our combined spectroscopic, kinetic, and chemical trapping evidence suggested that an N‐radical was not the active oxidant. We concluded that a CoIV−(F)2 species was the likely active oxidant and CoIII−F was the likely F‐atom donor to a carbon centered radical producing a C−F bond.
Porous Halogen‐Bonded Frameworks Assembled through Hetero‐polytopic Ion Pair Templation
Authors: Smith Jordan N. , Hunter Callum I. , Doan Huan V. , Ting Valeska P. , White Nicholas G. 
Published: December 2024

AbstractHalogen‐bonding (XB) interactions have been extensively studied in the preparation of crystalline frameworks, yet porous 3D framework materials built on XBs remain elusive. The donor‐acceptor interactions are strengthened by use of anionic XB acceptors; however, the requisite charge‐balancing cations typically disrupt the framework and occupy potential void space. In this work, we prepare a tetratopic XB donor bearing a crown ether moiety for sodium cation sequestration. We show that when this ionpair receptor is crystallised with NaCl it gives a 3D framework that is porous to solvent and vapour, and undergoes single‐crystal‐to‐single‐crystal reactions.
Fragment Discovery by X‐Ray Crystallographic Screening Targeting the CTP Binding Site of Pseudomonas Aeruginosa IspD
Authors: Willocx Daan , D'Auria Lucia , Walsh Danica , Scherer Hugo , Alhayek Alaa , Hamed Mostafa M. , Borel Franck , Diamanti Eleonora , Hirsch Anna K. H. 
Published: December 2024

AbstractWith antimicrobial resistance (AMR) reaching alarming levels, new anti‐infectives with unprecedented mechanisms of action are urgently needed. The 2‐C‐methylerythritol‐D‐erythritol‐4‐phosphate (MEP) pathway represents an attractive source of drug targets due to its essential role in numerous pathogenic Gram‐negative bacteria and Mycobacterium tuberculosis (Mt), whilst being absent in human cells. Here, we solved the first crystal structure of Pseudomonas aeruginosa (Pa) IspD, the third enzyme in the MEP pathway and present the discovery of a fragment‐based compound class identified through crystallographic screening of PaIspD. The initial fragment occupies the CTP binding cavity within the active site. Confirmation of fragment–protein interactions was achieved through 1H saturation–transfer difference nuclear magnetic resonance (1H‐STD NMR spectroscopy). Building upon these findings and insights from the co‐crystal structures, we identified two growth vectors for fragment growing. We synthesized derivatives addressing both growth vectors, which showed improved affinities for PaIspD. Our new fragment class targets PaIspD, displays promising affinity and favorable growth vectors for further optimization.
Calcium Chemistry as A New Member of Post‐Lithium Battery Family: What Can We Learn from Sodium and Magnesium Systems
Authors: Li Zhenyou , Cui Shuangshuang , Häcker Joachim , Nojabaee Maryam , Fichtner Maximilian , Cui Guanglei , Zhao‐Karger Zhirong 
Published: December 2024

AbstractThe development of next‐generation battery technologies needs to consider their environmental impact throughout the whole cycle life, which has brought new chemistries based on earth‐abundant elements into the spotlight. Rechargeable calcium batteries are such an emerging technology, which shows the potential to provide high cell voltage and high energy density close to lithium‐ion batteries. Additionally, the use of Ca2+ as a charge carrier renders significant sustainable values. Although pioneering work on the electrochemistry of Ca has been carried out for more than half a century, demonstration of reversible Ca0/Ca2+ redox chemistry in non‐aqueous media was only achieved within the past decade. In this review, we will present recent development of rechargeable calcium batteries, focusing on mainly the similarities but also differences between Ca chemistry and other post‐lithium chemistry. According to the periodic nature of elements, magnesium (an alkaline earth element as Ca) and sodium (a diagonally adjacent element to Ca) have similar chemical properties to Ca in various aspects. We shall elaborate on how the solution chemistry, metal behaviors and transport mechanisms of Ca‐ions can be better understood in light of the established principles in the respective Mg/Na systems. We hope the discussion will inspire synergetic development between Ca batteries and other post‐lithium systems.
Genetic Incorporation of a Thioxanthone‐Containing Amino Acid for the Design of Artificial Photoenzymes
Authors: Chen Kai‐Yue , Ming Hui , Wang He‐Xiang , Wang Hua‐Qi , Xiang Zheng 
Published: December 2024

AbstractGenetically encodable photosensitizers allow the design of artificial photoenzymes to expand the scope of abiological reactions. Herein, we report the genetic incorporation of a thioxanthone‐containing amino acid into a protein scaffold via an engineered pyrrolysyl‐tRNA/pyrrolysyl‐tRNA synthetase pair. The designer enzyme was engineered to catalyze a dearomative [2+2] cycloaddition reaction in high yields (up to>99 % yield) with excellent enantioselectivity (up to 98 : 2 e.r.). This work provides a robust and facile method for photoenzyme design and lays the foundation for the development of further photoenzymatic reactions.
Engineering of HO−Zn−N2 Active Sites in Zeolitic Imidazolate Frameworks for Enhanced (Photo)Electrocatalytic Hydrogen Evolution
Authors: Huang Zheao , Wang Zhouzhou , Zhou Qiancheng , Rabl Hannah , Naghdi Shaghayegh , Yang Ze , Eder Dominik 
Published: December 2024

AbstractCurrently, lack of ways to engineer specific and well‐defined active sites in zeolitic imidazolate frameworks (ZIFs) limits our fundamental knowledge with respect to the mechanistic details for (photo)electrocatalytic hydrogen evolution reaction (HER). Here, we introduce the open metal sites into ZIFs through the selective ligand removal (SeLiRe) strategy, comprehensively characterize the altered structural and electronic features, and evaluate their role in HER. In situ electrochemical analysis and X‐ray absorption spectroscopy reveal the formation of high‐valence HO−Zn−N2 sites through the binding of Zn−N2 with electrolyte hydroxide. The optimal OMS‐ZIF exhibits a low overpotential of 0.41 V to achieve an ampere‐level 1.0 A cm−2 with 120‐hour stability. Theoretical simulations indicate that these active sites accelerate the water molecules activation kinetics, consequently enhancing the efficiency of the Volmer step. This work demonstrates a versatile strategy to introduce highly active catalytic sites in ZIFs, providing new insights into the electrocatalytic mechanism in alkaline media.
Epiglottic injury and airway management – a challenging and unexpected diagnosis
Authors: Gutierres M. , Guedes F. , Rosa F. , Oliveira F. , Castro R. , Fernandes V. 
Published: December 2024

SummaryPatients with facial trauma are complex; difficult airway management is often anticipated and challenging for the anaesthetist. Awake tracheal intubation is the gold standard in the management of predicted difficult airway because of its high success rate and safety profile. We present the case of a patient with facial trauma who underwent orotracheal intubation with combined videolaryngoscopy and flexible bronchoscopy, under conscious sedation with intermittent boluses of ketamine and dexmedetomidine. Videolaryngoscopy showed significant oedema and epiglottic laceration, not diagnosed by the computed tomography scan, with visualisation of a false passage that could have led to a failed intubation and further trauma. Airway management in patients with facial trauma is challenging and should be planned and discussed by a multidisciplinary team. A technique combining videolaryngoscopy and flexible bronchoscopy during awake intubation has previously been described and, when used in this case, was successful.
Deep Eutectic Solvent Engineered Dendritic Fibrous Nano‐Silica Catalyst for Sustainable Fixation of CO2 Into Value‐Added Product at Atmospheric Condition
Authors: Alla Sarat Chandra , Sudhakaran Allwin , Bembalge Omkar B. , Samal Akshaya K. , Torrejos Rey Eliseo , Norrrahim Mohd Nor Faiz , Jadhav Arvind H. 
Published: December 2024

ABSTRACTDeveloping efficient carbon dioxide (CO2) capture and conversion methods is vital for climate change mitigation. Cycloaddition of CO2 with epoxides to form cyclic carbonates is a promising utilization method. In this study, a deep eutectic solvent‐modified dendritic fibrous nano‐silica (DES@DFNS) catalyst was synthesized by functionalizing DFNS with DES. This catalyst was used for the cycloaddition of CO2 with styrene oxide to produce styrene carbonate. The material's morphology and properties were characterized using various analytical techniques, revealing a high surface area, good porosity, and significant concentrations of Lewis acidic and basic sites. Rietveld refinement analysis provided insights into its phase composition, crystallite size, microstrain, stress, and other microstructural properties. Despite a lower surface area, DES@DFNS demonstrated superior catalytic activity. The interaction between DES and DFNS showed that DES was physically adsorbed onto the DFNS surface, contributing to its enhanced performance. Factors such as smaller crystallite size, higher microstrain, increased dislocation density, and improved elastic properties provided more active sites and greater mechanical stability, boosting overall efficiency and durability. The DES@DFNS catalyst achieved 99% conversion of styrene oxide with 96% selectivity and 95% yield of styrene carbonate at 120 °C for 10 h under solvent‐free, atmospheric conditions. The synergistic effect of Lewis acidic and basic sites on DES@DFNS supported catalytic activity under moderate conditions. Additionally, the catalyst demonstrated reusability, maintaining performance for up to six cycles without significant loss of activity, making it a promising candidate for sustainable CO2 fixation and valorization processes.
Mn (III)‐Porphyrin Complex as an Efficient and Recyclable Homogeneous Catalyst for Convenient Synthesis of Thioxo‐4,5‐Dihydro‐3H‐thiazolo Pyrimidin‐2‐One Derivatives in Aqueous Media via a One‐Pot Multicomponent Reaction
Authors: Alzahrani Abdullah Yahya Abdullah , Eskander Thomas Nady A. , Soliman Ahmed M.M. , Alraih Alhafez M. , Ali El‐Remaily Mahmoud Abd El Aleem Ali 
Published: December 2024

ABSTRACTThis study successfully utilized the Mn (III)–porphyrin complex (Mn (PT)Cl) as an efficient and recyclable catalyst for a one‐pot, three‐component reaction involving aromatic aldehydes, 2,4‐thiazolidinedione, and thiourea. The reaction yielded thioxo‐4,5‐dihydro‐3H‐thiazolo pyrimidin‐2‐one derivatives under eco‐friendly conditions. Elemental and spectral analyses confirmed the structures of the synthesized compounds, validating the successful formation of the target products. The reactions were conducted in a sustainable environment using a green solvent mixture of H₂O and EtOH. The results showcased the excellent catalytic activity and selectivity of the complexes, resulting in good yields of the desired products. This research provides valuable insights into the synthetic applications of the Mn (PT)Cl complex and emphasizes the potential of such catalysts for various organic transformations. The method's simplicity, safety, commercial availability, stability, rapid reaction times, and high yields indicate promising future applications in industry.
Utilization of a One‐Pot Prepared Cobalt Selenide Embedded Carbon Matrix Electrode From ZIF‐12 for High‐Performance Asymmetric Supercapacitors
Authors: Siyahjani Gultekin Sirin , Bugday Nesrin , Sahin Damla , Ocakoglu Kasim , Gultekin Burak , Yaşar Sedat 
Published: December 2024

ABSTRACTIt is becoming increasingly important to create novel energy storage devices with excellent cycle stability, high power density and high energy density due to the fast advancement in technology. Rechargeable batteries and electrochemical supercapacitors (SCs) are developed as energy storage devices to meet these energy requirements. In this work, a cobalt selenide embedded in a carbon matrix (Co6.8Se8@C) produced from ZIF‐12 via a one‐pot method by our group for the first time was used as an asymmetric SC electrode. In this work, a cobalt selenide embedded in a carbon matrix (Co6.8Se8@C) produced from ZIF‐12 as a precursor by our group previously has been used as an asymmetric SC electrode. The effects of the structural and morphological properties of this composite material on its electrochemical behaviour and capacitive performance were examined both in a three‐electrode system as a single electrode and in an asymmetric SC. The superior electrochemical storage performance with a specific capacitance of 77.06 Fg−1 at 1 Ag−1 and energy density of 27.09 Wh kg−1 at a power density of 441.90 W kg−1 were obtained with high stability and cycle life via the prepared electrode in asymmetric SC device.
Improved Electromagnetic Interference Shielding in Lightweight Polyvinylidene Fluoride‐Carbon Nanotube Composite Films
Authors: Dani Santhoshkumar , Hasamkal Arshad Ayub , Patil Praveen , Arun B. , Raju K. C. James , Udaykumar Khadke 
Published: December 2024

ABSTRACTAs electronic devices become smaller and more common, the problem of electromagnetic interference (EMI) becomes more serious, requiring better shielding solutions. In this study, lightweight polyvinylidene fluoride (PVDF) composite films mixed with multiwalled carbon nanotubes (MWCNT) were developed to improve EMI shielding. A solution casting method and a thin film applicator ensured uniform thickness and flexibility in PVDF‐MWCNT films with varying MWCNT concentrations (0, 0.1, 1, and 2 wt%). Structural and surface properties were analyzed using X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and energy dispersive X‐ray spectroscopy (EDS). Dielectric response, AC conductivity, and EMI shielding effectiveness (EMI‐SE) in the Ku band (12–18 GHz) were measured. The PVDF film with 2 wt% MWCNT, at a thickness of 190 ± 10 μm, showed the highest complex permittivity and a record EMI‐SE value of 53.08 dB. This high EMI‐SE is attributed to increased multiple internal reflections within the thin film, enhancing attenuation and reducing reflection losses. These polymer nanocomposites offer a promising and lightweight option for advanced EMI shielding in the growing number of electronic devices.