bluuebunny/crossref_metadata_2025_split huggingface dataset:
Insight into Hydrovoltaic Technology: from Mechanism to Applications
Authors: Gu Chen , Luo Yixiang , Ji Huachao , Wang Shiyan , Huang BaoYu , Zhu Xianjun , Wang Longlu 
Published: December 2024

AbstractWater encompasses vast quantities of energy in diverse forms, yet this energy is rarely exploited. Hydrovoltaic technology, as an emergent clean energy generation technology, has garnered extensive attention in recent years. Distinct from conventional hydroelectric power generation, hydrovoltaic technology ingeniously employs the interaction between functional materials and water, and achieves the direct conversion of water energy into electrical energy. This review initially delineates the mechanism of hydrovoltaic technology and deliberate on the various materials currently employed for hydroelectric power generation. Subsequently, experimental advancements in power generation from water droplets, water evaporation, and moisture are summarized to demonstrate the relevance of their fundamental mechanisms and their potential for harvesting energy from the water cycle. This work further expounds on the potential device applications of hydrovoltaic technology and proposes prospects for the development of emerging technologies.
A New Strategy for Photo‐Electrochemical Reduction of Carbon Dioxide Using a Carbazole‐BODIPY Based Metal‐Free Catalyst
Authors: Özdemir Mücahit , Uluçay Sude , Altınışık Sinem , Köksoy Baybars , Yalçın Bahattin , Koyuncu Sermet 
Published: December 2024

AbstractIn this study, a cross‐linked boron dipyrromethene (BODIPY) photocatalyst containing a carbazole donor group designed for photoelectrocatalytic carbon dioxide (CO2) reduction is synthesized and characterized. The BODIPY‐based system, coated onto a platinum surface, is evaluated for its electrochemical and photocatalytic performance under light illumination. Cyclic voltammetry (CV) and chronoamperometry measurements reveals enhanced photocurrent responses, confirming the catalyst's ability to effectively drive CO2 reduction. Gas chromatography/mass spectrometry (GC‐MS) analysis identifies the formation of ethanol (C2H5OH) as a major reaction product, showing that its yield increased with extended reaction times. Additionally, the photocatalyst demonstrates remarkable performance with significantly increasing turnover numbers (TON) and turnover frequencies (TOF) over time, indicating stable and sustained catalytic activity. With a Faradaic efficiency of 34.79% at a potential of ‐1.15 V, this BODIPY system exhibits both high activity and long‐term stability. The combination of efficient electron transfer and visible light absorption by the carbazole‐BODIPY donor‐acceptor structure positions this system as a highly promising candidate for sustainable CO2 conversion applications.
Switchable Radical Polymerization of α‐Olefins via Remote Hydrogen Atom or Group Transfer for Enhanced Battery Performance
Authors: Song Silin , Wang Shuo , Wang Ziqiang , Sun Hao , Wang Xianjin , Zhu Chen 
Published: December 2024

AbstractIntroducing polar groups into non‐polar polyolefins can significantly enhance the important properties of materials. However, producing polyolefin backbones consisting of polar blocks remains elusive, due to the substantial difference of reactivity ratios between polar and non‐polar olefin monomers in radical polymerization or the poisoning of transition‐metal catalysts by polar groups in coordination polymerization. Herein we present a practical way for the preparation of polyethylene‐based polymers with distinct polar groups by radical polymerization of α‐olefins. A strategy of switchable remote hydrogen atom or group transfer is devised, leading to a diverse range of AAB or ABC sequence‐defined carbon‐chain polyolefins. The utility of these polymers is demonstrated by using poly(ethyl 2‐cyanohept‐6‐enoate) (P2) as an interphase layer material in anode‐free Li metal battery, which effectively improves the cycling stability of the battery and indicates its potential in energy storage applications.
A New Bis‐Urea Based Cage Receptor for Anions: Synthesis, Solid State Structures and Binding Studies
Authors: Paderni Daniele , Formica Mauro , Macedi Eleonora , Giorgi Luca , Rossi Patrizia , Retini Michele , De Cata Nicola , Zappia Giovanni , Piersanti Giovanni , Fusi Vieri 
Published: December 2024

AbstractThe synthesis and characterization of a novel bis‐urea‐based cage receptor for anions (3S,15S)‐3,15,20,25‐tetramethyl‐1,4,6,12,14,17,20,25‐octaazatricyclo[15.5.5.17.11]octacosa‐7(28),10‐diene‐2,5,13,16‐tetraone (L) is reported. L is a macro‐bicyclic ligand built on the 1,7‐dimethyl‐1,4,7,10‐tetraazacyclododecane scaffold to obtain a cage topology in which two ureido moieties have been inserted as binding sites for anions. L can interact with anion guests (G) via H‐bonding; in particular, it binds both spherical (Cl−) and V‐shaped anions (AcO−) as well as more complex carboxylate anions, such as the norfloxacin (Nor−). NMR experiments highlight that the interaction between L and G mainly occurs at the ureido moieties. L forms L‐G adducts of 1 : 1 ([LG]−) and 1 : 2 ([LG2]2−) stoichiometry with Cl− and AcO−. Otherwise, in the case of Nor− only the formation of the [LG]− complex is observed. L shows higher formation constants values for [LAcO]− (2.9) and [LNor]− (3.6) than [LCl]− suggesting a stronger interaction with the carboxylate anions. In the solid state, three crystal structures of the HL⋅G species were obtained (G=Cl−, AcO−, ClO4−) highlighting the H‐bonding interaction between the chloride, acetate or perchlorate anions and the −NH functions of the ureido fragment. The comparison between the two parent open chain receptors (Lb‐c) and L has been reported and discussed.
Building Block for Designing Bright Type I AIE‐Active Photosensitizers with Deep/Near‐infrared Red Fluorescence
Authors: Tang Yiwen , Xie Yili , Bai Xue , Zhao Chunhui , Zheng Yaoqiu , Liang Hongbo , Ma Zihang , Wang Zhiming , Wan Qing 
Published: December 2024

AbstractBright deep red/near‐infrared red (DR/NIR) active type I photosensitizers (PSs) with generating superoxide anion and hydroxyl radical have been regarded as powerful functional materials to fight the “Achilles's heel” of hypoxia from solid tumor. But some problems have still existed, for example, lacking effective molecular designed strategy or typical building block to design precisely type I PSs. In addition, the relationship between fluorescent quantum efficiency and NIR fluorescent color is inconsistent according to energy gap rule. To overcome above mentioned problems, in this work, we propose a typical building block to design precisely type I PSs with DR/NIR fluorescence and high photoluminescent quantum yield at aggregation by combining molecular design of aggregation‐induced emission and hybrid locally and charge transfer (HLCT) theory. The synthetic small molecular PSs just produce superoxide anion without any singlet oxygen production, which is ascribed to their lower T1 energy levels to suppress energy transfer from triplet state to oxygen. Two strategies of small molecular structural designing and polymeric nanoparticles modification are utilized to improve efficiency of type I ROS. More interestingly, original small molecular PSs is in capable to produce hydroxyl radical, once forming BSA encapsulated nanoparticles, obvious hydroxyl radical is appeared.
Conversion of Isolated Voids into Channel Spaces by Modulating the Stacking Manner of Hydrogen‐Bonded Ladders
Authors: Murakami Naoto , Oketani Ryusei , Hisaki Ichiro 
Published: December 2024

Abstract1,2,3,4‐Tetrakis(carboxyphenyl)benzene (CPB) forms a predictable ladder‐shaped porous motif through intermolecular hydrogen‐bonding of the carboxy groups. The stacking manner of the ladder motif, on the other hand, cannot be controlled, yielding a crystal structure with discrete inclusion spaces. To modulate the stacking manner, its derivative CPB(OMe) with methoxy substituent groups at 5,6‐positions was synthesized and crystallized to yield a crystalline hydrogen‐bonded organic framework (HOF), in which the ladder motifs are stacking with a different manner to form 1D inclusion channels, instead of discrete voids. Because of the channel structure, removal of the included solvent molecules can be easily conducted, and the resultant activated HOF CPB(OMe)‐a exhibited micropores with BET surface area of 199 m2 g−1, which is larger than that of the other HOF CPB‐a.
The Potential Therapeutic Targets of Anlotinib in Osteosarcoma: Characterization Based on Patient‐Derived Xenografts and Next‐Generation Sequencing
Authors: Long Zuoyao , Lu Yajie , Li Minghui , Li Jing , Chen Guojing , Wang Fengwei , Wang Qi , Xiang Liangbi , Wang Zhen 
Published: December 2024

ABSTRACTBackgroundThe aim of this study was to analyze the potential therapeutic targets of anlotinib using the patient‐derived xenografts (PDX) and evaluate the efficacy of the combination of chemotherapy and anlotinib in osteosarcoma patients before surgery.MethodsForty‐three osteosarcoma specimens were used to establish the PDX model in mice, resulting in Twenty‐one PDX successful models. Eventually, six models were randomly selected for the pharmacodynamic experiment. The tumor‐bearing mice were randomly divided into the anlotinib (3 mg/kg) and placebo groups (n = 5 each). After treatment, the tumors were harvested and analyzed by immunohistochemistry (IHC) and western blotting.ResultsIn PDX model establishment, the tumors from donors with relapse, metastasis or chemoresistance demonstrated higher engraftment capacity. Histology results suggested that anlotinib significantly inhibited the growth of osteosarcoma by inducing mitotic arrest, necrosis and apoptosis, and selective against tumors with high expression of VEGFR2, PDGFRβ and CD31. Based on these results, five osteosarcoma patients who had progressed during NAC were treated with the combination of anlotinib and chemotherapy before surgery, which led to tumor regression in four patients. Next‐generation sequencing showed that most patients with tumor reduction expressed medium or high levels of VEGFR2 and PDGFRβ mRNA. The toxicities were tolerable.ConclusionsIn conclusion, osteosarcoma with high expression of VEGFR2, PDGFRβ and CD31 is more sensitive to anlotinib. However, the potential of synergistic effect of anlotinib and chemotherapy in osteosarcoma patients needs further investigation.
Change in Cardiorespiratory Fitness and the Risk of Colorectal and Prostate Cancer Incidence in Men
Authors: Bojsen‐Møller Emil , Bolam Kate A. , Väisänen Daniel , Paulsson Sofia , Lindwall Magnus , Rundqvist Helene , Nyberg Jenny , Åberg Maria , Ekblom‐Bak Elin 
Published: December 2024

ABSTRACTIntroductionThe aim of this prospective cohort study was to investigate the associations between changes in cardiorespiratory fitness (CRF) and the risk of colorectal and prostate cancer in men.MethodsData from men who completed a health assessment both in military conscription in youth and an occupational health profile assessment (HPA) later in life were used. CRF was assessed as estimated V̇O2max, using a cycle ergometer fitness test at both time points. We linked the assessment data to national register data on colorectal and prostate cancer incidence, and hazard ratios and confidence intervals were estimated using Cox proportional hazard regression.Results139,764 men with a mean age of 18 (SD 0.6) at conscription and 43 (SD 8.9) at HPA were included. The average time between the two assessments was 25.9 (SD 9.0) years and mean follow‐up time following HPA test was 10.0 (SD 5.6) years for prostate and colorectal cancer. Annual percentage change in relative and absolute V̇O2max from conscription to HPA was inversely associated with the risk of colorectal cancer incidence, hazard ratio of 0.83 (95% CI [0.72–0.94]) and 0.88 (95% CI [0.79–0.99]), respectively. These associations were driven by data from individuals in the lowest and moderate level fitness tertials at conscription. Change in CRF was not associated with prostate cancer incidence risk.ConclusionsChanges in, not only level of, CRF from youth to adulthood are related to colorectal cancer incidence risk and therefore, improving CRF should be considered as an important colorectal cancer risk reduction strategy.
Angio‐Seal Vascular Closure Device for Percutaneous Management of Iatrogenic Right Ventricular Perforation During Pericardiocentesis
Authors: Skalidis Ioannis , Rubimbura Vladimir , Eeckhout Eric 
Published: December 2024

ABSTRACTThis case report presents an instance of iatrogenic right ventricular perforation during pericardial paracentesis, a rare complication with potentially fatal consequences. Despite initial unsuccessful pericardial drainage, successful closure of the perforation was achieved using an Angio‐Seal vascular closure device, leading to cessation of hemorrhage and resolution of hemodynamic instability. The case highlights the efficacy of Angio‐Seal in managing such complications, emphasizing its utility in complex clinical scenarios involving pericardial interventions.
A Novel Bailout Snare Technique Sparing Recross the Aortic Valve During Transcatheter Aortic Valve Implantation
Authors: Jiang Zhengming , Yao Jing , Xi Ziwei , Song Guangyuan 
Published: December 2024

ABSTRACTTranscatheter aortic valve replacement (TAVR) procedure was planned for a 68‐year‐old female patient diagnosed with severe aortic stenosis by transthoracic echocardiography. The first valve unexpectedly dislodged during catheter tip withdrawal after full deployment. A second valve deployment became necessary, posing challenges due to the difficulty of passing the second valve delivery system through the first valve frame. The snare technique is typically used in cases where there are difficulties in delivering the transcatheter heart valve system across the native aortic valve during the TAVR procedure. We described a novel bailout technique to capture the delivery system in the main access using a snare catheter from the secondary access, while retaining the stiff wire in the left ventricle. This technique could be particularly applicable in scenarios where recrossing is challenging and risky.
Supramolecular Preorganization Rhodium and Iridium Metal Complexes Within M12L24 Self‐Assembled Nanospheres for the Confined Synthesis Rh/Ir Alloyed Nanoparticles
Authors: Metz Lotte L. , Bobylev Eduard O. , vandePoll Rim C. J. , Hensen Emiel J. M. , Hoogsteder Igor , Albrecht Wiebke , Reek Joost N. H. 
Published: December 2024

AbstractControlling the size and composition of metal nanoparticles is of considerable interest, as these are essential to their catalytic properties. Recently, our group has developed a preorganization strategy for controlled Ir nanoparticle synthesis inside Pt12L24 nanospheres. In the current contribution, we expand this method to the controlled synthesis of Rh nanoparticles. The encapsulated RhI complexes (Rh‐s @ G‐sphere) led to reasonable size control (2.8 ± 0.9 nm). Next, we demonstrated the formation of Rh‐Ir alloyed nanoparticles with varying Rh/Ir compositions, by preorganization of the respective metal complexes inside Pt12L24 nanospheres based on complementary hydrogen bonds before the reduction step that leads to nanoparticle formation. These heterometallic particles were evaluated in the hydrogenation of cinnamaldehyde (7) as a probe reaction. Besides a high activity in this probe reaction, the Rh particles also catalyzed the conversion of the solvent (CH3CN). The formed basic amine leads to follow‐up reactions of the product and compatibility issues with the hosting nanosphere. The solvent hydrogenation was effectively suppressed by using the Rh:Ir alloyed nanoparticles, provided that they contain > 66% Ir. Compared to the monometallic Ir particles (Ir‐s @ G‐sphere), the Rh:Ir alloyed nanoparticles displayed higher catalytic activity, reaching optimal selectivity and activity at an 8:16–Rh:Ir ratio. The combined catalytic results illustrate that preorganization of the metal complexes in the nanosphere before the reduction with hydrogen effectively facilitates the formation of Rh:Ir alloyed nanoparticles, which allows for tuning a catalyst to create a more active and selective catalyst compared to monometallic or nonencapsulated Rh/Ir particles.
Cyclodextrin‐Encapsulated NHCs: Increased Selectivity and Reactivity of CO2 in Amine Formylation
Authors: Bijouard Kajetan , Nicolas Emmanuel , Anthore‐Dalion Lucile , Sollogoub Matthieu , Cantat Thibault 
Published: December 2024

AbstractHerein, we describe the confinement of a N‐Heterocyclic Carbene (NHC) organocatalyst in the cavity of cyclodextrins (CDs). These confined organocatalysts allow the formylation of amines through CO2 hydrosilylation. The presence of the cavity of the CDs leads to substrate‐selectivity between amines in competition reactions. The use of the smallest α‐CD induces the best selectivities but also increased reactivity compared to the bigger β‐CD. A careful study conducted by NMR and DFT revealed that in α‐CD, the complexed CO2 interacts with the cavity through hydrogen bonds. These H‐bonds destabilize the NHC–CO2 adduct and are accountable for the higher reactivity observed using α‐CD.
Ordered Assembly of Natural Phenolic Building Blocks for Supramolecular Crystalline Materials
Authors: Xie Qiuping , Pu Yiran , Huang Huijun , Li Shuyun , He Yunxiang , Guo Junling 
Published: December 2024

AbstractBiomacromolecules such as DNA, proteins, and lipids in nature are constructed by ‘bottom‐up’ assembly with diverse functions and structural ordered characteristics. Supramolecular assemblies have been employed to mimic the natural complexity by manipulating the subtle variations of functional groups. Nevertheless, the intricate design of the driving forces or sophisticated synthesis of molecular skeletons poses challenges in fabricating highly ordered assemblies. Natural phenolic molecules with anisotropic functional groups exhibit potential as versatile building blocks for a wide range of supramolecular crystalline materials with tailored assembly and controlled functionalities. The inherent and anisotropic phenolic groups engage in ordered assembly with various materials via directional covalent bonds (e. g., condensation and coordination) as well as multiple molecular interactions (e. g., hydrogen bonding and π–π interactions), leading to the formation of supramolecular crystalline materials with diverse functionalities. This Concept presents the assembly mechanisms of crystalline phenolic materials and their applications, showcasing the effective utilization of ordered assembly by natural phenolic building blocks.
Mechanistic Insights into Chloride‐Dependent Uncaging Reaction of Propargyl and Allene‐Protected Substrates by Pd‐Complexes
Authors: Ferreira Thuany M. , Navo Claudio D. , Agnes Jonathan P. , Cardozo Filipe , de Oliveira Daniela C. , Zanotto‐Filho Alfeu , Jiménez‐Osés Gonzalo , Domingos Josiel B. 
Published: December 2024

AbstractThis study investigates the effect of chloride levels on the mode of action of palladium complexes for the activation of propargyl‐ and allene‐protected fluorophores and chemotherapeutic drugs through uncaging reactions. Four Pd(II) complexes were synthesized and characterized using various spectroscopic techniques to confirm their structure and electronic properties. Kinetic studies and density functional theory calculations revealed that chloride ions in phosphate buffered saline (PBS) significantly enhance catalytic efficiency, particularly for allenyl‐protected substrates compared to propargylic counterparts. This enhancement is attributed to the neutral charge nature of the Pd complex. The data suggest that neutral complexes are less prone to chloride exchange by water molecules. Additionally, chloride ligands counterbalance the unusually high stability of the key σ‐bound η1‐Pd intermediates in the aquo complexes in PB, leading to an overall higher reactivity. These results highlight the impact of fine‐tuning the electronic properties of the metal center through both designed ligands and environmental factors. Bench evaluations and tests with living breast cancer cells demonstrated that a Pd catalyst complex with a bidentate ligand effectively activates the prodrugs propargyl‐5‐fluorouracil (Prop‐5FU) and allene‐5‐Fluorouracil (Alle‐5FU), the latter being a novel prodrug. The Pd catalyst successfully released the active drug, inducing significant cytotoxicity, especially with Alle‐5FU, which operates at lower catalyst concentrations than Pro‐5FU.
Harnessing Cyanine‐like Properties to Develop Bright Fluorogenic Probes Based on Viscosity‐Sensitive Molecular Rotors
Authors: Dumat Blaise , Chieffo Carolina 
Published: December 2024

AbstractDipolar fluorescent molecular rotors (FMRs) are environmentally‐sensitive fluorophores that can be used in bioimaging applications to sense local viscosity and polarity. Their sensitivity to viscosity can also be used for the fluorogenic labeling of biomolecules such as DNA or proteins. In particular, we have previously used FMRs to develop a series of tunable fluorogens targeting the self‐labeling protein tag Halotag for wash‐free protein imaging in live cells. Despite these very useful properties, FMRs typically display moderate molar absorption coefficients that limits their overall fluorescence brightness. Herein, we synthesized a series of three model hemicyanines based on a styrylindolenium scaffold and performed a detailed study of their photophysical properties in solvents with various polarity and viscosity. We show that with a strong julolidine electron‐donating group it is possible to combine intense cyanine‐like absorption with the high sensitivity to viscosity of FMRs. We use this property to develop a lysosomal pH sensor and two bright cell‐impermeant fluorogens targeting HaloTag for imaging membrane proteins. We believe that this bright fluorogenic scaffold based on a simple chemical structure can be used in the future to build up a variety of probes and sensors with efficient photophysical properties.
DABCO‐Mediated Photoelectrochemical Three‐Component Sulfonocyclization of 3‐Aza‐1,5‐dienes
Authors: Ding Lucai , Yang Guihong , Luo Li , Ma Yingchun , Shi Jifu , Liang Deqiang , Li Yanni 
Published: December 2024

Comprehensive SummaryHerein, we report a rare example of three‐component net‐oxidative sulfonylation of a SO2 surrogate with an oxidatively activated radical precursor under mild and metal‐ and external‐oxidant‐free conditions. The mildness and sustainability of the reaction are enabled by photoelectrocatalysis, and 3‐aza‐1,5‐dienes, organotrifluoroborates and 1,4‐diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO) undergo sulfonylative cyclization to afford sulfono 4‐pyrrolin‐2‐ones in an atom‐economical manner with a broad substrate scope and good functional‐group tolerance. The protocol is amenable to the late‐stage diversification of complex molecular architectures as well as the gram‐scale synthesis. Sunlight could be used as the light source, and the reaction could be conducted in an all‐solar mode using a commercially available photovoltaic panel to generate electricity in situ. Mechanistic studies reveal that the in situ generated 1,4‐diazabicyclo[2.2.2]octane (DABCO), which was generally innocent in previous reactions, functions as an electron shuttle between the photocatalytic cycle and the reactants.