bluuebunny/crossref_metadata_2025_split huggingface dataset:
Biphase Pd Nanosheets with Atomic‐Hybrid RhOx/Pd Amorphous Skins Disentangle the Activity‐Stability Trade‐Off in Oxygen Reduction Reaction
Authors: Lyu Zixi , Cai Junlin , Zhang Xia‐Guang , Li Huiqi , Huang Hongpu , Wang Shupeng , Li Tianyu , Wang Qiuxiang , Xie Zhaoxiong , Xie Shuifen 
Published: March 2024

AbstractThe activity‐stability trade‐off relationship of oxygen reduction reaction (ORR) is a tricky issue that strikes the electrocatalyst population and hinders the widespread application of fuel cells. Here neoteric biphase Pd nanosheets that are structured with ultrathin two‐dimensional crystalline Pd inner cores and ≈1 nm thin atomic‐hybrid RhOx/Pd amorphous skins, named c/a‐Pd@PdRh NSs, for disentangling this trade‐off dilemma for alkaline ORR are developed. The superthin amorphous skins significantly amplify the quantity of flexibly low‐coordinated atoms for electrocatalysis. An in situ selected oxidation of the top‐surface Rh dopants creates atomically hybrid RhOx/Pd disorder surfaces. Detailed energy spectra and theoretical simulation confirm that these RhOx/Pd interfaces can arouse a surface charge redistribution, causing significant electron deficiency and lowered d‐band center for surface Pd. Meanwhile, anticorrosive Rh/RhOx species can thermodynamically passivate the neighboring Pd atoms from oxidative dissolution. Thanks to these amplified interfacial effects, the biphase c/a‐Pd@PdRh NSs simultaneously exhibit a superhigh ORR activity (5.92 A mg−1, 22.8 times that of Pt/C) and an outstanding long‐lasting stability after 100k cycles of accelerated durability test, showcasing unprecedented electrocatalysts for breaking the activity‐stability trade‐off relationship of ORR. This work paves a bran‐new strategy for designing high‐performance electrocatalysts through creating modulated amorphous skins on low‐dimensional nanomaterials.
An Encapsulation‐Free and Hierarchical Porous Triboelectric Scaffold with Dynamic Hydrophilicity for Efficient Cartilage Regeneration
Authors: Luo Bin , Wang Sinan , Song Xingqi , Chen Shuo , Qi Qiaoyu , Chen Wenyi , Deng Xiaoyuan , Ni Yufeng , Chu Chengzhen , Zhou Guangdong , Qin Xiaohong , Lei Dong , You Zhengwei 
Published: March 2024

AbstractTissue engineering and electrotherapy are two promising methods to promote tissue repair. However, their integration remains an underexplored area, because their requirements on devices are usually distinct. Triboelectric nanogenerators (TENGs) have shown great potential to develop self‐powered devices. However, due to their susceptibility to moisture, TENGs have to be encapsulated in vivo. Therefore, existing TENGs cannot be employed as tissue engineering scaffolds, which require direct interaction with surrounding cells. Here, the concept of triboelectric scaffolds (TESs) is proposed. Poly(glycerol sebacate), a biodegradable and relatively hydrophobic elastomer, is selected as the matrix of TESs. Each hydrophobic micropore in multi‐hierarchical porous TESs efficiently serves as a moisture‐resistant working unit of TENGs. Integration of tons of micropores ensures the electrotherapy ability of TESs in vivo without encapsulation. Originally hydrophobic TESs are degraded by surface erosion and transformed into hydrophilic surfaces, facilitating their role as tissue engineering scaffolds. Notably, TESs seeded with chondrocytes obtain dense and large matured cartilages after subcutaneous implantation in nude mice. Importantly, rabbits with osteochondral defects receiving TES implantation show favorable hyaline cartilage regeneration and complete cartilage healing. This work provides a promising electronic biomedical device and will inspire a series of new in vivo applications.
Narrow Bandgap Schottky Heterojunction Sonosensitizer with High Electron–Hole Separation Boosted Sonodynamic Therapy in Bladder Cancer
Authors: Li Guanlin , Wu Sicheng , Liu Jinggong , Wang Kaiyuan , Chen Xiaoyuan , Liu Hongxing 
Published: March 2024

AbstractSonodynamic therapy (SDT) is applied to bladder cancer (BC) given its advantages of high depth of tissue penetration and nontoxicity due to the unique anatomical location of the bladder near the abdominal surface. However, low electron–hole separation efficiency and wide bandgap of sonosensitizers limit the effectiveness of SDT. This study aims to develop a TiO2‐Ru‐PEG Schottky heterojunction sonosensitizer with high electron–hole separation and narrow bandgap for SDT in BC. Density functional theory (DFT) calculations and experiments collectively demonstrate that the bandgap of TiO2‐Ru‐PEG is reduced due to the Schottky heterojunction with the characteristic of crystalline‐amorphous interface formed by the deposition of ruthenium (Ru) within the shell layer of TiO2. Thanks to the enhancement of oxygen adsorption and the efficient separation of electron–hole pairs, TiO2‐Ru‐PEG promotes the generation of reactive oxygen species (ROS) under ultrasound (US) irradiation, resulting in cell cycle arrest and apoptosis of bladder tumor cells. The in vivo results prove that TiO2‐Ru‐PEG boosted the subcutaneous and orthotopic bladder tumor models while exhibiting good safety. This study adopts the ruthenium complex for optimizing sonosensitizers, contributing to the progress of SDT improvement strategies and presenting a paradigm for BC therapy.
Remote Control of Energy Transformation‐Based Cancer Imaging and Therapy
Authors: Xu Hai , Kim Dahee , Zhao Yuan‐Yuan , Kim Chowon , Song Guosheng , Hu Qiongzheng , Kang Heemin , Yoon Juyoung 
Published: March 2024

AbstractCancer treatment requires precise tumor‐specific targeting at specific sites that allows for high‐resolution diagnostic imaging and long‐term patient‐tailorable cancer therapy; while, minimizing side effects largely arising from non‐targetability. This can be realized by harnessing exogenous remote stimuli, such as tissue‐penetrative ultrasound, magnetic field, light, and radiation, that enable local activation for cancer imaging and therapy in deep tumors. A myriad of nanomedicines can be efficiently activated when the energy of such remote stimuli can be transformed into another type of energy. This review discusses the remote control of energy transformation for targetable, efficient, and long‐term cancer imaging and therapy. Such ultrasonic, magnetic, photonic, radiative, and radioactive energy can be transformed into mechanical, thermal, chemical, and radiative energy to enable a variety of cancer imaging and treatment modalities. The current review article describes multimodal energy transformation where a serial cascade or multiple types of energy transformation occur. This review includes not only mechanical, chemical, hyperthermia, and radiation therapy but also emerging thermoelectric, pyroelectric, and piezoelectric therapies for cancer treatment. It also illustrates ultrasound, magnetic resonance, fluorescence, computed tomography, photoluminescence, and photoacoustic imaging‐guided cancer therapies. It highlights afterglow imaging that can eliminate autofluorescence for sustained signal emission after the excitation.
Mendelian randomization analysis using GWAS and eQTL data to investigate the relationship between chronotype and neuropsychiatric disorders and their molecular basis
Authors: Crinion Shane , Wyse Cathy A. , Donohoe Gary , Lopez Lorna M. , Morris Derek W. 
Published: March 2024

AbstractChronotype is a proxy sleep measure that has been associated with neuropsychiatric disorders. By investigating how chronotype influences risk for neuropsychiatric disorders and vice versa, we may identify modifiable risk factors for each phenotype. Here we used Mendelian randomization (MR), to explore causal effects by (1) studying the causal relationships between neuropsychiatric disorders and chronotype and (2) characterizing the genetic components of these phenotypes. Firstly, we investigated if a causal role exists between five neuropsychiatric disorders and chronotype using the largest genome‐wide association studies (GWAS) available. Secondly, we integrated data from expression quantitative trait loci (eQTLs) to investigate the role of gene expression alterations on these phenotypes. Evening chronotype was causal for increased risk of schizophrenia and autism spectrum disorder and schizophrenia was causal for a tendency toward evening chronotype. We identified 12 eQTLs where gene expression changes in brain or blood were causal for one of the phenotypes, including two eQTLs for SNX19 in hippocampus and hypothalamus that were causal for schizophrenia. These findings provide important evidence for the complex, bidirectional relationship that exists between a sleep‐based phenotype and neuropsychiatric disorders, and use gene expression data to identify causal roles for genes at associated loci.
Theoretical Prediction Leads to Synthesize GDY Supported InOx Quantum Dots for CO2 Reduction
Authors: He Feng , Chen Xi , Xue Yurui , Li Yuliang 
Published: March 2024

AbstractThe preparation of formic acid by direct reduction of carbon dioxide is an important basis for the future chemical industry and is of great significance. Due to the serious shortage of highly active and selective electrocatalysts leading to the development of direct reduction of carbon dioxide is limited. Herein the target catalysts with high CO2RR activity and selectivity were identified by integrating DFT calculations and high‐throughput screening and by using graphdiyne (GDY) supported metal oxides quantum dots (QDs) as the ideal model. It is theoretically predicted that GDY supported indium oxide QDs (i.e., InOx/GDY) is a new heterostructure electrocatalyst candidate with optimal CO2RR performance. The interfacial electronic strong interactions effectively regulate the surface charge distribution of QDs and affect the adsorption/desorption behavior of HCOO* intermediate during CO2RR to achieve highly efficient CO2 conversion. Based on the predicted composition and structure, we synthesized the advanced catalytic system, and demonstrates superior CO2‐to‐HCOOH conversion performance. The study presents an effective strategy for rational design of highly efficient heterostructure electrocatalysts to promote green chemical production.
Lewis Säure‐Getriebene Inverse Hydrid‐Shuttle Katalyse
Authors: Jones Benjamin T. , Maulide Nuno 
Published: March 2024

AbstractInverse Hydrid‐Shuttle Katalyse bildet eine Plattform für die hocheffiziente und diastereoselektive Synthese von Alkaloidstrukturen durch Multikomponentenreaktionen. Mehrere Einschränkungen hindern jedoch die breite Anwendbarkeit dieses Ansatzes, darunter vor allem die Notwendigkeit nach besonders elektronenarmen Akzeptoren. Hier präsentieren wir einen allgemeinen, durch Lewis Säuren getriebenen Ansatz, um diese Einschränkung anzugehen, und haben zwei Strategien entwickelt, die die modulare Synthese komplexer azabicyclischer Systeme ermöglichen, die mit der früheren Methode unerreichbar waren. Die so gewonnene synthetische Flexibilität führt zu einer verbesserten asymmetrischen Cyclisierung, die eine kurze Totalsynthese des Alkaloids (−)‐Tashiromin ermöglicht hat.
Lewis Acid‐Driven Inverse Hydride Shuttle Catalysis
Authors: Jones Benjamin T. , Maulide Nuno 
Published: March 2024

AbstractInverse hydride shuttle catalysis provides a multicomponent platform for the highly efficient synthesis of alkaloid frameworks with exquisite diastereoselectivity. However, a number of limitations hinder this method, primarily the strict requirement for highly electron‐deficient acceptors. Herein, we present a general Lewis acid‐driven approach to address this constraint, and have developed two broad strategies enabling the modular synthesis of complex azabicycles that were entirely unattainable using the previous method. The enhanced synthetic flexibility facilitates a streamlined asymmetric cyclization, leading to a concise total synthesis of the alkaloid (−)‐tashiromine.
Production of Aromatic Hydrocarbons from Co‐Hydropyrolysis of Biomass Components and HDPE with Application of Modified HZSM‐5 Catalyst
Authors: Ren Long , Xu Yupu , Chen Wenjun , Zhang Changsen 
Published: March 2024

AbstractExperiments were conducted in this study on the co‐hydropyrolysis of three components of biomass (cellulose, hemicellulose, and lignin) and HDPE by using SR‐Pd/Trap‐HZ‐5 as catalyst. To control the variable, we use the same experiment conditions in co‐hydropyrolysis: Si/Al ratio of 50, Pd load 1 %, catalyst to reactant ratio of 1 : 10, 1 MPa, 400 °C, reaction time 1 h. Use XRD, TEM, BET, and NH3‐TPD to confirm catalyst successful synthesis; use pine sawdust (PW) co‐hydropyrolysis with HDPE to analyse catalytic activity; and use GC/MS to characterize the chemical composition of the bio‐oil from the co‐hydropyrolysis of biomass components and HDPE. The results show that cellulose has a significant synergistic effect with aromatic hydrocarbon production, whose selectivity was 93.3 %; hemicellulose has a synergistic effect; aromatic selectivity can reach 75.1 %; and a negative synergistic effect between lignin and HDPE was shown as the selectivity of aromatic hydrocarbons decreased from 62.1 % to 15.6 %.
Peptide‐conjugated Nanoparticle Platforms for Targeted Delivery, Imaging, and Biosensing Applications
Authors: Ilieş Bogdan Dragoş , Yildiz Ibrahim , Abbas Manzar 
Published: March 2024

AbstractPeptides have become an indispensable tool in engineering of multifunctional nanostructure platforms for biomedical applications such as targeted drug and gene delivery, imaging and biosensing. They can be covalently incorporated into a variety of nanoparticles (NPs) including polymers, metallic nanoparticles, and others. Using different bioconjugation techniques, multifunctional peptide‐modified NPs can be formulated to produce therapeutical and diagnostic platforms offering high specificity, lower toxicity, biocompatibility, and stimuli responsive behavior. Targeting peptides can direct the nanoparticles into specific tissues for targeted drug and gene delivery and imaging applications due to their specificity towards certain receptors. Furthermore, due to their stimuli‐responsive features, they can offer controlled release of therapeutics into desired sites of disease. In addition, peptide‐based biosensors and imaging agents can provide non‐invasive detection and monitoring of diseases including cancer, infectious diseases, and neurological disorders. In this review, we covered the design and formulation of recent peptide‐based NP platforms, as well as their utilization in in vitro and in vivo applications such as targeted drug and gene delivery, targeting, sensing, and imaging applications. In the end, we provided the future outlook to design new peptide conjugated nanomaterials for biomedical applications.
A Family of Hexacopper Phenylsilsesquioxane/Acetate Complexes: Synthesis, Solvent‐Controlled Cage Structures, and Catalytic Activity
Authors: Zueva Anna Y. , Bilyachenko Alexey N. , Arteev Ivan S. , Khrustalev Victor N. , Dorovatovskii Pavel V. , Shul'pina Lidia S. , Ikonnikov Nikolay S. , Gutsul Evgenii I. , Rahimov Karim G. , Shubina Elena S. , Reis Conceição Nuno , Mahmudov Kamran T. , Guedes da Silva M. Fátima C. , Pombeiro Armando J. L. 
Published: March 2024

AbstractConvenient self‐assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich‐like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4‐cyclic and Si6‐condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6‐complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer‐Villiger oxidation of cyclohexanone by m‐chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ‐caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer‐Villiger oxidation reaction using the same oxidant.
A computational method for predicting color palette discriminability
Authors: Westland Stephen , Finlayson Graham , Lai Peihua , Pan Qianqian , Yang Jie , Chen Yun 
Published: March 2024

AbstractAutomatic analysis of images is increasingly being used to generate color insights and this has led to various methods for generating palettes. Several studies have recently been published that explore methods to predict the visual similarity between pairs of palettes and these methods are often used to evaluate different generative methods. This work is concerned with being able to predict visual similarity between color palettes. Three data sets (two of which were previously published) are used to evaluate two methods for predicting visual similarity between palettes. A novel palette‐difference metric (based on the Hungarian algorithm) is compared to the previously published minimum color difference model (MICD) and was found to agree better with the visual data for two of the three data sets. Agreement between models and visual data was also better for CIEDE2000 (1, 2) than for CIELAB metrics.
Continuous‐Flow Catalysis Using Phosphine‐Metal Complexes on Porous Polymers: Designing Ligands, Pores, and Reactors
Authors: Matsumoto Hikaru , Iwai Tomohiro , Sawamura Masaya , Miura Yoshiko 
Published: March 2024

AbstractContinuous‐flow syntheses using immobilized catalysts can offer efficient chemical processes with easy separation and purification. Porous polymers have gained significant interests for their applications to catalytic systems in the field of organic chemistry. The porous polymers are recognized for their large surface area, high chemical stability, facile modulation of surface chemistry, and cost‐effectiveness. It is crucial to immobilize transition‐metal catalysts due to their difficult separation and high toxicity. Supported phosphine ligands represent a noteworthy system for the effective immobilization of metal catalysts and modulation of catalytic properties. Researchers have been actively pursuing strategies involving phosphine‐metal complexes supported on porous polymers, aiming for high activities, durabilities, selectivities, and applicability to continuous‐flow systems. This review provides a concise overview of phosphine‐metal complexes supported on porous polymers for continuous‐flow catalytic reactions. Polymer catalysts are categorized based on pore sizes, including micro‐, meso‐, and macroporous polymers. The characteristics of these porous polymers are explored concerning their efficiency in immobilized catalysis and continuous‐flow systems.
Adherence to GLP1‐RA and SGLT2‐I affects clinical outcomes and costs in patients with type 2 diabetes
Authors: Ciardullo Stefano , Savaré Laura , Rea Federico , Perseghin Gianluca , Corrao Giovanni 
Published: March 2024

AbstractAimsTo evaluate the impact of adherence to glucagon like peptide‐1 receptor agonists (GLP1‐RA) and sodium‐glucose transporter two inhibitors (SGLT2‐I) on clinical outcomes and costs in patients with type 2 diabetes mellitus (T2DM).Materials and MethodsThe 121,115 residents of the Lombardy Region (Italy) aged ≥40 years newly treated with metformin during 2007–2015 were followed to identify those who started therapy with GLP1‐RA or SGLT2‐I. Adherence to drug therapy over the first year was defined as the proportion of days covered >80%. Within each drug class, for each adherent patient, one non‐adherent patient was matched for age, sex, duration, adherence to metformin treatment and propensity score. The primary clinical outcome was a composite of insulin initiation, hospitalisation for micro‐ and macrovascular complications and all‐cause mortality after the first year of drug treatment. Costs were evaluated based on reimbursements from the national healthcare system.ResultsAfter matching, 1182 pairs of adherent and non‐adherent GLP1‐RA users and 1126 pairs of adherent and non‐adherent SGLT2‐I users were included. In both groups, adherent patients experienced a significantly lower incidence of the primary outcome (HR: 0.85, 95% CI 0.72–0.98 for GLP1‐RA and HR: 0.69, 95% CI 0.55–0.87 for SGLT2‐I). A significant reduction in hospitalizations was found for adherent patients in the GLP1‐RA group but not for the SGLT2‐I group. Results were consistent when analyses were stratified by age and sex. While higher drug‐related costs in the adherent group were counterbalanced by decreased hospitalisation costs in SGLT2‐I treated patients, this was not the case for GLP1‐RA.ConclusionsHigher adherence to drug treatment with GLP1‐RA and SGLT2‐I during the first year of the drug intake is associated with a lower incidence of adverse clinical outcomes in a real‐world setting.
N‐Directed defluorinative γ‐C(sp3)−H allylation of sulfamate esters for synthesis of gem‐difluoroalkenes via photoredox catalysis
Authors: Yang Jia‐Wen , Li Meng , Tan Guang‐Qiang , Liu Feng , Qin Hai‐Tao 
Published: March 2024

Abstractgem‐Difluoroalkenes are unique structural motifs with important applications ranging from drugs to materials. Herein, we report a novel radical‐mediated defluorinative allylation of sulfamate esters with through distal C(sp3)−H functionalization under photoredox conditions. The reaction could readily incorporate various gem‐difluoroalkene motifs into previously unfunctionalized sp3 carbon centers. The transformation allows directly dual activation of N−H and C(sp3)−H bonds via a photocatalytic and redox‐neutral process, as well as using water as environmentally friendly co‐solvent. The reaction could provide a general and operationally simple method to access gem‐difluoroalkene compounds with high diversity.