bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dual‐Metal Sites Drive Tandem Electrocatalytic CO2 to C2+ Products
Authors: Xie Guixian , Guo Weiwei , Fang Zijian , Duan Zongxia , Lang Xianzhen , Liu Doudou , Mei Guoliang , Zhai Yanling , Sun Xiaofu , Lu Xiaoquan 
Published: August 2024

AbstractThe electrochemical conversion of CO2 into valuable chemicals is a promising route for renowable energy storage and the mitigation of greenhouse gas emission, and production of multicarbon (C2+) products is highly desired. Here, we report a 1.4 %Pd−Cu@CuPz2 comprising of dispersive CuOx and PdO dual nanoclusters embedded in the MOF CuPz2 (Pz=Pyrazole), which achieves a high C2+ Faradaic efficiency (FEC2+) of 81.9 % and C2+ alcohol FE of 47.5 % with remarkable stability when using 0.1 M KCl aqueous solution as electrolyte in a typical H‐cell. Particularly, the FE of alcohol is obviously improved on 1.4 %Pd−Cu@CuPz2 compared to Cu@CuPz2. Theoretical calculations have revealed that the enhanced interfacial electron transfer facilitates the adsorption of *CO intermediate and *CO−*CO dimerization on the Cu−Pd dual sites bridged by Cu nodes of CuPz2. Additionally, the oxophilicity of Pd can stabilize the key intermediate *CH2CHO and promote subsequent proton‐coupled electron transfer more efficiently, confirming that the formation pathway is skew towards *C2H5OH. Consequently, the Cu−Pd dual sites play a synergistic tandem role in cooperatively improving the selectivity of alcohol and accelerating reductive conversion of CO2 to C2+.
Unraveling C‐Selective Ring‐Opening of Phosphiranes with Carboxylic Acids and Other Nucleophiles: A Mechanistically‐Driven Approach
Authors: Ghosh Avisek , Van Nguyen Thi Hong , Bellanger Corentin , Chelli Saloua , Ahmad Mohammad , Saffon‐Merceron Nathalie , Taillier Catherine , Dalla Vincent , Mayer Robert J. , Dixon Isabelle M. , Lakhdar Sami 
Published: August 2024

AbstractPhosphiranes are weak Lewis bases reacting with only a limited number of electrophiles to produce the corresponding phosphiranium ions. These salts are recognized for their propensity to undergo reactions with oxygen pronucleophiles at the phosphorus site, leading to the formation of phosphine oxide adducts. Building on a thorough mechanistic understanding, we have developed an unprecedented approach that enables the selective reaction of carboxylic acids, and other nucleophiles, at the carbon site of phosphiranes. This method involves the photochemical generation of highly reactive carbenes, which react with 1‐mesitylphosphirane to yield ylides. The latter undergoes a stepwise reaction with carboxylic acids, resulting in the production of the desired phosphines. In addition to DFT calculations, we have successfully isolated and fully characterized the key intermediates involved in the reaction.
Preserving Molecular Tuning for Enhanced Electrocatalytic CO2‐to‐Ethanol Conversion
Authors: Fu Weiwei , Li Yuke , Chen Jiayi , Chen Jingyi , Xi Shibo , Zhang Jia , Wang Lei 
Published: August 2024

AbstractModifying catalyst surface with small molecular‐additives presents a promising avenue for enhancing electrocatalytic performance. However, challenges arise in preserving the molecular‐additives and maximizing their tuning effect, particularly at high current densities. Herein, we develop an effective strategy to preserve the molecular‐additives on electrode surface by applying a thin protective layer. Taking 4‐dimethylaminopyridine (DMAP) as an example of a molecular‐additive, the hydrophobic protection layer on top of the DMAP‐functionalized Cu‐catalyst effectively prevents its leaching during CO2 electroreduction (CO2R). Consequently, the confined DMAP molecules substantially promote the CO2‐to‐multicarbon conversion at low overpotentials. For instance, at a potential as low as −0.47 V vs. reversible hydrogen electrode, the DMAP‐functionalized Cu exhibits over 80 % selectivity towards multi‐carbon products, while the pristine Cu shows only ~35 % selectivity for multi‐carbon products. Notably, ethanol appears as the primary product on DMAP‐functionalized Cu, with selectivity approaching 50 % at a high current density of 400 mA cm−2. Detailed kinetic analysis, in situ spectroscopies, and theoretical calculations indicate that DMAP‐induced electron accumulations on surface Cu‐sites decrease the reaction energy for C−C coupling. Additionally, the interactions between DMAP and oxygenated intermediates facilitate the ethanol formation pathway in CO2R. Overall, this study showcases an effective strategy to guide future endeavors involving molecular tuning effects.
Preparation of Magnetic Fe‐Decorated Carbon Nanosheets From Waste Facemasks for Quantitative Detection of Flavonoids
Authors: Lian Jiajia , Chai Silin , Han Ying , Yang Dan , Liu Pei , Liu Qingyun 
Published: August 2024

ABSTRACTMany studies relating to the preparation of magnetic composites from various raw materials have been reported. However, for the first time, the magnetic Fe‐decorated carbon nanosheets (FeCNs) were prepared using waste facemasks with iron‐containing nose strip as both carbon source and iron source. The uniform decoration of Fe3O4 nanoparticles not only endows carbon matrix with magnetic separation property but also enriches the lamellar structure to furnish more catalytically active sites. The as‐prepared FeCNs nanozymes behave optimal peroxidase‐like activity under pH of 4 and temperature of 50°C, excellent reusability, and substrate affinity. Based on FeCNs, a convenient colorimetric strategy was successfully constructed for flavonoid detection in simulated and real samples. Experimental and theoretical results show that hydroxyl radicals (•OH) and superoxide radical (•O2−) are the major active species in the reactions that are catalyzed by FeCNs in the presence of H2O2. And the generation of these radicals can be attributed to the electron transfer between Fe2+/Fe3+ pairs and H2O2 molecules. This work provides a new way for preparing magnetic carbon‐based nanozymes and realizes the resource utilization of waste facemasks.
Assessment of the synergy of hydrophobicity and thermal conductivity in epoxy/graphite oxide composite coatings
Authors: Gholamnejad Zeinab , Abdeali Golnoosh , Bahramian Ahmad Reza 
Published: August 2024

AbstractIn various industrial applications, especially within the internal pipes of heat exchanger devices, there is a crucial need for surface coatings that offer both superhydrophobic properties and high thermal conductivity. Achieving the balance between these two characteristics is essential for optimizing heat transfer performance along metal pipe walls and mitigating the formation of water droplets on the surface. This research focuses on the development of polymer composite coatings to address these dual requirements, providing protection against humid environments, resistance to dew formation, and simultaneous enhancement of thermal conductivity. The key challenge lies in selecting a coating type that provides low surface energy and polarity, thereby achieving the desired hydrophobic properties while also maintaining adequate thermal conductivity. This study formulates polymer composite coatings utilizing laser‐modified epoxy resin and strategically integrates graphite oxide particles. These graphite particles undergo modification through oxidation to enhance compatibility with epoxy. In conjunction with graphite oxide modification, the resulting laser‐modified coatings exhibit super‐hydrophobic characteristics with an enhanced water contact angle of 162° and a low contact angle hysteresis (<5°). Furthermore, the epoxy/graphite oxide composite coatings demonstrate improved thermal conductivity, marking a significant 261% increase compared to pure epoxy, elevating it from .234 to .846 W/mK.
Biobased rubber toughened poly(lactic acid) blend for sustainable packaging films: The role of optical purity of poly(lactic acid)
Authors: Rosli Noor Afizah , Chen Ruey Shan , Dufresne Alain , Ahmad Ishak , Ahmad Sahrim , Shahdan Dalila , Shamene Bathumalai 
Published: August 2024

AbstractThis study investigates the novel effect of poly(lactic acid) (PLA) optical purity on PLA/liquid natural rubber (LNR) blend films fabricated by solution casting. An investigation was conducted to examine how different levels of PLA optical purity affect the mechanical, structural, morphological, thermal, and barrier properties of PLA/LNR films. Infrared spectroscopy analysis revealed that the D‐isomer content of PLA significantly affected the chemical interactions between the LNR and PLA. The favorable chemical interaction between the LNR and PLA with a high D‐isomer content also increased the elongation at break by 300%. Morphological investigations proved that the chemical interaction also improved the dispersion and reduced the size of the LNR droplets formed in the PLA matrix. Notably, while low D‐isomer PLA blends showed decreased crystallinity (Xc) upon LNR addition, high D‐isomer PLA blends exhibited increased Xc by 460%, leading to a 42% increase in oxygen transmission rate. Additionally, hydrolytic degradation of high D‐isomer PLA increased by 259% with increasing LNR content. Overall, optical purity of PLA plays an important role in determining the properties of PLA blends.
The influence of the molecular structure of binary block‐type styrene‐butadiene rubber on dynamic mechanical properties under normal and high‐pressure conditions
Authors: Wang Wenheng , Zhang Chunqing , Liao Mingyi 
Published: August 2024

AbstractThrough anionic two‐stage polymerization, block‐type styrene‐butadiene rubber (SSBR) with systematically regulable low‐temperature loss peaks is successfully prepared. The influence of 1,2‐Bd unit in the soft segment of block‐type SSBR on mechanical properties, dynamic mechanical properties, and microscopic morphology is studied, while pressure factors are introduced into dynamic mechanical studies. The block‐type SSBR with a soft segment containing 21.9 wt% of 1,2‐Bd exhibits the highest tensile strength, elongation at break, and tear strength. Under atmospheric pressure, the soft segment 1,2‐Bd unit influences the dynamic mechanical properties by altering the chain segment's motion loss capability. As the mass fraction of 1,2‐Bd increases from 21.9 to 58.6 wt%, tanδmaxincreases, the glass transition temperature of the soft segment increases from −59.0 to −18.9°C. Additionally, influenced by thermodynamic compatibility, the microscopic morphology transitions from strong separation to weak separation. Pressure affects dynamic mechanical properties by altering the free volume of the chain segments. Pressure reduces tanδmax, increasesTg, and raises the averageTgof the soft segment by 11°C. TheKvalue of the linear equation representing the relationship between the soft segmentTgand the mass fraction of 1,2‐Bd is unaffected by pressure.
Thermal kinetic, mechanical and wear properties of glass fiber reinforced polyamide 6 thermoplastic composites
Authors: Vikram Kamlendra , Pramanik Sumit , Bhaumik Shubrajit 
Published: August 2024

AbstractPolyamide 6 (PA6) thermoplastic‐based composites are often used in automobile, aerospace, marine, and biomedical applications. Here, PA6 and its composites with varied chopped glass fiber (GF) concentrations of 5, 10, and 20 mass% were fabricated by injection molding. The specimens were characterized by structural, thermal kinetic, mechanical, as well as tribological analyses. Tribological performance was evaluated in dry pin‐on‐disc test apparatus with three different levels of time, speed, and load factors. The PA6/GF composites showed high decomposition activation energy compared to pure PA6. Thermal activation, Ea increased to 46.16% with increasing of GF content up to 10 mass% in the composites compared to PA6. PA6/5GF exhibited best mechanical properties (e.g., strength = 44.46 MPa and Hardness = 45.2). Addition of GF in PA6 significantly improved tribological properties, coefficient of friction (COF) and specific wear rate (WR) besides thermal stability and mechanical properties of the composites. Especially, COF and WR of PA6/5GF composite decreased by 17%–65% and 68%–92%, respectively, compared to PA6. ANOVA statistical results determined the significant contribution of the tribological factors to the performance metrics of the composites for COF and WR. Therefore, the PA6/5GF composite would highly be useful for tie‐rod gears and bearings as a crucial structural component in automotive bodywork.
Fabrication of POE/POE‐g‐PHEMA/EuFT light conversion films for photovoltaic modules
Authors: Xu Mengnan , Zhang Zhiyuan , Tao Jiajun , Nai Yan , Su Chenglong , Jiang Shan 
Published: August 2024

AbstractIn this paper, the rare earth europium complex Eu(FTFA)3TPPO2 (EuFT) was synthesized by using europium as the central ion, 4‐trifluoro‐1‐(2‐furanyl)‐1,3‐butanedione (FTFA) as the first ligand, and triphenylphosphine oxide (TPPO) as the second ligand. The structure was characterized by Fourier transform infrared spectroscopy (FTIR), and the photoluminescence process was investigated by UV and fluorescence spectra. The luminescent film was prepared by adding EuFT and the compatibilizer POE‐g‐PHEMA into the POE matrix, which can convert the UV light to the red light, and improve the photovoltaic conversion efficiency while reducing the effect of UV aging on the cell. Experimental results show that the complex can absorb UV light (200–400 nm) and emit red light (612 nm), the luminescent film also maintains good luminescence performance. The peel strength of POE/POE‐g‐PHEMA/EuFT film achieves 23.9 N cm−1，while that of POE film is 12.8 N cm−1. The silicon cell prepared by POE/POE‐g‐PHEMA/EuFT film also showed higher EQE in UV region, and its current density–voltage (J–V) curve revealed that Jsc increased from 33.05 to 34.25 mA/cm2, the conversion efficiency increased from 12.99% to 13.39%, and the relative efficiency increased by 3.08%. The rare earth europium complex effectively improved the photoelectric conversion efficiency of solar cells.
Nc‐RNA‐mediated low expression of AZIN1 correlated with unfavorable prognosis in kidney renal clear cell carcinoma
Authors: Zeng Xinyi , Du Shen , Geng Lou , Ma Jiexian 
Published: August 2024

AbstractObjectiveKidney renal clear cell carcinoma (KIRC, ccRCC) is the most common type of renal cancer with high recurrence and mortality. It has long been recognized that Antizyme inhibitor 1 (AZIN1) serves as a pro‐oncogenic molecule in multiple cancers. However, the clinicopathological features of AZIN1 in KIRC remain unexplored.Materials and MethodsThe Cancer Genome Atlas (TCGA, TIMER, and GEPIA) were employed for pan‐cancer expression and survival analysis of AZIN1, indicating the unique anti‐tumor role of AZIN1 in KIRC. The expression and clinical characteristics of AZIN1 in KIRC were further proven via Human Protein Atlas and TCGA. single‐sample GSEA was employed to investigate the immune infiltration of AZIN1. Then the downstream pathways were illustrated via the LinkedOmics, Metascape, and Cytoscape databases. The possible upper regulating noncoding RNAs (ncRNAs) were analyzed from five programs‐TargetScan, StarBase, miRanda, PITA, and miRmap.ResultsAZIN1 is downregulated in KIRC patients. Lower levels of AZIN1 were linked with unfavorable outcomes in KIRC patients. The AZIN1 expression was positively related to immune cell infiltration in KIRC. We also elucidated a possible upstream regulatory ncRNA of AZIN1 in KIRC namely STK4‐AS1/AC068338.2‐miR‐106b‐5p‐AZIN1 axis as well as the downstream signaling pathways.ConclusionThis study illustrated the unique anti‐tumor role of AZIN1 in KIRC and provided potential value for guiding immunotherapy and targeted therapy.
Orthogonal Control of Nucleic Acid Function via Chemical Caging‐Decaging Strategies
Authors: Wang Xiangnan , Wen Siyu , Wu Zhenkun , Jiang Jian‐Hui 
Published: August 2024

AbstractThe ability to precisely control the function of nucleic acids plays an important role in biosensing and biomedicine. In recent years, novel strategies employing biological, physical, and chemical triggers have been developed to modulate the function of nucleic acids spatiotemporally. These approaches commonly involve the incorporation of stimuli‐responsive groups onto nucleic acids to block their functions until triggers‐induced decaging restore activity. These inventive strategies deepen our comprehension of nucleic acid molecules’ dynamic behavior and provide new techniques for precise disease diagnosis and treatment. Focusing on the spatiotemporal regulation of nucleic acid molecules through the chemical caging‐decaging strategy, we here present an overview of the innovative triggered control mechanisms and accentuate their implications across the fields of chemical biology, biomedicine, and biosensing.
Dioxygen Controlled Chemodivergent Cross‐Coupling of Primary and Secondary Alcohols Using Noninnocent Azo Aromatic Complexes of Cobalt(II) as Catalysts
Authors: Kamal  , Samanta Subhas 
Published: August 2024

AbstractHerein, employing pincer like cobalt (II) complexes containing redox noninnocent azo‐benzimidazole ligand a switchable and chemodivergent catalytic cross‐coupling of primary and secondary alcohols is reported. The reactions are environmentally benign and atom efficient. It liberates water and hydrogen gas as the only byproducts. While the reaction in inert condition gives
alkylated ketones, in presence of air as well as lower temperature and base loading selectively results in
unsaturated ketones. Both the catalytic protocols have very good functional group tolerance. Thus, a wide range of substrates have been found to be effective for the synthesis of
alkylated ketones as well as
unsaturated ketones via dehydrogenative cross‐coupling reaction of alcohols. Several control experiments and kinetic studies were performed to elucidate the reaction pathways.
Electrocatalytic Synthesis of Organonitrogen Compounds via C−N Coupling from NOx and Carbon Source
Authors: Zhou Yiyang , Ding Chunmei , Li Can 
Published: August 2024

AbstractNitrogen oxide (NOx) is an attractive nitrogen source. Electrocatalytic NOx reduction coupled with the conversion of carbon source molecules offers a potential route for sustainable synthesis of valuable nitrogenous organics. This review discusses recent progress on the synthesis of electrocatalytic organonitrogen compounds (such as oximes, amino acids, amines, amides and urea) via C−N coupling from NOx and carbon source. The electrocatalytic performance, catalyst structure and especially reaction mechanism are discussed. Current challenges, catalyst design principles, the understanding on reaction mechanisms, as well as possible strategies for improving reaction selectivity and activity are proposed, which will guide future researches in the electrocatalytic conversion of NOx and carbon source.
Enhanced Oxygen Reduction Reaction Via Oxygen Vacancy‐Rich Silica‐Supported Ag/Pd Nanoshells
Authors: dos Santos Pereira Fellipe , Anchieta e Silva Felipe , Azevedo Silva Augusto César , de Jesus Gomes Varela Júnior Jaldyr , Mateus Pinatti Ivo , Rojas Alex , Mantilla Angeles , Alcântara Ana C. S. , Baraldi Dourado Andre Henrique , Tofanello Aryane , Atsushi Tanaka Auro , Silva Rodrigues Thenner , Suller Garcia Marco Aurélio 
Published: August 2024

AbstractHerein, we demonstrated the fine‐tuning of catalysts’ active phase by employing AgPd nanoshells with distinct Ag/Pd ratios synthesized via a galvanic replacement method for the oxygen reduction reaction (ORR). However, more interestingly, the subsequent immobilization of such Ag/Pd ratios onto silica further influenced the support characteristics, creating an increasing concentration of oxygen vacancies in this typically inert support — a surprising and unparalleled outcome attested by electrochemical impedance spectroscopy, electron paramagnetic resonance, and theoretical calculation. Such a phenomenon promoted obtaining an optimized electro/photocatalyst with exceptional activity, facilitating not just the ORR but also the photochemical water‐splitting reaction. Curiously, adjusting the Ag/Pd ratio also affected the ORR mechanism, which was switched from a 2‐electron to a 4‐electron after optimization. Finally, Ag38Pd62/SiO2, the catalyst with the best proportion, exhibited a remarkable hydrogen production rate of 1039.8 μmol/gcatalyst during 300 minutes of water splitting, surpassing the performance of the conventional Degussa TiO2 P25 catalyst.
Co‐W (Hydr)oxide with Ultralow Ru Promotes Water Dissociation Coupled H+ Abstraction in Alkaline HER
Authors: M Rama Prakash , G Nasrin Banu , Neppolian Bernaurdshaw , Sengeni Anantharaj 
Published: August 2024

AbstractThe hydrogen evolution reaction in alkaline water electrolysis is facilitated through the electrodeposition of trimetallic catalyst on nickel foam using the chronoamperometry technique. Specifically, the trimetallic catalyst CoWRu@NF is deposited onto a nickel foam substrate. The catalytic performance of this trimetallic catalytic electrode for the Hydrogen Evolution Reaction (HER) is then assessed in a 1.0 M potassium hydroxide (KOH) solution. This specially designed trimetallic catalytic electrode system efficiently provides the more active sites through the Co component. Subsequently, it facilitates the reduction of protons (H+) to generate hydrogen gas using the Ru component. Tungsten acts as a co‐catalyst in the system for water dissociation promotor by removing hydroxide formed after water dissociation and preventing the deactivation of Ruthenium by certain reaction intermediates. The CoWRu@NF trimetallic catalyst demonstrates excellent activity, showcasing a low overpotential (−8 mV) to achieve a current density of (−10 mA/cm2. Additionally, it exhibits low Tafel slope values (101.2 mV dec−1), credited to the presence of cobalt and tungsten alongside Ruthenium in the catalytic system. This configuration is specifically designed to enhance the kinetics of the hydrogen‐evolving reaction.
Controlled Photooxidation via Singlet Oxygen Generation by Triplet Harvesting in a Heavy Atom Free Pure Organic Dithienylethene‐Naphthalene Diimide
Authors: Bag Sayan Kumar , Mondal Bijan , Karmakar Manisha , Das Subhadeep , Patra Abhijit , Thakur Arunabha 
Published: August 2024

AbstractNoninvasive control over the reversible generation of singlet oxygen (1O2) has found the enormous practical implications in the field of biomedical science. However, metal‐free pure organic emitters, connected with a photoswitch, capable of generating “on‐demand” 1O2 via triplet harvesting remain exceedingly rare; therefore, the utilization of these organic materials for the reversible control of singlet oxygen production remains at its infancy. Herein, an ambient triplet mediated emission in quinoline‐dithienylethene (DTE)‐core‐substituted naphthalene diimide (cNDI) derivative is unveiled via delayed fluorescence. The quinoline‐DTE‐cNDI triad displayed enhanced photoswitching efficiency via double FRET mechanism. It was found to have direct utilization in controlled photosensitized organic transformations via efficient generation of singlet oxygen (yield ΦΔ~0.55 in DCM and 0.73 in methanol). The designed molecule exhibits a long‐lived emission (τ∼1.1 μs) and very small singlet‐triplet splitting (ΔEST) of 0.13 eV empowering it to display delayed fluorescence. Comprehensive steady state and time‐resolved emission spectroscopy (TRES) analyses along with DFT calculations offer detailed understandings into the excited‐state manifolds of organic compound and energy transfer (ET) pathways involved in 1O2 generation.