bluuebunny/crossref_metadata_2025_split huggingface dataset:
Catalytic Asymmetric Synthesis and Applications of Stereogenic β′‐Methyl Enones and β,β′‐Dimethyl Ketones
Authors: Zhang Zongpeng , Zhu Bing‐Ke , Yi Zhi‐Yuan , Fang Ting , Jin Zhuan , He Ling , Chen Bo‐Bin , Qi Xiaotian , Wang Chun‐Jiang 
Published: December 2024

AbstractThe “Magic Methyl” effect has received tremendous interest in medicinal chemistry due to the significant pharmacological and physical modification of properties that have been observed upon introducing a methyl group, especially, a stereogenic methyl group into potential chiral drug candidates. The prevalence of stereogenic β‐methyl ketone structural motifs in bioactive compounds and natural products has long motivated the development of enantioselective strategies toward their synthesis. Herein, we have rationally designed a Rh‐catalyzed asymmetric monohydrogenation of readily‐available β′‐methylene conjugated enones with high efficiency and remarkable site‐selectivity and enantioselectivity control for the practical construction of enantioenriched β′‐methyl unsaturated enones that are difficult to access by other methods. Control experiments revealed that the conjugated C=C bond in β′‐methylene conjugated enones plays a significant role in enhancing the reactivity of monohydrogenation. This methodology is applicable for the preparation of chiral β,β′‐dimethyl ketones through consecutive double asymmetric hydrogenation of β,β′‐dimethylene ketones. Detailed mechanistic investigation and DFT studies further provided strong support for a unique processive catalysis pathway for double asymmetric hydrogenation. The synthetic utilities have been demonstrated in the concise synthesis of several key intermediates for bioactive molecules, asymmetric total synthesis of natural products (S)‐(+)‐ar‐Turmerone and (S)‐(+)‐dihydro‐ar‐Turmerone, and two C2‐symmetric chiral spirocyclic diol frameworks.
Halting Oxygen Evolution to Achieve Long Cycle Life in Sodium Layered Cathodes
Authors: Wang Haoji , Gao Jinqiang , Mei Yu , Ni Lianshan , He Yi , Hong Ningyun , Huang Jiangnan , Deng Wentao , Zou Guoqiang , Hou Hongshuai , Liu Tongchao , Liang Chaoping , Ji Xiaobo , Amine Khalil 
Published: December 2024

AbstractOxygen redox chemistries at high voltage have materialized as a revolutionary paradigm for cathodes with high‐energy density; however, they are plagued by the challenges of labile oxygen loss and rapid degradations upon cycling, even after concerted endeavors from the research community. Here we propose a multi‐concentration stratagem propelled by entropy reinforcement to enhance the electronic structure disorder (ESD) at high desodiation states for impeding undesired oxygen mobility and ensuring controlled oxygen activity, elucidated by density functional theory calculations. The increased disorder strengthens the reversible electrochemistry of lattice oxygen redox, leading to effectively suppressed P−O structural evolution and highly stable localized TMO6 octahedral environments, as demonstrated by soft/hard X‐ray absorption spectroscopy. Furthermore, through a comparative analysis of sodium‐layered cathodes with different configuration entropy, we reveal that a high‐entropy state induced by cationic disordering has the capacity to perturb cationic redox boundaries, significantly restraining the formation of detrimental O′3 phases. As a consequence, the high‐voltage cycling stability has been greatly upgraded, up to 4.4 V versus Na+/Na, with an impressive 90.1 % capacity retention at 1 C over 100 cycles and 76.1 % capacity retention at 2 C over 300 cycles. The resilient oxygen redox, enabled through the control of ESD, broadens the horizons for entropy engineering and lays the foundation for advancements in high‐energy, long‐cycling, and safe batteries.
Control of Bilayer Transport through a Photoswitchable Membrane‐Stiffening Agent
Authors: Bos Jasper E. , Duindam Nol , Kock Thomas J. F. , Siegler Maxime A. , Wezenberg Sander J. 
Published: December 2024

AbstractThe mobility of proteins in the bilayer membrane is affected by (local) changes in lipid environment, which is important to their biological functioning. Artificial molecular systems that—to some extent—imitate tasks of membrane‐embedded proteins are increasingly developed, however, they are usually controlled through responsive units in their core structure. Here we present an alternative approach based on an amphiphilic stiff‐stilbene derivative that enables control of membrane fluidity by light. The fluidity increase upon E‐to‐Z isomerization is shown to enhance the activity of known synthetic anion transporters as a result of a higher mobility. The photoisomerization process is studied by UV/Vis and 1H NMR spectroscopy in solution and in POPC vesicles, where the light‐induced changes in fluidity and hence, activity of anion transporters, are monitored by fluorescence spectroscopy. Dynamic light‐scattering (DLS) and cryo‐EM studies show that vesicle integrity is not impaired by photoswitching. Our work introduces a versatile approach to control solute transport by carrier molecules. Moreover, the photocontrol over membrane fluidity and, with that, mobility could eventually be used for directed motion, which we expect to be key in achieving active transport in the future.
A Hydrolytically Stable Metal–Organic Framework for Simultaneous Desulfurization and Dehydration of Wet Flue Gas
Authors: Pang Jing‐Jing , Yao Zhao‐Quan , Huang Hong‐Liang , Li Lin , Li Quan‐Wen , Lu Nan , Song Zi‐Han , Xu Jian , Bu Xian‐He 
Published: December 2024

AbstractMetal–organic frameworks (MOFs) have great prospects as adsorbents for industrial gas purification, but often suffer from issues of water stability and competitive water adsorption. Herein, we present a hydrolytically stable MOF that could selectively capture and recover trace SO2 from flue gas, and exhibits remarkable recyclability in the breakthrough experiments under wet flue‐gas conditions, due to its excellent resistance to the corrosion of SO2 and the water‐derived capillary forces. More strikingly, its SO2 capture efficiency is barely influenced by the increasing humidity, even if the pore filling with water is reached. Mechanistic studies demonstrate that the delicate pore structure with diverse pore dimensions and chemistry leads to different adsorption kinetics and thermodynamics as well as segregated adsorption domains of SO2 and H2O. Significantly, this non‐competitive adsorption mechanism enables simultaneous desulfurization and dehydration by a single adsorbent, opening an avenue toward cost‐effective and simplified processing flowcharts for flue gas purification.
Engineering d‐p Orbital Hybridization in a Single‐Atom‐Based Solid‐State Electrolyte for Lithium‐Metal Batteries
Authors: Shen Jiadong , Chen Junjie , Xu Xiaosa , Li Jin , Wang Zhenyu , Wang Yu , Lin Pengzhu , Sun Jing , Huang Baoling , Zhao Tianshou 
Published: December 2024

AbstractRegulating lithium salt dissociation kinetics by enhancing the interaction between inorganic fillers and lithium salts is vital for enhancing the ionic conductivity in solid‐state composite polymer electrolytes (CPEs). However, the influence of fillers’ external electronic environments on lithium salt dissociation dynamics remains unclear. Here, we design single‐atom sites in metal–organic framework fillers for poly(ethylene oxide) (PEO)‐based CPEs, boosting lithium salt dissociation through an electrocatalytic strategy. This strategy enhances lithium‐ion conductivity by tuning the coupling strength between the d and p orbitals of the fillers, as captured by a newly identified descriptor (λ) via high‐throughput density functional theory (DFT) calculations and machine learning. The optimal single atom (Ti) sites are incorporated into a ZIF‐8 matrix for PEO‐based CPEs, achieving an ionic conductivity exceeding 10−3 S cm−1 at 30 °C. Additionally, the electrolyte forms a robust solid electrolyte interphase and is compatible with LiCoO2, LiNi0.9Co0.05Mn0.05O2, and sulfur cathodes. Consequently, the solid‐state lithium metal battery with the electrolyte demonstrates excellent cycling stability, maintaining performance over 5000 cycles at 10 C with LiFePO4 cathodes and stable operation at −30 °C. These findings highlight the transformative potential of engineering d‐p orbital hybridization by incorporating single‐atom sites into inorganic fillers for designing highly ion‐conductive CPEs.
Photoredox Activation of Donor‐Acceptor Cyclopropanes: Distonic Radical Cation Reactivity in [3+2] Cycloaddition Reactions
Authors: Mondal Subhashis , Debnath Saradindu , Lo Rabindranath , Maity Soumitra 
Published: December 2024

AbstractAltering the reactivity model of a molecule can potentially eliminate limitations existing in its current paradigm. When it comes to the activation of Donor‐Acceptor Cyclopropanes (DACs), Lewis acids have been the state‐of‐the‐art. Although a variety of polarized 2π components have been successfully coupled with DACs for [3+2] cycloaddition, unpolarized alkenes prove to be a roadblock due to an inherent polarity mismatch with the Lewis acid‐mediated 1,3‐zwitterionic intermediate. Hereby, harnessing the distonic radical cation mode of cleavage by photoredox catalysis overcomes this mismatched reactivity of the zwitterionic intermediate, providing a unique route to highly substituted cyclopentanes and cyclopentenes. Expansion of this strategy to bicyclo[1.1.0]butanes enables access to bicyclo[3.1.1]heptanes (BCHs) through a facile [3σ+2σ] cycloaddition. Detailed mechanistic insights are also provided using dispersion‐corrected density functional theory.
Tailored Silica‐Based Sensors (SBA‐Pr‐Ald‐MA) for Efficient Detection of Iron (III) Ions: A Comprehensive Theoretical and Experimental Viewpoint
Authors: Mohammadi Ziarani Ghodsi , Ebrahimi Dorsa , Feizi‐Dehnayebi Mehran , Badiei Alireza , Abu‐Dief Ahmed M. 
Published: December 2024

ABSTRACTThe synthesis and characterization of SBA‐Pr‐Ald‐MA as a modified mesoporous silica material made from SBA‐15 are presented in this work. Meldrum's acid (MA), 2‐chloroquinoline‐3‐carbaldehyde, and 3‐(chloropropyl)‐trimethoxysilane were used to functionalize the SBA‐15. The detection limit of 7.80 × 10−8 M for SBA‐Pr‐Ald‐MA demonstrated its exceptional selectivity toward Fe3+ ions. Density functional theory (DFT) calculations were conducted using B3LYP/6‐311g(d,p)/LANL2DZ to investigate the molecular electrostatic potential (MEP), geometry optimization, molecular orbital analysis, quantum chemical descriptors, and photoinduced electron transfer (PET). Geometry optimization and the MEP diagram verified the mechanism of the interaction obtained from experimental results. PET analysis indicated that the electrons transition to the LUMO of the Pr‐Ald‐MA + Fe3+ complex, leading to maximum fluorescence quenching efficiency. Future research could explore the sensor's application in real‐world environmental monitoring systems and extend its application to detect other hazardous metal ions.
Investigation of the Products and the Migration of Sodium and Chlorine During Pyrolysis of High‐Sodium Coal Mixed With Phosphorite
Authors: Tian Zhihua , Wang Qinhui 
Published: December 2024

ABSTRACTThe impact of adding phosphorite during the pyrolysis of high‐sodium Shaerhu coal to address severe deposition and corrosion issues caused by the release of volatile sodium and chlorine compounds was explored. During pyrolysis, sodium compounds volatilize and condense on cooler surfaces, leading to deposits that corrode metal and reduce boiler efficiency. By copyrolyzing phosphorite with coal, the study finds that tar yield decreases, whereas char yield increases, with slightly improved char reactivity. The pyrolysis gas yield also increases, with higher concentrations of methane and hydrogen, enhancing energy utilization. Calcium compounds in phosphorite react with sodium chloride and sodium sulfate, forming high‐melting‐point, insoluble sodium compounds and water‐soluble chlorides, thereby reducing the release of sodium and chlorine. This reduces fouling and corrosion, improving equipment efficiency. Additionally, recycling copyrolyzed phosphorite for yellow phosphorus production can enhance conversion ratios, supporting the production of higher‐value phosphorus chemicals.
Shape Memory Behavior of Polyacrylamide/Multi‐Walled Carbon Nanotubes Nanocomposite Aerogel
Authors: Yousefpour Navid Zahra , Alamdarnejad Ghazaleh , Kokabi Mehrdad 
Published: December 2024

ABSTRACTThe development of lightweight, stimuli‐responsive materials remains a significant challenge in materials science. Shape memory aerogels represent a promising category of smart materials, yet their widespread application has been limited by performance constraints. This study explores the synthesis and characterization of polyacrylamide (PAAm) hydrogels enhanced with multi‐walled carbon nanotubes (MWCNTs) and transformed into aerogels through freeze‐drying. The obtained aerogels were characterized using mercury intrusion porosimetry, weighing method, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy. The results revealed that the aerogels possessed high porosity (over 80%), low density (0.098 g cm−3), high specific surface area (152 m2 g−1), and an average pore diameter of 1280 nm. Electrical conductivity analysis demonstrated an electrical percolation threshold at 2.5 wt.% of MWCNTs. Furthermore, dynamic mechanical analysis indicated a 400% increase in the Young's modulus in the presence of nanoparticles. The mentioned aerogel exhibited shape memory behavior under direct thermal stimulation, and the results also showed that the shape recovery ratio and shape recovery speed of the nanocomposite aerogel were 14% and 74% higher than those of the PAAm aerogel, respectively. The enhancements in mechanical and shape memory properties, combined with inherent lightweight nature, suggest promising applications across various technical fields, from aerospace to biomedical engineering.
Supporting minority cultures during initial engagements with body donors in the dissecting room: A pilot study exploring perspectives of Pasifika medical students around culture and cultural safety
Authors: Madgwick Jacob , Anderson Lynley , Cornwall Jon 
Published: December 2024

AbstractThe first experience of medical students in the dissecting room (DR) is a challenging event. Few data exist around whether or how culturally appropriate support is required in the DR for students from ethnic minorities. This pilot study explored Pasifika (peoples with heritage from the Pacific Islands) students' first experience of the DR and exposure to body donors to explore cultural perspectives around this event. Participants were second year Pasifika medical students with no prior engagement with body donors. Following a first exposure to body donors, semi‐structured face‐to‐face interviews were conducted. Questioning explored how Pasifika students experienced initial DR engagement in regard to Pasifika culture and cultural safety. Interviews were recorded, transcribed, and analyzed thematically. Eight Pasifika students were interviewed (ages 18–32 years, mean 21.3 years, five females); mean interview duration 24.5 min. Four themes were identified: cultural observations, student behaviors, cultural safety, and cultural comfort. Dominant messages included the cultural challenges presented by this event, conformity of cultural behavior, identification of cultural safety being appropriate, and illumination of potential cultural support strategies. Current mechanisms supporting cultural safety were identified as adequate, which juxtaposed against behavior where students could not act in a culturally authentic manner. Suggestions were made around improving cultural comfort, such as the presence of elders or Christian‐focused elements such as prayer. Enhanced cultural support could increase cultural comfort for the initial DR and body donor experience of Pasifika students, which may facilitate increased cultural knowledge and promote cultural diversity within the medical student cohort.
Non‐Covalent Self‐Assembly Behaviors Based on Racemic Binaphthol Scaffolds
Authors: Feng Zhimin , Sun Tingting , Luo Xu , Luo Yi , Tan Jiao , Ni Xin‐Long 
Published: December 2024

AbstractUnderstanding the fundamental mechanisms involved in the construction and organization of multi‐scale structures is crucial for the design and manufacture of complex functional systems with long‐range molecular arrangements. In this paper, a series of compounds have been synthesized using racemic binaphthols as the skeleton and a Suzuki coupling reaction for derivatization at the 6,6′ positions, which resulted in various structures bearing different functional groups. Control over the self‐assembly of these racemic binaphthol derivatives was successfully achieved by adjusting the types and positions of the substituents in the parent binaphthol compound, which revealed the key factors influencing the types of the non‐covalent interactions and the self‐assembly process. For example, the single‐crystal structures of the resulting compounds indicated that assembly structures such as single helix and double helix based on non‐traditional hydrogen bond motifs could be obtained, and fascinating non‐covalent self‐assembly structures such as molecular ladders and catenane discovered.
Distributed generalized Nash equilibrium seeking strategy design for multi‐cluster games of high‐order players
Authors: Liu Cong , Liu Yangyang , Wang Jing , Hu Yang , Liu Yongmin , Deng Zhenhua 
Published: December 2024

AbstractIn this paper, a multi‐cluster game (MCG) of autonomous players is explored. Different from the existing MCGs, the high‐order dynamics of players is taken into account in our problem. Owing to the high‐order dynamics of players, existing strategies for MCGs are unable to tackle our problem. For purpose of seeking the variational generalized Nash equilibrium (vGNE) of the game, a distributed strategy is designed on the basis of gradient descent and state feedback, in which a distributed estimator is embedded for the players to estimate the decisions of other players. Furthermore, the asymptotical convergence of the strategy is analyzed via Lyapunov stability theory and variational analysis. Finally, the effectiveness of our method is verified through a numerical simulation.
Highly Stable Cyclic Performance of Benzoquinone‐Based Organic Cathode in Aqueous Zinc Ion Batteries
Authors: Sajid Muhammad , Ur Rahman Sami , Tao Fang‐Yu , Xie Dan , Ur Rehman Muhammad Saif , Salah Abdulwahab , Zhang Jing‐Ping 
Published: December 2024

AbstractAn organic polymer, poly‐(2,3‐dithio‐1,4‐Benzoquinone) (PDBQ) was synthesized through condensation polymerization and characterized by SEM, EDS, XRD, FT‐IR, BET, TGA, NMR and XPS. FT‐IR results displayed the carbonyl and thio functionality of the material, elemental composition, and chemical states were confirmed by XPS and EDS. The material exhibited a sheet‐like interconnected morphology and good thermal stability. The fabricated cathode delivered a high specific capacity of 157.39 mAh g−1 at a current density of 100 mAg−1 with high reversibility in full‐cell aqueous zinc ion batteries (AZIBs). The congenital soft structure enhances the reversibility, Zn+2 insertion‐desertion, and stability of the electrode material in coin‐cell batteries. Owing to these characteristics the battery delivered higher stability with capacity retention of 97.65 % after 1500 cycles and remained at 73.2 % after 20,000 cycles at a high current density of 2.0 Ag−1 with almost 100 % columbic efficiency. The energy storage behavior of the fabricated cathode was further studied by cyclic voltammetry and electrochemical impedance spectroscopy, as well as the charge storage mechanism through ex‐situ FT‐IR, EDS, and XPS. These results are promising to achieve the objective of stable organic material as a cathode for AZIBs.
Does the transfer of knowledge from the pioneer generation to the second‐generation speed‐up the learning curve of robot‐assisted partial nephrectomies? TRANSFER trial (UroCCR n°83)
Authors: Vignot Louis , Khene Zine‐Eddine , Mellouki Adil , Morrone Arnoult , Bernhard Jean‐Christophe , Bensalah Karim , Chevallier Daniel , Doumerc Nicolas , Roupret Morgan , Nouhaud Francois‐Xavier , Lebacle Cédric , Long Jean‐Alexandre , Pillot Pierre , Tillou Xavier , Tibi Brannwel , Durand Matthieu , Ahallal Younes , Bentellis Imad 
Published: December 2024

AbstractObjectivesThe objective is to compare the learning curves between two pioneer and three second‐generation surgeons for RAPN in terms of WIT, CD and positive surgical margins.Materials and methodsThe charts of consecutive RAPNs of three centres were reviewed from the UroCCR prospective database. The experience was assessed by a regression model for each group. There was a univariate analysis on three consecutive sequences of 15 procedures. The learning speed for WIT was explored graphically by polynomial regression after cubic splines. Finally, CUSUM charts were obtained.ResultsThere were 1203 RAPN in the pioneer group and 119 performed by second‐generation surgeons. There was a significant difference in the distribution of tumour size (p < 0.001) and the RENAL score (p < 0.001). The operative time was longer in the first group (p > 0.001). Independent factors for a higher WIT were the second group (p < 0.001), higher experience (p < 0.001) the collinearity between the group and experience (p < 0.001), the RENAL score (p < 0.001) and blood loss (p < 0.001). Adjusted Loess regressions showed a plateau of WIT at 400 procedures for the pioneers and a significant decrease at 20 procedures for the second generation. CUSUM chart analysis showed a ‘staircase’ pattern of the learning process, with three major steps at 150, 200 and 300 procedures. The major limitation is the difference in sample size between the two arms.ConclusionsLearning curve patterns would reflect a transfer of knowledge to the second‐generation, as opposed to the establishment of standards by the pioneers.
Facile Approach to Develop Peptide‐Stabilized CdS/CdSe Quantum Dots for Cellular Imaging
Authors: Singh Rohit Kumar , Suryakanta Uday , Panigrahi Bijayananda , Mishra Sourav , Das Swatilekha , Bhatta Sushil Ranjan , Ghosh Sunil K. , Mandal Dindyal 
Published: December 2024

ABSTRACTThis study presents a mild, one‐pot synthetic approach for the synthesis of multicolor, water soluble, photo luminescent CdS and CdSe quantum dots (QDs). To achieve this goal, cyclic peptides containing cysteine residues are rationally designed and synthesized. Among the peptides tested, those containing two cysteine residues exhibit superior stabilizing properties, ensuring the solubility and long‐term stability of the QDs in aqueous solutions for several months. The newly synthesized QDs exhibit unique excitation‐dependent multicolor photoluminescence with a quantum yield of 20.55% and 45.50% for CdS and CdSe, respectively, providing versatility for imaging applications. Cellular uptake studies using HCT 116 cells reveal effective internalization of the QDs into both the cytoplasm and nucleus, highlighting their potential applications in bioimaging and drug delivery. This green synthesis approach underscores the crucial role of peptide chemistry in nanoparticle stabilization, paving the way for the development of functional nanomaterials tailored for specific uses in bioimaging and nanomedicine.