bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficient Pump Scheduling for Large‐Scale Multiproduct Pipelines Using Deep Reinforcement Learning
Authors: Shao Kai , Wang Xinmin , Liu Min , Xu Aobo , Jian Ling
Published: September 2024

Optimizing pump scheduling in multiproduct pipelines can significantly reduce energy consumption and carbon emissions. For pump scheduling in multiproduct pipelines, to describe hydraulic losses more accurately, the model needs to adopt shorter discrete time intervals, which will lead to longer decision‐making time. It combined with the large solution space of large‐scale pipelines, will lead to low solution efficiency with dynamic programming methods and poor solution quality with heuristic optimization algorithms. Given that, this article develops a multiproduct refined oil transmission simulation system and employs the enhanced Proximal Policy Optimization (PPO) algorithm with action space shaping trick to optimize pump scheduling for large‐scale multiproduct pipelines. The method of converting discrete action space to multi‐discrete action space through action shaping can address PPO's low convergence efficiency issue resulting from the large discrete action space challenge common in large‐scale multiproduct pipelines. The experimental results indicate that the proposed method, that is, PPO algorithm with multidiscrete action space exhibits significant advantages in terms of efficiency and robustness in large‐scale pipelines compared to mainstream methods for pump scheduling such as dynamic programming (DP), genetic algorithms (GA), and ant colony optimization (ACO). Furthermore, we demonstrate the effectiveness of action space shaping in large‐scale pipelines from the perspectives of exploration and exploitation.
Design of Broadband Phased Array Feed Using Stereolithographic Additive Manufacturing Heterogeneous Integrating Technology for Fast Radio Burst Observation
Authors: Wang Shao‐Fei , Liu Haiwen , Du Chao , Qi Huan‐Huan , Xu Hao
Published: September 2024

Herein, a stereolithography appearance 3‐D printed phased array feed (PAF) on radio telescopes based on broadband Vivaldi antenna elements covering 4–10 GHz, which meets the requirements of low cost, lightweight, and compact volume, is designed and proposed. The prototype is integrated with two orthogonal linear polarized 4 × 5 arrays, each of which is composed of 20 Vivaldi antenna elements. The distance between adjacent antenna elements is 1/2 λ in both E‐plane and H‐plane. By increasing thickness of the slice elements compared with traditional end‐fire arrays on printed circuit board, the wide‐band impedance matching is realized. The mutual impedance matrix of the dual‐polarization array is calculated and the equivalent circuit of the active and parasitic elements is demonstrated. Due to the orthogonal parasitic elements inserted between the adjacent active antennas, equivalent capacitance is introduced in the tightly coupled array. The measured active voltage standing wave ratio of the manufactured PAF exhibits 4–10 GHz operating bandwidth for both broadside radiation and 45° scan in both E‐ and H‐plane polarization. The proposed wideband PAF has a promising potential application prospect in fast radio burst and other astronomic observation.
Lightweight, Highly Extensible, and Anti‐Leak Liquid Metal Elastomer Composites with an Interpenetrating Architecture
Authors: Ding Xilong , Jiang Yunpeng
Published: September 2024

In this study, a reformed sugar template‐based method is employed to prepare gallium‐based liquid‐metal‐filled elastomer composites (LMECs), which allows the uniform dispersion of LM droplets within the elastomer matrix in the form of an interpenetrating morphology. In the current preparation, a portion of the liquid metal (LM) is extracted from the elastomer foam following a complete vacuum infusion, resulting in a 10% volume fraction of LM droplets remaining. These droplets exhibit strong adhesion to the inner surfaces of the elastomer foams through the Ga2O3 layer. Nevertheless, the electrical and thermal conductivities are found to be 0.72 × 103 S m−1 and 0.48 W m−1 K−1, respectively. The mechanical performance, piezo‐resistive effect, and thermal conductivity are measured to establish the structure–property relationships. Furthermore, the intrinsic microphysical mechanisms are identified from their distinctive architectures. The reformation of the conventional sugar template approach results in the low concentration and homogeneous dispersion of LM droplets, endowing the resulting LMECs with lightweight and versatile properties, and also mitigating LM leakage to some extent. Herein, this work may prove instrumental in the development of stretchable electronics, soft robots, and multifunctional materials with interpenetrating networks.
S‐Scheme Heterojunction Fabricated from Covalent Organic Framework and Quantum Dot for Enhanced Photosynthesis of Hydrogen Peroxide from Water and Air
Authors: Ma Xiaolin , Li Senzhi , Gao Ying , Li Ning , Han Yuesheng , Pan Houhe , Bian Yongzhong , Jiang Jianzhuang
Published: September 2024

Covalent organic frameworks (COFs) with stable crystalline porous structures and flexible assembly properties contribute to the direct photocatalytic synthesis of H2O2 to meet the growing global demand. To address the challenges of insufficient redox capacity and photogenerated carrier recombination of COFs, S‐scheme heterojunction is constructed from COFs with quantum dots (QDs) to improve the photocatalytic production of H2O2. Herein, 0D ZnCdS QDs (ZCS) uniformly anchor on the surface of a 2D conjugated tetrathiafulvalene‐based COF (TT‐COF), affording the S‐scheme heterojunction TT‐COF/ZCS. Formation of S‐scheme heterojunction effectively prevents the agglomeration of ZCS, modulates the energy band structure of TT‐COF, and enhances the migration of photogenerated carriers and redox ability. As a total consequence, the optimized heterojunction (TZ‐40) is able to afford H2O2 in the yield up to 5171 µmol g−1 h−1 under visible light irradiation with H2O and O2, much higher than those for TT‐COF, 2520 µmol g−1 h−1, and ZCS, 2647 µmol g−1 h−1. The present result demonstrates the great potential of COFs/QDs‐based S‐scheme heterojunctions for photocatalytic applications including photocatalytic H2O2 production.
High‐Efficiency Thick Film Binary Organic Photovoltaics via Asymmetric Alkyl Chain Engineering
Authors: Zhu Shengtian , Chen Shihao , Hong Ling , Hao Lu , Xie Juxuan , Zhong Zuiyi , Zhang Jiabin , Jing Jianhua , Zhang Kai , Huang Fei
Published: September 2024

The development of high‐performance organic photovoltaics (OPVs) with thick film active layers is key to moving this technology from laboratory preparation to industrial production. Design and synthesis of active layer materials to achieve a bi‐continuous interpenetrating morphology with appropriate nanoscale phase separation has been demonstrated as an effective method to realize high‐efficiency thick film devices. Here, two non‐fullerene acceptors are developed to compare the effect of symmetric (diDT‐BO) and asymmetric (DTC11‐BO) substituted alkyl chains on active layer morphology and device performance by introducing asymmetric side chains to the central core pyrrole ring. Based on the solubility and crystallinity differences of DTC11‐BO and diDT‐BO, the power conversion efficiencies (PCEs) of 19.0% and 18.1% are realized with D18 as the donor. Importantly, D18:DTC11‐BO devices with 300 and 500 nm active layers achieve excellent PCEs of 17.7% and 16.1%, which are among the top‐class values for thick film OPVs reported to date. The work demonstrates that tunning the crystallinity by optimizing the asymmetric alkyl chains is an effective material design strategy to achieve high‐efficiency thick film OPVs.
Unveiling the Role of Boron on Nickel‐Based Catalyst for Efficient Urea Oxidation Assisted Hydrogen Production
Authors: Hu Yitao , Shao Li , Jiang Zhiqi , Shi Lei , Li Qiuju , Shu Kaiqian , Chen Hui , Li Guodong , Dong Yan , Wang Tongzhou , Li Jihong , Jiao Lifang , Deng Yida
Published: September 2024

Urea oxidation reaction (UOR) is an ideal alternative to oxygen evolution reaction (OER) for efficient hydrogen production but is immensely plagued by slow kinetics. Herein, a multilayer hole amorphous boron‐nickel catalyst (a‐NiBx) is fabricated through a simple chemical plating method, which displays intriguing catalytic activity toward UOR, demanding a low working potential of 1.4 V to reach 100 mA cm−2. The high performance is credited to the formation of metaborate (BO2−), which can promote the formation of high‐oxidation‐state NiOOH active phase and optimize the adsorption of urea molecules. This can be confirmed by the operando spectroscopy characteristics and density functional theory calculations. Consequently, the assembled electrolyzer utilizing NiBx as bifunctional catalysts exhibited splendid catalytic activity, requiring an evidently lower voltage of 1.66 V to reach a current density of 100 mA cm−2 and 1.57 V when using Pt/C as a cathode catalyst. Moreover, the assembled electrolyzer secured a robust stability of over 200 h, as well as a four times higher hydrogen production rate than traditional water electrolysis.
Conductive Li2S‐NbSe2 Cathode Material Capable of Bidirectional Self‐Activation for High‐Performance All‐Solid‐State Lithium Metal Batteries
Authors: Hu Yaqi , Liu Yanchen , Lu Yang , Zhang Zongliang , Liu Siliang , He Fangbo , Liu Yang , Chen Yongle , Liu Fangyang
Published: September 2024

All‐solid‐state lithium metal batteries (ASSLBs) offer an alternative route to safe and high energy density power sources. Sulfur‐based cathodes with high theoretical specific capacity and low cost are crucial for advancing ASSLBs. However, the electronic insulation and sluggish kinetics of sulfide materials like Li2S severely limit battery performance. Herein, the strategy is proposed that a highly electronic conductive Li2S‐NbSe2 material enhances the electrochemical performance through bidirectional self‐activation. The chemical interaction between Li2S and NbSe2 induces NbSe2‐xSx and Li2Se derivatization, serving as the basis for activation. The carrier transport properties, chemical evolution and self‐activation mechanism of Li2S‐NbSe2 during the oxidation–reduction process are revealed. The chemical activation of NbSe2‐xSx is explored to accelerate the electrochemical processes by modifying the conductivity of sulfur species and the conversion pathways without insulating Li2S and S aggregation. Therefore, ASSLBs using Li2S‐NbSe2 as cathode active material achieve an electrode‐level energy density of 394 Wh kg−1 and a power density of 524 W kg−1 at 1 C (4.35 mA cm−2) and 25 °C. The capacity retention after 100 cycles at 0.5 C is ≈99.3% with almost no degradation. This work provides new options and insights for the rational design and development of chalcogenide cathode active materials for high‐performance ASSLBs.
Fabrication of Mechanical Strong Supramolecular Waterborne Polyurethane Elastomers With the Inspiration of Hierarchical Dynamic Structures of Scallop Byssal Threads
Authors: Zhang Mingguang , Wang Yining , Yang Minghang , Deng Yu , Zhou Wenhui , Wang Haidong , Jian Xigao , Chen Yousi
Published: September 2024

Advancing the development of eco‐friendly waterborne polyurethane elastomers (WPUEs) can significantly reduce the reliance on organic solvents, which is crucial for environmental conservation. Nevertheless, achieving superior mechanical properties and self‐healing capabilities in WPUEs presents a considerable challenge. Drawing inspiration from the hierarchical dynamic structures observed in scallop byssal threads, a high‐strength supramolecular waterborne polyurethane elastomer (SWPUE), designated SWPU‐DESH‐Zn, is developed in this study. Owing to the precise regulation of the hydrogen bonding state of acylsemicarbazide (ASC) fragments via disulfide bonds, and the formation of coordination interactions between carboxyl and zinc ions, the as‐prepared elastomer exhibited a robust mechanical strength of 52.07 MPa, comparable to that of solvent‐based polyurethane elastomers. Additionally, it exhibited notable self‐healing capability and excellent reprocessability. Meanwhile, high‐performance ionic skins and electromagnetic interference (EMI) shielding materials are also fabricated using SWPU‐DESH‐Zn as the matrix, further illustrating its potential applications. This novel biomimetic approach, inspired by scallop byssal threads, offers valuable insights for designing healable waterborne polymers with enhanced mechanical properties.
Atomic‐Scale Structural Dynamics at a‐Si:H/c‐Si Heterointerface During Low‐Temperature Thermal Annealing
Authors: Qu Xianlin , Chu Feihong , He Yongcai , Chen Xiaoqing , Zheng Zilong , Xu Xixiang , Li Zhenguo , Yan Hui , Zhang Yongzhe , Zheng Kun
Published: September 2024

The integrity of the hydrogenated amorphous silicon/crystalline silicon (a‐Si:H/c‐Si) interface is essential for the enhanced performance of a‐Si:H/c‐Si heterojunction‐based devices. However, during annealing processes aimed at passivating silicon dangling bonds, unexpected Si epitaxy and nanotwin formation tend to emerge, even under low‐temperature conditions. Therefore, understanding the influence of such annealing on the a‐Si:H/c‐Si interfacial structure is therefore pivotal for device optimization. In this study, the atomic‐scale structural transformation of the a‐Si:H/c‐Si heterointerface subjected to low‐temperature annealing is delved into. The dynamic evolution of this interface is captured by employing in situ spherical aberration (CS)‐corrected transmission electron microscopy (TEM), molecular dynamics (MD) simulations, and density functional theory (DFT) calculations. The TEM observations indicated that Si epitaxy initiated before Si nanotwin formation, and these nanotwins are inclined to revert to epitaxial structures upon sustained annealing. Through MD and DFT insights, the thermodynamic and kinetic intricacies driving the concerted tri‐layer atomic shift characterizing the Si nanotwin‐to‐epitaxy transition are decoded. The findings shed light on the thermal behavior of a‐Si:H/c‐Si interfaces, offering new perspectives on the thermal management in silicon heterojunction devices.
Unveiling Hierarchical Self‐Assembly of Triazolylferrocenyl Dendrimers: Producing Non‐Traditional Intrinsically Green Fluorescent Vesosomes for Nanotheranostics
Authors: Braga Carolyne B. , Perli Gabriel , Wang Qi , Wylie Luke , Bertuzzi Diego L. , Soares Marco C. P. , Ramos Miguel D. , Ruiz Jaime , Padua Agilio , Astruc Didier , Ornelas Catia
Published: September 2024

Dendrimers and supramolecular chemistry continue to fascinate researchers due to the endless unrevealed potential of their combination. This study investigates the self‐assembly process of a series of hydrophobic triazolylferrocenyl dendrimers in aqueous medium. Deep investigation through NMR spectroscopy, absorption UV–vis spectroscopy along with theoretical simulations demonstrates that the ferrocenyl moieties interact intramolecularly and intermolecularly driving the self‐assembly process. Data obtained by DLS, NTA, SEM, TEM, and EF‐TEM demonstrate that these dendrimers, in water, spontaneously self‐assemble through a hierarchical process. The dendrimers first self‐assemble into uniform nanovesicles, which in turn self‐assemble into larger vesosomes. The resulting vesosomes emit green non‐traditional intrinsic fluorescence, which is a property that emerged from the self‐assembled architectures. The vesosomes are efficiently uptaken by cancer cells and induce significant cytotoxic activity against the cancer cell line MCF‐7, up to the submicromolar concentration. Positive dendritic effects are identified in the fluorescence intensity and in the cytotoxic activity of the vesosomes, which follow the trend G0‐9Fc < G1‐27Fc < G2‐81Fc. This work showcases the remarkable potential of combining the two dynamic fields of dendrimers and supramolecular chemistry, which resulted in green fluorescent vesosomes capable of performing the dual role of cell imaging and killing, with potential applications in nanotheranostics.
Phase‐Separated Nano‐Antibiotics Enhanced Survival in Multidrug‐Resistant Escherichia coli Sepsis by Precise Periplasmic EcDsbA Targeting
Authors: Zou Pengfei , Huang Lin , Li Yi , Liu Dan , Che Junwei , Zhao Te , Li Hui , Li Jiaxin , Cui Ya‐Nan , Yang Guobao , Li Zhiping , Li Li‐Li , Gao Chunsheng
Published: September 2024

Disulfide bond (Dsb) proteins, especially DsbA, represent a promising but as‐yet‐unrealized target in combating multidrug‐resistant (MDR) bacteria because their precise subcellular targeting through multibarrier remains a significant challenge. Here, a novel heterogenization‐phase‐separated nano‐antibiotics (NCefoTs) is proposed, through the co‐assembly of enzyme‐inhibiting lipopeptides (ELp component), membrane‐recognizing and disrupting lipopeptides (MLp component), and cefoperazone. The self‐sorting components of MLp “concentrated island‐liked clusters” on the surface of NCefoTs promote the efficient penetration of NCefoTs through the outer membrane. Triggered by the DsbA, the precisely spatiotemporal engineered NCefoTs transform to nanofibers in situ and further significantly enhance the inhibition of DsbA. The hydrolytic activity of β‐lactamase and the motility function of flagella are thereby impeded, confirming the efficacy of NCefoTs in restoring susceptibility to antibiotics and inhibiting infection dissemination. By these synergistic effects of NCefoTs, the minimum inhibitory concentration of antibiotics decreases from over 300 µM to 1.56 µM for clinically isolated E. coli MDR. The survival rate of sepsis‐inflicted mice is significantly enhanced from 0% to 92% upon encapsulation of cefoperazone in NCefoTs, which rapidly eliminates invading pathogens and mitigates inflammation. The universally applicable delivery system, based on an “on demands” strategy, presents a promising prospect for undruggable antibiotic targets in the periplasm to combat MDR bacteria.
Responsive Protection of Magnesium Alloys From Multicorrosive Media by Constructing Nanofluidic Channels in Self‐Repairing Coatings
Authors: Yang Yajie , Zha Min , Wang Dawei , Wang Tianshuai , Wang Yufei , Wang Cheng , Yuan Ye , Wang Hui‐Yuan
Published: September 2024

Low‐density magnesium (Mg) alloys are excellent engineering materials, and can significantly reduce energy consumption by replacing existing steel and aluminum materials. However, Mg species are susceptible to corrosion, especially in harsh environments (high‐temperature or acidic), severely limiting the range of practical applications. Here, 2D covalent organic framework (COF) is synthesized with pore diameters ranging from 1.5 to 2.9 nm to obtain ultrafast nanofluidic channels. Loaded with silver (Ag+) ions, 2‐mercaptobenzimidazole (2‐MB) inhibitors are immobilized in the COF channels through the silver bridges. Based on the strong metal‐complexing capability, Ag+ ions precipitated with various corrosive media (Cl−, Br−, I−, SO32−, S2−, S2O32− SO42−, CO32−, PO43−); meanwhile, the 2‐MB inhibitors are rapidly released through the nanofluidic channels, forming a passivation film as a corrosion barrier to protect the Mg substrate. After integration with commercial polyethersulfone (PES), the COF‐based coating exhibits high repairing capability achieving 100% damage restoration within 7 h, outperforming all existing coatings of Mg alloys. Notably, the coating shows almost complete protection of Mg alloys after being treated in respective 473 K, acidic (pH ≈4.0), and alkaline (pH ≈10.0) environments.
Monomer Trapping Synthesis Toward Dynamic Nanoconfinement Self‐healing Eutectogels for Strain Sensing
Authors: Lv Yuesong , Li Changchun , Yang Zhangqin , Gan Mingxi , Wang Yuyan , Lu Minxun , Zhang Xinxing , Min Li
Published: September 2024

The rapid advancement in attractive platforms such as biomedicine and human‐machine interaction has generated urgent demands for intelligent materials with high strength, flexibility, and self‐healing capabilities. However, existing self‐healing ability materials are challenged by a trade‐off between high strength, low elastic modulus, and healing ability due to the inherent low strength of noncovalent bonding. Here, drawing inspiration from human fibroblasts, a monomer trapping synthesis strategy is presented based on the dissociation and reconfiguration in amphiphilic ionic restrictors (7000‐times volume monomer trapping) to develop a eutectogel. Benefiting from the nanoconfinement and dynamic interfacial interactions, the molecular chain backbone of the formed confined domains is mechanically reinforced while preserving soft movement capabilities. The resulting eutectogels demonstrate superior mechanical properties (1799% and 2753% higher tensile strength and toughness than pure polymerized deep eutectic solvent), excellent self‐healing efficiency (>90%), low tangential modulus (0.367 MPa during the working stage), and the ability to sensitively monitor human activities. This strategy is poised to offer a new perspective for developing high strength, low modulus, and self‐healing wearable electronics tailored to human body motion.
Inflammatory protein associations with brain MRI measures: Framingham Offspring Cohort
Authors: Chen Jiachen , Ragab Ahmed A. Y. , Doyle Margaret F. , Alosco Michael L. , Fang Yuan , Mez Jesse , Satizabal Claudia L. , Qiu Wei Qiao , Murabito Joanne M. , Lunetta Kathryn L.
Published: September 2024

INTRODUCTION

Brain magnetic resonance imaging (MRI) and inflammatory biomarkers are crucial for investigating preclinical neurocognitive disorders. Current investigations focus on a few inflammatory markers. The study aims to investigate the associations between inflammatory biomarkers and MRI measures and to examine sex differences among the associations in the Framingham Heart Study.

METHODS

Dementia and stroke‐free participants underwent OLINK Proteomics profiling and MRI measurements within 5 years. Pairwise cross‐sectional analysis assessed 68 biomarkers with 13 brain MRI volumes, adjusting for covariates and familial correlations.

RESULTS

Elevated CDCP1, IL6, OPG, and 4E.BP1 were related to smaller total cerebral brain volume (TCBV), whereas higher HGF, IL8, and MMP10 were associated with smaller TCBV, total and frontal white matter volumes. Higher SCF and TWEAK were associated with larger TCBV. In sex‐stratified analyses, associations were observed exclusively among males.

DISCUSSION

We report several associations between inflammatory biomarkers and brain volumes, highlighting different associations within sex subgroups.

Highlights

Higher CDCP1, IL6, OPG, and 4E.BP1 levels were associated with smaller TCBV.

Higher levels of HGF, IL8 and MMP10 were associated with smaller TCBV, CWV and FWV.

Higher levels of SCF and TWEAK, were associated with larger TCBV.

Significance diminished in models adjusting for CVD risk factors.

Associations were observed exclusively in males.
Effective Alkyl‐Alkyl Cross‐Coupling with an Iron‐Xantphos Catalyst: Mechanistic and Structural Insights
Authors: Gimeno Magali , Aguilera Maria Camila , Fleischauer Valerie E. , Brennessel William W. , Neidig Michael L.
Published: September 2024

While iron‐catalyzed C(sp2)−C(sp3) cross‐couplings have been widely studied and developed in the last decade, alkyl‐alkyl cross‐coupling systems with iron remain underdeveloped despite the importance of C(sp3)−C(sp3) bonds in organic synthesis. A major challenge to the development of these reactions is the current lack of fundamental insight into ligand effects and organoiron intermediates that enable effective alkyl‐alkyl couplings. The current study addresses this longstanding limitation using a combination of 57Fe Mössbauer spectroscopy, SC‐XRD (single‐crystal X‐ray diffraction) and reactivity studies of alkyl‐alkyl coupling with iron‐Xantphos to define the in situ formed iron‐Xantphos intermediates in catalysis. Combined with detailed reactivity studies, the nature of the key mechanistic pathways in catalysis and ligands effects to achieve effective alkyl‐alkyl cross‐coupling over competing β‐H elimination pathways are probed. Overall, these foundational studies provide a platform for future bespoke ligand and pre‐catalyst design for alkyl‐alkyl cross‐coupling methods development with sustainable iron catalysis.
A Strongly Reducing sp2 Carbon‐Conjugated Covalent Organic Framework Formed by N‐Heterocyclic Carbene Dimerization
Authors: Pitt Tristan A. , Azbell Tyler J. , Kim Jaehwan , Shi Zixiao , Muller David A. , Addicoat Matthew A. , Milner Phillip J.
Published: September 2024

Covalent organic frameworks linked by carbon‐carbon double bonds (C=C COFs) are an emerging class of crystalline, porous, and conjugated polymeric materials with potential applications in organic electronics, photocatalysis, and energy storage. Despite the rapidly growing interest in sp2 carbon‐conjugated COFs, only a small number of closely related condensation reactions have been successfully employed for their synthesis to date. Herein, we report the first example of a C=C COF, CORN‐COF‐1 (CORN=Cornell University), prepared by N‐heterocyclic carbene (NHC) dimerization. In‐depth characterization reveals that CORN‐COF‐1 possesses a two‐dimensional layered structure and hexagonal guest‐accessible pores decorated with a high density of strongly reducing tetraazafulvalene linkages. Exposure of CORN‐COF‐1 to tetracyanoethylene (TCNE, E1/2=0.13 V and −0.87 V vs. SCE) oxidizes the COF and encapsulates the radical anion TCNE⋅− and the dianion TCNE2− as guest molecules, as confirmed by spectroscopic and magnetic analysis. Notably, the reactive TCNE⋅− radical anion, which generally dimerizes in the solid state, is uniquely stabilized within the pores of CORN‐COF‐1. Overall, our findings broaden the toolbox of reactions available for the synthesis of redox‐active C=C COFs, paving the way for the design of novel materials.
A Modular Approach for Accessing 3D Heterocycles via 1,2‐Dicyanation of Planar N‐Heteroarenes
Authors: Pradhan Sukumar , Maiti Sudip , Dutta Suparna , Adam Russell C. , Tyagi Sameer , Maiti Debabrata
Published: September 2024

The rapid construction of three‐dimensional (3D) heterocyclic frameworks is a key challenge in contemporary medicinal chemistry. The molecules with three‐dimensional complexity hold a greater probability to improve clinical outcomes, solubility, selectivity for target proteins, and metabolic stability. However, the prevalence of flat molecules persists among new drug candidates, primarily owing to the multitude of chemical methods available for their synthesis. In principle, the dearomative functionalization of N‐heteroarene allows for the conversion of readily available planar molecules into partially or fully saturated nitrogen heterocycles, which are most significant structural motifs of pharmaceuticals and natural products. Unfortunately, these reactions are very rare because of the inherent challenge imposed by heteroarenes’ poor reactivity, rendering the process thermodynamically unfavorable. Herein, we report a modular approach for accessing 3D chemical space in translating planar heteroarenes into valuable 3D heterocycles via the installation of a highly versatile cyano group as a new vector. This approach is enabled by the in situ generation of reactive, non‐symmetric iodane by combining cyanide anion and bench‐stable PhI(OAc)2. This reaction represents a rare example of 1,2‐dicyanation of N‐heteroarenes that meets the numerous requirements for broad implementation in drug and agrochemical discovery. The transformation is highly selective and amenable to a wide range of N‐heteroarenes and late‐stage partial saturation of drugs and agrochemicals.
Conformation‐Confined Organic Butterfly‐Molecule with High Photoluminescence Efficiency, Deep‐Blue Amplified Spontaneous Emission, and Unique Piezochromic Luminescence
Authors: Dai Shuting , Li Xiao‐Ze , Liu Jiawen , Zhang Chenchen , Hu Jiasong , Liu Zhaoyang , Fang Hong‐Hua , Sun Hong‐Bo , Xu Bin , Tian Wenjing
Published: September 2024

Organic fluorophores with tunable π‐conjugated paths have attracted considerable attention owing to their diverse properties and promising applications. Herein, we present a tailored butterfly‐like molecule, 2,2’‐(2,5‐bis (2,2‐diphenylvinyl)‐1,4‐phenylene)dinaphthalene (BDVPN), which exhibits diverse photophysical features in its two polymorphs. The BP phase crystal, with its “aligned wings” conformation, possesses emissive characteristics that are nearly identical to those in dilute solutions. In contrast, the BN phase crystal, which adopts an “orthogonal wings” conformation, exhibits an unusual hypsochromic‐shifted emission compared to its dilute solution counterparts. This intriguing hypsochromic‐shifted emission originates from the reduction in the effective conjugated length of the molecular skeleton. Notably, BN phase crystals also exhibit exceptional optical performance, featuring high‐efficiency emission (76.6 %), low‐loss optical waveguides (0.571 dB mm−1), deep‐blue amplified spontaneous emission (ASE) with narrow full width at half maximum (FWHM: 6.4 nm), and a unique 200 nm bathochromic shift of piezochromic luminescence.
Sign Inversion of Circularly Polarized Luminescence in Cholesteric Liquid Crystals Induced by Mercury Ions through Binaphthyl Dopants′ Conjugation Control
Authors: Li Lulu , Jiang Peiting , Zhang Xueyan , Li Yang
Published: September 2024

Stimuli‐responsive circularly polarized luminescence (CPL) materials based on cholesteric liquid crystal (CLC) platforms show great promise for applications in information encryption and anticounterfeiting. In this study, we constructed a mercury ion‐responsive CPL system in CLCs by controlling the conjugation degree of axially chiral binaphthyl derivatives. Two chiral binaphthyl derivatives (R/S‐1 and R/S‐2) were initially used as chiral dopants to demonstrate that CPL inversion (glum values from 0.5/‐0.44 to −0.53/0.48) in CLCs could be achieved by modulating the conjugation degree of the chiral binaphthyls. Based on this concept, the thioacetal binaphthyl R‐2S was developed and used as a mercury‐responsive chiral dopant in CLCs. Under Hg ion treatment, the CPL sign inverted (glum value changed from 0.22 to −0.29) due to the transformation of the thioacetal into an aldehyde group. Additionally, the mercury ion‐responsive CPL material was applied in information encryption.
Tailor‐made production of mannosylerythritol lipids: From genetic modification to chemical synthesis
Authors: Saika Azusa , Fukuoka Tokuma
Published: September 2024

Mannosylerythritol lipids (MELs) are glycolipid biosurfactants produced by basidiomycetous yeasts. Mannosylerythritol lipids have received increasing attention because they not only have excellent interfacial activity but also have anti‐inflammatory and antimicrobial activity, and against cancer cell line, repair damaged skin, as carriers for drug delivery, and to interact with proteins. These properties are dependent on their structures; therefore, the tailored production of targeted MELs is required to obtain the desired properties. Over the past two decades, the genomes of MEL producers have been analyzed, revealing the MELs synthesis pathway and related genes. Using this information, it has become possible to tailor‐produce MELs by modifying the synthesis pathway. Furthermore, in recent years, novel chemical synthesis methods for MELs have been developed, enabling precise control over the fatty acid chain lengths of chemically synthesized MELs. This review compiles examples of the tailored production of MELs using methods ranging from the genetic modification of MELs producers to chemical synthesis methods.
Short‐Term Risk of Cardiovascular Events in People Newly Diagnosed With Gout
Authors: Cipolletta Edoardo , Nakafero Georgina , Richette Pascal , Avery Anthony J. , Mamas Mamas A. , Tata Laila J. , Abhishek Abhishek
Published: September 2024

Objective

To investigate the temporal association between the first diagnosis of gout and cardiovascular events in the short term.

Methods

We performed a self‐controlled case series analysis and a cohort study using data from linked primary care, hospitalization, and mortality records from the United Kingdom's Clinical Practice Research Database‐GOLD. We included individuals with a new diagnosis of gout either in the primary care or secondary care between January 1, 1997 and December 31, 2020. The first consultation at which gout was diagnosed was the exposure of interest. The main outcome consisted of cardiovascular events (ie, a composite of fatal and nonfatal myocardial infarction, ischemic or hemorrhagic stroke, and transient ischemic attack).

Results

The 4,398 patients (66.9% male, mean age 74.6 years) had a cardiovascular event within at least two years of their first recorded diagnosis of gout. The incidence of cardiovascular events was significantly higher in the 30 days after the first diagnosis of gout compared to baseline (adjusted incidence rate ratio 1.55, 95% confidence interval [CI] 1.33–1.83). Among 76,440 patients (72.9% male, mean age 63.2 years) included in the cohort study, the incidence of cardiovascular events in the 30 days after the first gout diagnosis (31.2 events per 1,000 person‐years, 95% CI 27.1–35.9) was significantly higher than in days 31 to 730 after gout diagnosis (21.6 events per 1,000 person‐years, 95% CI 20.8–22.4) with a rate difference of −9.6 events per 1,000 person‐years (95% CI −14.0 to −5.1).

Conclusion

Individuals had a short‐term increased risk of cardiovascular events in the 30 days following the first consultation at which gout was diagnosed.
IĸBζ as a Central Modulator of Inflammatory Arthritis Pathogenesis
Authors: Swarnkar Gaurav , Naaz Musarrat , Mims Dorothy , Gupta Prashant , Peterson Timothy , Christopher Matthew J. , Singamaneni Srikanth , Mbalaviele Gabriel , Abu‐Amer Yousef
Published: September 2024

Objective

Current therapies targeting individual factors in inflammatory arthritis show variable efficacy, often requiring treatment with combinations of drugs, and are associated with undesirable side effects. NF‐ĸB is critical for the production and function of most inflammatory cytokines. However, given its essential role in physiologic processes, targeting NF‐ĸB is precarious. Hence, identifying pathways downstream of NF‐ĸB that selectively govern the expression of inflammatory cytokines in inflammatory arthritis would be advantageous. We have previously identified IĸBζ as a unique inflammatory signature of NF‐ĸB that controls the transcription of inflammatory cytokines only under pathologic conditions while sparing physiologic NF‐ĸB signals.

Methods

We generated mice harboring myeloid, lymphoid, and global deletion of Nfkbiz (the gene encoding IĸBζ). These models were subjected to serum transfer‐induced arthritis. Additionally, pharmacologic inhibitors of IĸBζ were injected intraperitonially. Joint swelling, microcomputed tomography, immunohistochemistry, flow cytometry, and cytokine measurements were conducted using synovial tissue samples.

Results

Global deletion of Nfkbiz or depletion of neutrophils (vastly IĸBζ+ cells) reduced inflammatory synovial cells and increased anti‐inflammatory and regenerative synovial cells, plummeted expression of inflammatory factors and ameliorated experimental mouse inflammatory arthritis. Further, expression of immune responsive gene‐1, the enzyme responsible for itaconate production, was increased in synovial cells. Accordingly, the itaconate derivative dimethyl itaconate (DI) inhibited IĸBζ‐mediated inflammatory factors. Further, in silico screen identified 8‐hydroxyquinoline (HQ) as a putative inhibitor of IĸBζ not affecting physiologic NF‐ĸB activity. Congruently, systemic administration of either DI or HQ inhibited joint swelling and damage.

Conclusion

Our study positions IĸBζ as an inflammation‐specific target for therapeutic consideration in rheumatoid arthritis because its inhibition spares the beneficial functions of NF‐ĸB.

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Special Educational Needs and Disability tribunals: Dyslexia, scientific validity and equity
Authors: Elliott Julian , Stanbridge Joanna , Branigan Kirsten
Published: September 2024

This paper examines the operation of the English Special Educational Needs and Disability tribunal system in relation to children who present with a dyslexia diagnosis. It identifies a number of significant weaknesses; in particular, the absence of clear diagnostic criteria capable of differentiating such children from large numbers of other struggling readers. It then explains why it is inappropriate to identify particular cognitive processes as indicating the presence of dyslexia, as distinct from a broader reading difficulty. The paper subsequently explores the erroneous nature of claims about specialised dyslexia teaching and resourcing that, while often asserted with confidence by some privately funded assessors, are not supported by the scientific literature. It is argued that the tribunal system is an inappropriate method for reconciling the competing needs of a diagnosed dyslexic subgroup in relation to the wider population of struggling readers, estimated to be 20% of the school population.
On the circular entrepreneurship across continents: An analysis of terms of business descriptors
Authors: Benita Francisco , Srinivasan Padmapriya
Published: September 2024

This study analyzes circular entrepreneurship trends across global regions using the 2014–2018 Global Entrepreneurship Monitor dataset. Content analysis of business descriptors from 79,663 unique entrepreneurs was used to position each startup within the 9R's framework. The results show that startups are mainly associated with “repurpose” and “recover”, which are less desirable for circularity. We further define circular entrepreneurs as those with the top 10% highest weighted score in circular strategies according to the type of business they run. The BERTopic approach is applied to identify specific business topics for these entrepreneurs. Similarities (North America and Latin America & the Caribbean) and differences (Europe) in popular topics are found across regions. Lastly, regression analysis reveals that entrepreneurial perception and the presence of role models are key factors driving circular entrepreneurship.
Assessment of membrane‐based downstream purification processes as a replacement to traditional resin bead for monoclonal antibody purification
Authors: Pasquier Victor , Botelho Ferreira Kevin , Lergenmuller Morgane , Tottoli Alexis , Perilleux Arnaud , Souquet Jonathan , Bielser Jean‐Marc
Published: September 2024

Membrane chromatography devices are a viable alternative to packed‐bed resins and enable highly productive purification cascades for monoclonal antibodies and Fc‐fusion proteins. In this study, ion exchange and protein A membrane chromatography performances were assessed and compared with their resin counterparts. Protein A dynamic binding capacities were higher than 50 g/L for two of the tested membranes and with a residence time of 0.2 min. For polishing, it was observed that aggregate clearance was generally less performant with membrane separation when compared to resins with similar ligands. However, the comparable yield and increased productivity of membranes could be enough to consider their implementation. In addition, lifetime studies demonstrated that the performance of membranes remained robust over cycles. One hundred cycles were reached for most of the tested membranes with no impact on the process performance nor product quality. Finally, purification cascades were fully operated with membranes, from capture to polishing, reaching good levels of host cells proteins (less than 50 ppm) and aggregates (equal to or less than 1%). The outcome of this study demonstrated that resin chromatography could be fully replaced by membranes for monoclonal antibody and Fc‐fusion protein purification processes.
Chemical Characterization, Evaluation of Acute Oral Toxicity, and Anti‐Diabetic Activity of Aloe sabaea Flowers Extract on Alloxan‐Induced Diabetic Rats
Authors: Raweh Salwa M. , El‐Shaibany Amina , Al‐Mahbashi Hassan , Abdelkhalek Ahmed S. , Elkomy Nesreen M. I. M. , Elnagar Gehad M. , Elsayed Mohamed G. , Elaasser Mahmoud M. , Raslan Ali E.
Published: September 2024

The study aimed to conduct chemical profiling, acute in‐vivo toxicity evaluation, and the potential anti‐diabetic effect of standardized Aloe sabaea flowers ethanolic extracts (ASFEE) on alloxan‐induced diabetic rats. The chemical composition was analyzed using GC–MS and TLC techniques. The oral acute toxicity study was performed according to the WHO 2000 and the OECD 420 guidelines. Furthermore, anti‐diabetic activity was investigated using two doses of ASFEE (0.2 and 0.5 g/kg/day BW, p.o.) compared with glibenclamide (5 mg/kg/day, p.o.). A molecular docking investigation of the identified components with the PTPN9 enzyme was performed to figure out the proposed anti‐diabetic mechanism. GC–MS analysis displayed the existence of 18 compounds; most of the compounds were fatty acids and their esters, and phytosterols. Total phenolic and flavonoid contents were 42.00±1.26 mg GAE/g DW and 22.21±1.55 mg QE/g DW, respectively. The results of the in‐vivo toxicity study revealed the absence of noticeable signs of toxicity or mortality at various doses establishing the safety of the tested extract. The estimated LD50 value was higher than 10 g/kg. Antidiabetic action exhibited a noticeable decline in fasting blood glucose (FBG) levels comparable to glibenclamide with no inducing intense hypoglycemia and considerable excess weight.
Destroyed lung syndrome in patients with drug‐susceptible pulmonary tuberculosis
Authors: Gyabaah Solomon , Gyan Kwadwo Faka , Mensah Harris Osei , Darkwa Eric Amoako , Owiredu Michael Asiedu , Nyamuame Vera Selorm , Amponsah Gordon Manu , Amenuke Divine Aseye
Published: September 2024

Key Clinical Message

Destroyed lung syndrome is a recognized devastating complication of pulmonary tuberculosis (TB) that affects the quality of life of patients. Clinicians in TB‐endemic countries should be aware of this complication aiming at prevention. TB control programs should intensify efforts at early detection and treatment and also provide interventions for post‐TB complications.
Research Progress of Catalysts with Atomic‐Scale Reactive Sites in Urea Electrosynthesis
Authors: Lu Lu , Zhan Peng , Chen Xuehan , Shi Wei , Si Zhihao , Qin Peiyong
Published: September 2024

Urea (CO(NH2)2) is the main component of nitrogen‐based fertilizers and is widely used in various industries. Until now, urea production is conducted under high‐temperature and high‐pressure conditions, which involves a considerable carbon footprint. Urea electrosynthesis, which is powered by renewable energy‐derived electricity, has emerged as a sustainable single‐step process for urea production. The development of efficient and stable catalysts is the key to improving the efficiency of urea electrosynthesis. In this review, we summarized the research progress and applications of catalysts with atomic‐scale reactive sites in urea electrosynthesis. First, the catalytic mechanisms of urea electrosynthesis from CO2 and various nitrogenous molecules are discussed. Then, typical electrocatalysts such as single‐atom electrocatalysts, dual‐atom electrocatalysts, clusters, atomic dopants, vacancies, and so forth, are discussed. Furthermore, characterization methods for atomic‐scale reactive sites are summarized. Finally, challenges and suggestions for urea electrosynthesis are proposed. We hope this review can provide some inspiration toward the development of catalysts for efficient and sustainable urea electrosynthesis.
Regulating Molecular Structure of S,N‐Heteroacene Non‐fullerene Acceptors to Achieve Efficient Photoelectric Properties†
Authors: Liu Mingtao , Zhu Peipei , Lai Shiting , Zhang Xiage , Fu Yuang , Xue Ling , Liu Dan , Feng Kui , Lu Xinhui , Guo Xugang , Liao Xunfan , Chen Yiwang
Published: September 2024

Comprehensive Summary

The ternary strategy has demonstrated its efficacy in improving charge transport in organic solar cells (OSCs). Here, three novel non‐fullerene acceptors, SN6C9‐4F, SN6C9‐4Cl and SN6C10‐4F, based on S,N‐heteroacene linear backbone were designed and synthesized. The three acceptors exhibit excellent molecular coplanarity, high crystallinity and possess a deep‐lying lowest unoccupied molecular orbital energy level, which is beneficial for charge transport and injection in organic field‐effect transistors (OFETs). Notably, the OFET devices based on all three acceptors achieved impressive electron mobilities, with SN6C10‐4F achieving up to 0.73 cm2·V–1·s–1, which is one of the highest values among A‐D‐A type small molecules. In addition, the OSCs device based on PBDB‐T:SN6C9‐4F exhibited the best power conversion efficiency of 12.07% owing to its optimal morphology and enhanced charge transport. Moreover, the incorporation of SN6C9‐4F into the efficient PM6:L8‐BO binary system to form ternary OSCs resulted in extended absorption range, enhanced donor crystallization, improved and more balanced charge transport, ultimately leading to an improvement of PCE from 17.78% to 18.32%. This study highlights the potential of developing acceptors with distinct structures from Y‐series acceptors to broaden absorption and regulate donor crystallization, providing a novel approach to enhance the PCE of OSCs.
Smoking prevalence and association with sociodemographic variables in cancer clinical trial participants
Authors: Presant Cary A. , Till Cathee , Vaidya Riha , Ashing Kimlin Tan , Warren Graham W. , Sun Virginia , Salgia Ravi , Massarelli Erminia , Mortimer Joanne E. , Pal Sumanta , Dorff Tanya , Amini Arya , Erhunmwunsee Loretta , Phillips Tanyanika , Hershman Dawn L. , Unger Joseph M.
Published: September 2024

Background

Tobacco use (smoking) causes adverse clinical outcomes among patients with cancer, including increased cancer‐related mortality. In participants in cancer clinical trials, the prevalence of tobacco use and the factors associated with tobacco use are not well described.

Methods

Data were examined from participants enrolled in SWOG cancer clinical treatment trials between 2016 and 2022 who reported their smoking status at trial enrollment. Baseline variables (smoking status, insurance type, zip code, and demographic factors) were obtained from patient registration forms. Bivariate and multivariable associations were examined via logistic regression.

Results

Among 4326 patients enrolled in 29 trials, 48.1% reported currently/previously smoking, including 12.4% currently, 4.9% recently, and 30.7% formerly. Ever smoking was more commonly reported in males, patients aged ≥65 years, patients with Medicaid or no insurance, patients from areas of high socioeconomic deprivation, and rural patients. Patients of Hispanic ethnicity and Asian and Pacific Islander patients were less likely to have ever smoked. In multivariable regression, patients with lung cancer were most likely to report ever smoking compared to patients with breast cancer (odds ratio, 4.98; p < .001).

Conclusions

In the first comprehensive evaluation of smoking status among trial participants enrolled in National Cancer Institute network group treatment trials, nearly half reported ever smoking and one in six reported current or recent smoking. Smoking was more common among vulnerable population patients defined by demographic and socioeconomic factors. Tobacco use should be routinely assessed and reported in clinical trials to help reduce the negative cancer and overall health effects of persistent tobacco use and to address disparities among patients with cancer.