bluuebunny/crossref_metadata_2025_split huggingface dataset:
Interception and Synthetic Application of Diradical and Diene Forms of Dual‐Nature Azabicyclic o‐Quinodimethanes Generated by 6π‐Azaelectrocyclization
Authors: Shankar Majji , Lee Daniel J. , Inaththappulige Supuni I. N. Hewa , Acharya Ayush , Yennawar Hemant P. , Giri Ramesh 
Published: July 2024

AbstractWe demonstrate that 2‐alkenylarylaldimines and ketimines undergo thermal 6π‐azaelectrocyclization to generate a wide range of azabicyclic o‐quinodimethanes (o‐QDMs). These o‐QDMs exist as a hybrid of a diene and a benzylic diradical. The diradical nature was confirmed by their ability to undergo dimerization and react with H‐atom donor, 2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) and O2. In addition, the interception of the diradicaloid o‐QDMs by H‐atom transfer was used to synthesize five tetrahydroisoquinoline alkaloids and related bioactive molecules. The diene form can undergo [4+2] cycloaddition reactions with different dienophiles to generate bridged azabicycles in high endo:exo selectivity. The azabicyclic o‐QDMs can be generated for [4+2] cycloaddition from a wide range of electronically and sterically varied 2‐alkenylarylimines, including mono, di, tri and tetrasubstituted alkenes, and imines derived from arylamine, alkylamine (1°, 2°, 3°), benzylamine, benzylsulfonamide and Boc‐amine.
Biosynthesis of the Non‐Canonical C17 Sesquiterpenoids Chlororaphen A and B from Pseudomonas Chlororaphis
Authors: Xu Houchao , Li Heng , Goldfuss Bernd , Schnakenburg Gregor , Dickschat Jeroen S. 
Published: July 2024

AbstractChlororaphens A and B are structurally unique non‐canonical C17 sesquiterpenoids from Pseudomonas chlororaphis that are made by two SAM‐dependent methyltransferases and a type I terpene synthase. This study addresses the mechanism of their formation in isotopic labelling experiments and DFT calculations. The results demonstrate an astonishing complexity with distribution of labellings within a cyclopentane core that is reversely connected to two acyclic fragments in chlororaphen A and B. In addition, the uptake of up to 14 deuterium atoms from D2O was observed. These findings are explainable by a repeated late stage multistep rearrangement sequence. The absolute configurations of the chlororaphens and their biosynthetic intermediates were elucidated in stereoselective labelling experiments.
A comparative study of comprehensive performances for transparent plasticized polyvinyl chloride films with different plasticizers
Authors: Chen Ming , Yang Beixue , Zhang Jun 
Published: July 2024

AbstractFor flexible polyvinyl chloride (PVC) films with excellent mechanical performances and high transparency, the demand for antistatic properties is becoming increasingly urgent in textile and electronic fields. This study compares the effects of 60 phr bis (2‐(2‐butoxyethoxy) ethyl) adipate (DBEEA) with other five equal amounts of plasticizers on the conductivity, electrical stability, transparency, and mechanical properties of plasticized PVC. The infrared spectra of plasticizers indicate that there are unique ether groups exist in DBEEA. Then the calculated solubility parameters suggest the good compatibility between DBEEA and PVC. For conductivity, the volume resistivity and surface resistivity of the PVC sample with DBEEA (PVC/DBEEA) are 107 Ω· m and 1010 Ω, respectively, which are both lower by 3–4 orders of magnitude than that of other plasticized PVC. For electrical stability, the results indicate that PVC/DBEEA placed in air still maintains lowest resistivities. Under 10, 23, and 30°C, PVC/DBEEA keeps high and stable electrical properties. The similar refractive indices of DBEEA and PVC resin prepared by suspension method indicate good transparency for PVC/DBEEA. Moreover, PVC/DBEEA still has good mechanical property.
Highly compressible porous polyethyleneimine/chitosan composite aerogel with excellent mechanical properties as wide detection range sensors for human motion monitoring
Authors: Sun Zhenfeng , Yang Junjun , Chen Zhengyan , Ren Fang , Jin Yanling , Ren Penggang 
Published: July 2024

AbstractBiomass three‐dimensional composite aerogels have garnered significant attention in the realm of wearable electronic skin owing to their favorable properties, including excellent human compatibility, environmentally benign degradability, and continuous porous architecture. However, conventional biomass aerogels suffer from inadequate mechanical flexibility, susceptibility to irreversible deformation under high compressive stress, and limited reusability, thereby constraining their applicability in sensing technologies. To address these limitations, this study presents the development of porous CCS/KH560/PEI/CNT‐COOH (CKPC) composite aerogels through a freeze–drying process. Chemical crosslinking was achieved using silane coupling agent (KH560) with carboxymethyl chitosan (CCS) and polyethyleneimine (PEI), while carboxylated carbon nanotubes (CNT‐COOH) were incorporated as conductive fillers. This approach successfully overcame the issues of poor mechanical properties, low elasticity, and unbalanced sensitivity‐sensing range trade‐off in chitosan‐based aerogel sensors. The results revealed that the porous CKPC aerogels exhibited a remarkable mechanical compressive strain of 86.3% while maintaining structural integrity post‐unloading. The CKPC composite aerogel‐based sensor demonstrated a high sensitivity of 42.9 within a wide strain range of 60%–76.3%, accompanied by a stable and repeatable electrical signal response across varying strains. The porous structure of the CKPC conductive aerogel sensor holds promising applications in human motion monitoring and flexible electronics.
Motional Resistance as Highly Selective Descriptor to Probe Dynamic Formation of Surface Films on Zinc Anode
Authors: Mohanty Sangram Keshari , Ok Yeongin , Kim Eun Su , Park Yuwon , Ryu Ji Heon , Mun Junyoung , Lee Jeonghyeon , Hyun Kyu , Srinivasa Madhusudana Koratikere , Jeong Hyein , Reddy Sri Charan , Yoo Hyun Deog 
Published: July 2024

AbstractZinc anodes are expected as a promising alternative to lithium‐based anodes in energy storage systems due to their low cost, high theoretical capacity, and environmental friendliness. However, the development of efficient and stable zinc anode requires a fundamental understanding of the interfacial processes occurring during zinc deposition and dissolution cycling. In this study, we employed electrochemical quartz crystal microbalance (EQCM) analysis to investigate the potential‐dependent formation and decomposition of surface films on zinc metal anodes in sulfate‐based aqueous electrolytes. Changes in frequency and motional resistance served as complementary descriptors, with motional resistance being a highly selective indicator for probing dynamic surface film formation driven by side reactions at the zinc anode. While the frequency change provided the overall changes in the mass of both zinc metal and surface films, changes in the motional resistance selectively reflected the amount and nature of the visco‐elastic interface that comprise the surface films. The two descriptors provide quantitative and complementary means to discover the complex interfacial processes such as the formation of surface visco‐elastic films, guiding to the development of more stable and efficient zinc‐based electrochemical systems.
Broadband sensitized near‐infrared emission in Eu2+‐Nd3+ co‐doped BaAl2O4 as a potential spectral modulator for silicon solar cells
Authors: Song Guoxiang , Lou Chaogang , Zhu Ruiqi , Diao Han , Shen Bowen 
Published: July 2024

AbstractThe near‐infrared (NIR) down‐conversion process for broadband sensitization has been studied in Eu2+‐Nd3+ co‐doped BaAl2O4. This material has a broad absorption band of 200–480 nm and can convert photons in the visible region into NIR photons. The NIR emission at 1064 nm, attributed to the Nd3+:4F3/2 → 4I11/2 transition, matches the bandgap of Si, allowing Si solar cells to utilize the solar spectrum better. The energy transfer (ET) process between Eu2+ and Nd3+ was demonstrated using photoluminescence spectra and luminescence decay curves, and Eu2+ may transfer energy to Nd3+ through the cooperative energy transfer (CET) to achieve the down‐conversion process. The energy transfer efficiency (ETE) and theoretical quantum efficiency (QE) were 68.61% and 156.34%, respectively, when 4 mol% Nd3+ was introduced. The results indicate that BaAl2O4:Eu2+‐Nd3+ can serve as a potential modulator of the solar spectrum and is expected to be applied to Si solar cells.
Predictive modeling for cell culture in commercial manufacturing of biotherapeutics
Authors: Panjwani Shyam , Almazan Alice , Hille Rubin , Spetsieris Konstantinos 
Published: July 2024

AbstractThe biopharmaceutical industry continually seeks advancements in the commercial manufacturing of therapeutic proteins, where mammalian cell culture plays a pivotal role. The current work presents a novel data‐driven predictive modeling application designed to enhance the efficiency and predictability of cell culture processes in biotherapeutic production. The capability of the cloud‐based digital data science application, developed using open‐source tools, is demonstrated with respect to predicting bioreactor potency from at‐line process parameters over a 5‐day horizon. The uncertainty in model's prediction is quantified, providing valuable insights for process control and decision‐making. Model validation on unseen data confirms the model's robust generalizability. An interactive dashboard, tailored to process scientist's requirements is also developed to streamline biopharmaceutical manufacturing processes, ultimately leading to enhanced productivity and product quality.
In vivo detection of the epimer metabolites of sweroside via ultra‐performance liquid chromatography time‐of‐flight mass spectrometry combined with DNPH derivatization
Authors: Li Hao , Tang Shuhan , Xu Yaqi , Sun Yidan , Li Pengyu , Li Xianna , Zhang Hailong , Hattori Masao , Wang Zhigang 
Published: July 2024

AbstractThe metabolites of sweroside were first investigated in vivo with ultra‐performance liquid chromatography time‐of‐flight mass spectrometry (UPLC–TOF–MS) in combination with 2,4‐dinitrophenylhydrazine derivatization. In addition, the mass detection sensitivity of the major metabolites, epinaucledal and naucledal, via UPLC–TOF–MS was significantly enhanced, and the epimer metabolites were distinctly discovered from plasma following gavage of sweroside in rats. The plasma concentration of epinaucledal and naucledal was quantified via UPLC–TOF–MS in negative mode using erythrocentaurin as the internal standard. The maximum mean plasma concentrations of naucledal and epinaucledal were 75.36 ± 20.10 and 43.52 ± 15.60 ng/ml within 2 h, respectively, following gavage of sweroside at 20 mg/kg. Moreover, the area under the concentration–time curve of naucledal was three times that of epinaucledal. The metabolic process of conversion of sweroside to epinaucledal and naucledal was deduced, and the pharmacological effects of epinaucledal and naucledal will clarify the clinical efficacy of sweroside.
Computer‐Aided Design of Large‐Scale Nanomaterials Synthesis Processes: A Detailed Review
Authors: GadelHak Yasser , Muhammad Ayyaz , El‐Azazy Marwa , El‐Shafie Ahmed S. , Shibl Mohamed F. , Mahmoud Rehab 
Published: July 2024

AbstractEfforts from the scientific community and the private sector are required to lower the costs of large‐scale production of nanomaterials (NMs) to enhance their commercialization. In this work, the computer‐aided process design of large‐scale NM synthesis procedures is comprehensively reviewed. Moreover, a generalized process flow diagram for all large‐scale production processes was constructed by surveying numerous scalable experimental procedures reported in the literature. Previous studies reporting simulation cases of large‐scale production processes of NMs and nanocomposites (NCs) are also reviewed based on the type of material produced, e.g., oxides, sulfides, carbonaceous materials, organic materials, metals, and other types of NMs. Finally, technical insights from classical chemical engineering specializations, such as altering process configurations, optimizing process variables, integrating chemical processes, utilizing renewable energy sources, conducting computational calculations, employing machine learning techniques, and studying the process's environmental impact, are reviewed for large‐scale NMs and NCs synthesis.
Conducting Nickel Hydroxide Thin Film on Molybdenum Disulfide – Reduced Graphene Oxide Composite Electrode for Simultaneous Detection of Uric Acid, Dopamine and Ascorbic Acid
Authors: Luhana Charles , Mashazi Philani 
Published: July 2024

AbstractHerein we report the fabrication of a simple electrochemical sensor based on an electrode containing reduced graphene oxide and molybdenum disulphide (RGO/MoS2) as a conducting film onto the glassy carbon electrode (GCE) via a drop dry method to form GCE‐RGO/MoS2. The surface (GCE‐RGO/MoS2) was further modified with nickel hydroxide thin film using electrodeposition method to form GCE‐RGO/MoS2/Ni(OH)2. The materials and modification steps were thoroughly characterized using microscopy and spectroscopy methods. The composite electrode, GCE‐RGO/MoS2/Ni(OH)2, showed excellent electrocatalytic potential separation for the detection of dopamine, uric acid, and ascorbic acid. The electrocatalytic oxidation peak potentials were at 3 mV, 157 mV and 303 mV for AA, DA and UA, respectively. The composite electrode was also selective towards the determination of ascorbic acid (AA), dopamine (DA), uric acid (UA), and simultaneously in mixture of analytes. The low detection limits for AA, DA and UA were 1.17 μM, 0.15 μM and 1.15 μM, respectively. The composite electrode was applied for the detection of AA, DA and UA in spiked newborn calf serum samples with high percentage recoveries ranging from 96.6–100.8 % for AA, 92.8–104.2 % for DA and 99.4–102.3 % for UA.
Transition State Stabilizing Effects of Oxygen and Sulfur Chalcogen Bond Interactions
Authors: Lin Binzhou , Liu Hao , Scott Harrison M. , Karki Ishwor , Vik Erik C. , Madukwe Daniel O. , Pellechia Perry J. , Shimizu Ken D. 
Published: July 2024

AbstractNon‐covalent chalcogen bond (ChB) interactions have found utility in many fields, including catalysis, organic semiconductors, and crystal engineering. In this study, the transition stabilizing effects of ChB interactions of oxygen and sulfur were experimentally measured using a series of molecular rotors. The rotors were designed to form ChB interactions in their bond rotation transition states. This enabled the kinetic influences to be assessed by monitoring changes in the rotational barriers. Despite forming weaker ChB interactions, the smaller chalcogens were able to stabilize transition states and had measurable kinetic effects on the rotational barriers. Sulfur stabilized the bond rotation transition state by as much as −7.2 kcal/mol without electron‐withdrawing groups. The key was to design a system where the sulfur
‐hole was aligned with the lone pairs of the chalcogen bond acceptor. Oxygen rotors also could form transition state stabilizing ChB interactions but required electron‐withdrawing groups. For both oxygen and sulfur ChB interactions, a strong correlation was observed between transition state stabilizing abilities and electrostatic potential (ESP) of the chalcogen, providing a useful predictive parameter for the rational design of future ChB systems.
An Artificial Light‐Harvesting System based on Supramolecular AIEgen Assembly
Authors: Jia Dan , Luo Quan , Liu Shicong , Hou Chunxi , Liu Junqiu 
Published: July 2024

AbstractPhotosynthesis is a complex multi‐step process in which light collection is the initial step of photosynthesis and plays an important role in the utilization of solar energy. In order to improve the utilization of sunlight, researchers have developed a variety of artificial light‐harvesting systems to simulate photosynthesis in nature. Here, we report a supramolecular artificial light‐harvesting system in aqueous solution. Since β‐cyclodextrin (β‐CD) has a hydrophobic cavity and a hydrophilic outer surface, we adopt β‐cyclodextrin (β‐CD) as the host molecule and use adamantane as the guest molecule. At the same time, we modified β‐CD with the donor molecule naphthalimide and adamantane with the tetraphenylethylene molecule which has aggregation‐induced emission (AIE) effects. By using fluorescent molecules with AIE, the self‐quenching effect caused by aggregation in aqueous solution can be effectively avoided. Due to the host‐guest interaction of β‐CD and adamantane, nanoparticles with stable structure and uniform size can be spontaneously assembled in water. Because of the close distance and strong spectral overlap between naphthalimide and tetraphenylethylene, Förster resonance energy transfer (FRET) was realized, and artificial light‐harvesting system was successfully constructed in aqueous solution. Therefore, this study provides a new strategy for constructing artificial light‐harvesting system, and the artificial light‐harvesting system shows broad application prospects in aqueous solutions.
Secondary Aggregation Induced by Volatile Additive for Improved Exciton Diffusion and Charge Separation in High Efficiency Organic Photovoltaic Devices
Authors: Ge Yufeng , Li Xuewu , Zhou Mingxu , Lu Peng , Hao Xiaotao 
Published: July 2024

Comprehensive SummaryThe morphology of the active layer plays a crucial role in the performance of organic photovoltaics. Although volatile additives are commonly used to manipulate the morphology, their mechanism of action remains poorly understood. In this study, we conducted a systematic exploration of the mechanism of the traditional volatile additive 1‐CN in film formation kinetics of typical PM6:Y6 system. We found that 1‐CN induces a secondary aggregation effect, improving film morphology and promoting face‐on crystalline orientation. Through elucidating its impact on exciton dynamics, we established a link between morphology optimization and increased exciton diffusion length and accelerated charge separation. Our findings unveil the unique mechanism of action of volatile additive, providing a new perspective for improving the morphology and enhancing the performance of organic photovoltaic devices.
Exploring the Impact of C‐Terminal Based Pentapeptides on the Disassembly of Aβ42 Fibrils
Authors: Kaur Apneet , Kaur Mankoo Opinder , Rani Diksha , Priyadarshi Nitesh , Goyal Deepti , Kumar Singhal Nitin , Goyal Bhupesh 
Published: July 2024

AbstractAn effective therapeutic strategy to suppress Alzheimer's disease (AD) progression is to disrupt β‐sheet rich neurotoxic soluble amyloid‐β (Aβ) aggregates. Previously, we identified new pentapeptides (RVVPI and RIAPA) with notably enhanced ability to block Aβ42 aggregation as compared to Aβ42 C‐terminal derived peptide RIIGL using integrated computational protocol. In this work, the potential of RIIGL, RVVPI, and RIAPA for the structural destabilization of Aβ42 protofibril was assessed by molecular dynamics (MD) simulations and in vitro studies. The binding free energy analysis depicts that charged residues influence Aβ42 protofibril‐pentapeptide interactions. Notably, RVVPI displays a more pronounced destabilization effect than other peptides due to higher conformational fluctuations, and disruption of salt bridge (K28‐A42) interactions in Aβ42 protofibril. RVVPI exhibited highest inhibitory activity (Inhibition=66.2 %, IC50=5.57±0.83 μM) against Aβ42 aggregation consistent with computational results. Remarkably, RVVPI displayed ~4.5 fold lower IC50 value as compared to RIIGL. ThT and TEM studies highlighted the enhanced efficiency of RVVPI (62.4 %) in the disassembly of pre‐formed Aβ42 fibrils than RIIGL and RIAPA. The combined in silico and in vitro studies identified a new peptide, RVVPI, as an efficient inhibitor of Aβ42 fibrillation and disassembly of Aβ42 aggregates.
Advancements in Scaling Up Perovskite Solar Cells: From Small‐Area Devices to Large‐Scale Modules
Authors: Hu Zhenyu , Wang Zijie , Gao Peng 
Published: July 2024

AbstractThe power conversion efficiency (PCE) of perovskite solar cells (PSCs) has exceeded those of conventional thin‐film solar cell technologies, and the speed at which this increase has been achieved is unprecedented in the history of photovoltaics. Despite the significant progress achieved by PSCs at the laboratory level, their commercial prospects still face two significant challenges: scaling up in size and ensuring long‐term stability. Small‐area devices (~1 cm2) are typically fabricated using spin‐coating. However, this approach may not be suitable for preparing the large‐area (>100 cm2) substrates required for commercialization. Thus, new materials and methods must be developed to facilitate the coating of large‐area PSCs. This review will discuss the development of scaling up organic‐inorganic hybrid PSCs and the challenges of increasing the device area. Furthermore, it will provide an overview of the methodologies for achieving high‐efficiency perovskite solar modules.
Synthesis Strategies and Structures of Molecular Heterometallic Oxo Clusters
Authors: Minato Takuo 
Published: July 2024

AbstractMultinuclear heterometallic oxo clusters, composed of two or more different metal cations bridged by oxo ligands, represent an important class of molecular complexes known for their unique magnetic, catalytic, and electrochemical properties resulting from cooperative interactions between the metal cations. If three or more types of metal cations can be arranged as designed, their chemical and physical properties can be precisely and flexibly controlled, potentially creating innovative materials. However, research on hetero‐trimetallic and hetero‐tetrametallic oxo clusters remains limited. This review presents an interdisciplinary search of multinuclear heterometallic oxo clusters, regardless of the type of ligand, to explain and classify their synthesis strategies and structures. By cataloging crystallographically characterized heterometallic oxo clusters using ligand‐per‐metal values and synthesis method notations, valuable insights have been gained into effective synthesis methods for the precise arrangement of metal cations. The advantages and disadvantages of one‐pot synthesis methods and synthesis strategies for achieving precise structural control of heterometallic oxo clusters are discussed with an emphasis on the prediction of their final structures. The insights from this review are expected to drive the development of synthetic and analytical techniques for the precise synthesis of heterometallic complexes in a predictable way.
Clinical signature of exosomal tetraspanin proteins in cancer
Authors: Das Asmit , Saha Priyanka , Kalele Ketki , Sonar Swarup 
Published: July 2024

AbstractExosomes are nano‐scale vesicles involved in intercellular communication and have a significant role in cancer progression. Tetraspanins, are transmembrane proteins enriched in exosomes. These proteins have significant role in exosome biogenesis, cargo sorting,and target‐cell interactions, influencing tumor development and therapeutic response. Exosomal tetraspanins, including CD9, CD63, CD81, and Tspan8, contribute to tumor cell proliferation, angiogenesis, extracellular matrix remodelling, immune evasion, and promote metastasis. Their ability to prepare distant organ sites for colonization highlights their role in establishing the premetastatic niche. Expression profiling of exosomal tetraspanin proteins in cancer become a promising diagnostic and prognostic biomarker. Exosomal tetraspanin proteins also be an effective therapeutic target in cancer.This article highlighted impactful role ofexosomal tetraspanin Proteins in Cancer.