bluuebunny/crossref_metadata_2025 huggingface dataset:
Cotunneling Effects in the Geometric Statistics of a Nonequilibrium Spin‐Resolved Junction
Authors: Sandilya Mriganka , Akhtar Javed , Sarmah Manash Jyoti , Goswami Himangshu Prabal
Published: July 2024

In the nonequilibrium steady state of electronic transport across a spin‐resolved quantronic junction, the role of cotunneling on the emergent statistics under phase‐different adiabatic modulation of the reservoirs' chemical potentials is investigated. By explicitly identifying the sequential and inelastic cotunneling rates, the geometric or Pancharatnam–Berry contribution to the spin exchange flux between the spin system and the right reservoir is numerically evaluated. The relevant conditions wherein the sequential and cotunneling processes compete and selectively influence the total geometric flux upshot are identified. The Fock space coherences are found to suppress the cotunneling effects when the system reservoir couplings are comparable. The cotunneling contribution to the total geometric flux can be made comparable to the sequential contribution by creating a right‐sided asymmetrically stronger system‐reservoir coupling strength. Using a recently proposed geometric thermodynamic uncertainty relationship, the total rate of minimal entropy production is estimated. The geometric flux and the minimum entropy is found to be nonlinear as a function of the interaction energy of the junctions' spin orbitals.
“Anions‐in‐Colloid” Hydrated Deep Eutectic Electrolyte for High Reversible Zinc Metal Anodes
Authors: Cheng Min , Li Diantao , Cao Junlun , Sun Tianjiang , Sun Qiong , Zhang Weijia , Zha Zhengtai , Shi Mengyao , Zhang Kai , Tao Zhanliang
Published: July 2024

Zn metal as a promising anode for aqueous batteries suffers from severe zinc dendrites, anion‐related side reactions, hydrogen evolution reaction (HER) and narrow electrochemical stable window (ESW). Herein, an “anions‐in‐colloid” hydrated deep eutectic electrolyte consisting of Zn(ClO4)2 ⋅ 6H2O, β‐cyclodextrin (β‐CD), and H2O with mass ratio of 7 : 4.5 : 3 (ACDE‐3) is designed to improve the stability of zinc anode. The ACDE‐3 reconfigures the hydrogen‐bond (HB) network and regulates the solvation shell. More importantly, the hydroxyl‐rich β‐cyclodextrins (β‐CDs) in ACDE‐3 self‐assemble into micelles, in which the steric effect between adjacent β‐CDs in micelles restricts the movement of anions. This unique “anions‐in‐colloid” structure enables the eutectic system with a high Zn2+ transference number (tZn2+) of 0.84. Thus, ACDE‐3 inhibits the formation of dendrite, prevents the anion‐involved side reactions, suppresses the HER, and enlarges the ESW to 2.32 V. The Zn//Zn symmetric cell delivers a long lifespan of 900 hours at 0.5 mA cm−2, and the Zn//Cu half cells have a high average columbic efficiency (ACE) of 97.9 % at 0.5 mA cm−2 from cycle 15 to 200 with a uniform and compact zinc deposition. When matched with a poly(1,5‐naphthalenediamine) (poly(1, 5‐NAPD)) cathode, the full battery with a low negative/positive capacity (N/P) ratio of 2 can still cycle steadily for 200 cycles at a current density of 1.0 A g−1. Additionally, this electrolyte has been proven to be operative over a wide temperature range from −40 °C to 40 °C.
Dual Channel Emissions of Kasha and Anti‐Kasha from a Single Radical Molecule
Authors: Zhu Zihao , Kuang Zhiyuan , Shen Li , Wang Shengjie , Ai Xin , Abdurahman Alim , Peng Qiming
Published: July 2024

Stable open‐shell luminescent radicals have recently attracted much attention due to their unique luminescence properties. However, a radical molecule with both Kasha and anti‐Kasha doublet emission properties has not been reported. Herein, we have successfully synthesized a stable chlorine‐substituted Chichibabin's hydrocarbon, TTM‐TTM, along with its mono‐radical counterpart, TTM‐HTTM. The emission of TTM‐TTM follows Kasha's rule in the near infrared region. However, TTM‐HTTM shows dual channel doublet emissions of Kasha and anti‐Kasha. Remarkably, these two types of emission compete dynamically in both solution and condensed states. Our findings provide valuable insights into the rational design and discovery of stable radicals that possess distinctive luminescent properties, thus broadening the horizons of luminescent materials research.
Bis‐Silylene‐Supported Aluminium Atoms with Aluminylene and Alane Character
Authors: Saddington Artemis , Dong Shicheng , Yao Shenglai , Zhu Jun , Driess Matthias
Published: July 2024

The suitability of electron‐rich bis‐silylenes, specifically the neutral chelating [SiII(Xant)SiII] ligand (SiII=PhC(NtBu)2Si, Xant=9,9‐dimethylxanthene) and the anionic [SiII(NAcrid)SiII)]− pincer ligand (NAcrid=2,7,9,9‐tetramethylacridane), has been successfully probed to stabilize monovalent bis‐silylene‐supported aluminium complexes (aluminylenes). At first, the unprecedented aluminium(III) iodide precursors [SiII(Xant)SiII]AlI2+ I− 1 and [SiII(NAcrid)SiII)]AlI2 2 were synthesized using AlI3 and [SiII(Xant)SiII] or [SiII(NAcrid)SiII)]Li(OEt2)], respectively, and structurally characterized. While reduction of 1 with KC8 led merely to unidentified products, the dehalogenation of 2 afforded the dimer of the desired {[SiII(NAcrid)SiII)]Al:} aluminylene with a four‐membered SiIV2AlIII2 ring. Remarkably, the proposed aluminylene intermediates [SiII(Xant)SiII]AlII and {[SiII(NAcrid)SiII)]Al:} could be produced through reaction of 1 and 2 with Collman's reagent, K2Fe(CO)4, and trapped as AlI:→Fe(CO)4 complexes 5 and 6, respectively. While 6 is stable in solution, 5 loses one CO ligand in solution to afford the silylene‐ and aluminylene‐coordinated iron(0) complex 7 from an intramolecular substitution reaction. The electronic structures of the novel compounds were investigated by Density Functional Theory calculations.
Reducing Dielectric Confinement Effect Enhances Carrier Separation in Two‐Dimensional Hybrid Perovskite Photocatalysts
Authors: Fang Zhaohui , Wang Guohong , Guan Chen , Zhang Jianjun , Xiang Quanjun
Published: July 2024

Two‐dimensional organic–inorganic hybrid perovskites (OIHPs) with alternating structure of the organic and inorganic layers have a natural quantum well structure. The difference of dielectric constants between organic and inorganic layers in this structure results in the enhancement of dielectric confinement effect, which exhibits a large exciton binding energy and hinders the separation of electron‐hole pairs. Herein, a strategy to reduce the dielectric confinement effect by narrowing the dielectric difference between organic amine molecule and [PbBr6]4− octahedron is put forward. The Ethanolamine (EOA) contains hydroxyl groups, resulting in the positive and negative charge centers of O and H non‐overlapping, which generated a larger polarity and dielectric constant. The reduced dielectric constant produces a smaller exciton binding energy (71.03 meV) of (C2H7NO)2PbBr4 ((EOA)2PbBr4) than (C8H11N)2PbBr4 ((PEA)2PbBr4 (156.07 meV), and promotes the dissociation of electrons and holes. The increasing of lifetime of photogenerated carrier in (EOA)2PbBr4 are proved by femtosecond transient absorption spectra. Density functional theory (DFT) calculations have also indicated that the small energy shift of the total density of states (DOS) between the C/H/N and the Pb/Br in (EOA)2PbBr4 favors the separation of electrons and holes. In addition, this work demonstrates the application of (PEA)2PbBr4 and (EOA)2PbBr4 in the field of photocatalytic CO2 reduction.
Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes
Authors: Fu Bin , Wang Lianghua , Chen Kexin , Yuan Xiuping , Yin Jianjun , Wang Simin , Shi Dazhen , Zhu Bo , Guan Wei , Zhang Qian , Xiong Tao
Published: July 2024

Despite impressive advances in the construction of enantioenriched silacarbocycles featuring silicon‐stereogenic centers via a selection of well‐defined sila‐synthons, the development of a more convenient and economic method with readily available starting materials is significantly less explored and remains a considerable challenge. Herein, we report the first example of copper‐catalyzed sequential hydrosilylation of readily accessible methylenecyclopropanes (MCPs) and primary silanes, affording an efficient and convenient route to a wide range of chiral silacyclopentanes bearing consecutive silicon‐ and carbon‐stereogenic centers with excellent enantio‐ and diastereoselectivities (generally ≥98 % ee, >25 : 1 dr). Mechanistic studies reveal that these reactions combine copper‐catalyzed intermolecular ring‐opening hydrosilylation of aryl MCPs and intramolecular asymmetric hydrosilylation of the resultant Z/E mixture of homoallylic silanes.
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

We 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

Chlororaphens 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

For 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

Biomass 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

Zinc 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

The 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

The 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

The 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

Efforts 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

Herein 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

Non‐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

Photosynthesis 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 Summary

The 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

An 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

The 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

Multinuclear 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

Exosomes 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.
Ubiquitin: Not just a one‐way ticket to the proteasome, but a therapeutic dial to fine‐tune the molecular landscape of disease
Authors: Kim A. Hyun , Chiknas P. Murdo , Lee Robin E. C.
Published: July 2024

Recently, there is a rise in studies that recognize the importance of targeting ubiquitin and related molecular machinery in various therapeutic contexts. Here we briefly discuss the history of ubiquitin, its biological roles in protein degradation and beyond, as well as the current state of ubiquitin‐targeting therapeutics across diseases. We conclude that targeting ubiquitin machinery is approaching a renaissance, and tapping its full potential will require embracing a wholistic perspective of ubiquitin's multifaceted roles.
An optimized deep learning model for a highly accurate DOA and channel estimation for massive MIMO systems
Authors: Pabbati Omkar H. , Joshi Rutvij C.
Published: July 2024

Massive multiple‐input multiple‐output (MA‐MIMO) has been hailed as an auspicious technology for the future generation of wireless communications because it can considerably increase the capacity of the communication network. However, using the maximum likelihood (ML) direction‐of‐arrival (DOA) estimate method is severely constrained in actual systems because of the computationally expensive multi‐dimensional searching procedure. This paper proposes a novel approach to estimate DOA and channels by incorporating deep learning into the MA‐MIMO system. Here, a deep belief network (DBN) is used to learn both the spatial structures in the angle domain and the statistics of the wireless channel through both online and offline learning procedures. Also, a bald eagle search (BES) Optimization is used along with DBN to attain high precision through optimal training. The proposed model can estimate the channel based on the predicted DOA and the complex gain. According to numerical results, the suggested method performs significantly better than state‐of‐the‐art methods, particularly in tough conditions like low signal‐to‐noise ratio (SNR) and a finite number of snapshots. The proposed DBN‐BES technique accomplishes less root mean square error (RMSE) as 0.01 for SNR of 5 dB in elevation calculation and 0.02 for SNR of 5 dB in azimuth calculation. Also, the proposed algorithm greatly reduces computational complexity.
Physical seed damage, not rodent's saliva, accelerates seed germination of trees in a subtropical forest
Authors: Zhu Yunlong , Yang Xifu , Teng Yuwei , Wang Zhenyu , Zhang Zhibin
Published: July 2024

Many tree species adopt fast seed germination to escape the predation risk by rodents. Physical seed damage and the saliva of rodents on partially consumed seeds may act as cues for seeds to accelerate germination process. However, the impacts of these factors on seed germination rate and speed remain unclear. In this study, we investigated such impacts on the germination rate and speed (reversal of germination time) of four tree species (Quercus variabilis, Q. serrata, Q. acutissima, Q. glauca) after partial consumption by four rodent species (Leopoldamys edwards, Niviventer fulvescens, N. confucianus, Apodemus draco), through a series of experiments. We also examined how seed traits may affect the seed damage degree by rodents by analyzing the relationship between the germination rate and time of rodent‐damaged seed and the traits. We found that, artificially‐ and rodent‐damaged seeds exhibited a significantly higher seed germination rate and speed, compared to intact seeds. Also, the rodent saliva on seeds showed no significant effect on seed germination rate and speed. Furthermore, we observed significant positive correlations between several seed traits (including the seed mass, coat thickness, and protein content) and the seed germination rate and speed. These correlations are likely due to their beneficial traits countering seed damage by rodents. Overall, our results highlight the significant role of physical seed damage by rodents (rather than their saliva) in facilitating seed germination of tree species, and potential mutualism between rodents and trees. Additionally, our results may have some implications in forest restoration, such that intentionally sowing or dispersing slightly damaged seeds by humans or drones may increase the likelihood of successful seed regeneration.
Potential of reproductive traits in functional ecology: A quantitative comparison of variability in floral, fruit, and leaf traits
Authors: Paź‐Dyderska Sonia , Jagodziński Andrzej M.
Published: July 2024

Despite their claimed low intraspecific variability, plant reproductive traits are less frequently used in functional ecology. Here we focused on underrepresented plant organs, i.e. flowers and fruits, by comparing their traits with well‐established leaf traits. We evaluated 16 functional traits (six floral, six fruit, and four leaf traits) in a randomly selected group of woody species under comparable environmental conditions. We aimed to assess interspecific and intraspecimen variability and explore the potential of the proposed flower and fruit traits for ecological research. Traits related to the dry mass of flowers and fruits exhibited the highest interspecific variability, while carbon content traits in flowers and leaves had the lowest. At a specimen level, specific leaf area revealed the highest variation. Carbon content traits for all organs demonstrated the least intraspecimen variability, with flower carbon content being the least variable. Our study revealed connections between the newly proposed traits and widely recognized functional traits, uncovering intriguing links between the established traits and the floral and fruit traits upon which we focused. This complements the already well‐recognized variability in plant form and function with additional insights into reproductive processes.
Aboveground versus soil‐mediated effects of an invasive grass on fire‐dependent forbs in an oak woodland
Authors: Williams G. L. , Stephen Brewer J.
Published: July 2024

Most work on plant competition intensity in general has focused on how aboveground and belowground competition for resources between plants changes with soil resource availability. In contrast, much work on the competitive effects of non‐native invasive species on native species has focused on other mechanisms (e.g., allelopathy and microbial changes) and has largely ignored how these effects interact with mechanisms of resource competition along productivity gradients. We examined aboveground effects of an invasive grass, Microstegium vimineum, along with soil differences between invaded and non‐invaded areas on two native perennial herbs at a productive and an unproductive oak woodland site in north Mississippi, USA. We transplanted 32 individuals each of Helianthus silphioides and Potentilla simplex from uninvaded areas into natural patches dominated by M. vimineum at each of the sites. Each transplant was randomly assigned to a pot with either native soil or soil from around M. vimineum roots. Aboveground competition was manipulated by securing M. vimineum shoots in a non‐shading position around the transplant. We monitored survival of all transplants weekly in the growing seasons of 2020 and 2021. Transplant survival of H. silphioides was lowest in M. vimineum soil at the more productive site when M. vimineum was not pinned back. Transplant survival of P. simplex was lower at the more productive site but was mostly unresponsive to pinning and soil treatments. Synthesis. Our results suggest that soil‐mediated legacy effects of an invader may reduce some native species' ability to compete for light at productive sites.
Flight behaviour diverges more between seasonal forms than between species in Pieris butterflies
Authors: Kleckova Irena , Linke Daniel , Rezende Francisko De Moraes , Rauscher Luca , Le Roy Camille , Matos‐Maraví Pável
Published: July 2024

In flying animals, wing morphology is typically assumed to influence flight behaviours. Whether seasonal polymorphism in butterfly morphology is linked to adaptive flight behaviour remains unresolved. Here, we compare the flight behaviours and wing morphologies of the spring and summer forms of two closely related butterfly species, Pieris napi and P. rapae. We first quantify three‐dimensional flight behaviour by reconstructing individual flight trajectories using stereoscopic high‐speed videography in an experimental outdoor cage. We then measure wing size and shape, which are characteristics assumed to influence flight behaviours in butterflies. We show that seasonal, but not interspecific, differences in flight behaviour might be associated with divergent forewing shapes. During spring, Pieris individuals are small and have elongated forewings, and generally fly at low speed and acceleration, while having a high flight curvature. On the contrary, summer individuals are larger and exhibit rounded forewings. They fly at high speed and acceleration, while having high turning acceleration and advance ratio. Our study provides one of the first quantitative pieces of evidence of different flight behaviours between seasonal forms of two Pieris butterfly species. We discuss the possibility that this co‐divergence in flight behaviour and morphology is an adaptation to distinct seasonal environments. Properly identifying the mechanisms underpinning such divergence, nonetheless, requires further investigations to disentangle the interacting effects of microhabitats, predator community, parasitoid pressure and behavioural differences between sexes.
Governance gaps and accountability traps in renewables extractivism
Authors: Park Susan , Kramarz Teresa , Johnson Craig
Published: July 2024

The global uptake of renewable technology is both a dramatic and insufficient contribution to achieving a 1.5–2° world. However, urgently decarbonizing energy use and systems by shifting to renewables relies on intensifying global supply chains, beginning with the extraction of “critical” minerals, an industry that has a long history of generating significant social and ecological harms. This paper examines the nature of transnational governance initiatives that have emerged to regulate what has been called “renewables extractivism.” We develop a novel database of 44 transnational initiatives for governing minerals for onshore wind, solar PV, and lithium‐ion batteries, which are driving renewable energy uptake. The database reveals “governance gaps” that refer to an absence of rules for many critical minerals and “accountability traps” where actors are held responsible for processes, standards, and sanctions that reflect their own normative logics, rather than the needs of affected communities and ecosystems. Current initiatives are designed in a way that measures, evaluates, and (very rarely) sanctions governance outcomes primarily in relation to supply chain security and energy access, as opposed to mitigating the social and environmental harms of resource extraction. The result is a transnational governance architecture that operates primarily (and systematically) with minimal scrutiny, transparency, and accountability. For stakeholders directly affected by the latest mining boom cycle, the absence of effective and legitimate accountability mechanisms reinforces a pattern of uneven development that shifts the most destructive forms of extraction to the social and ecological margins of the global commodity frontier.
Phenotype and prognostic factors in geriatric and non‐geriatric patients with transthyretin cardiomyopathy
Authors: Volpentesta Eugenia , Kharoubi Mounira , Donadio Cristiano , Rebiai Kahina , Fanen Pascale , Funalot Benoit , Gendre Thierry , Audard Vincent , Canoui‐Poitrine Florence , Itti Emmanuel , Teiger Emmanuel , Planté‐Bordeneuve Violaine , Oghina Silvia , Tixier Denis , Mallet Sophie , Broussier Amaury , Damy Thibaud , Zaroui Amira
Published: July 2024

Aims

Transthyretin cardiac amyloidosis (ATTR‐CM) may be an underestimated cause of heart failure among geriatric patients and represent a unique phenotype and prognostic profile.

Methods and results

This retrospective, observational, cohort study characterizes cardiac and extracardiac disorders at diagnosis and assesses prognosis among ATTR‐CM patients based on age (geriatric vs. non‐geriatric) and amyloidosis subtype (wild type, ATTRwt and hereditary, ATTRv). In total, 943 patients with ATTR‐CM were included, of which 306 had ATTRv and 637 had ATTRwt. Among these, 331 (35.1%) were non‐geriatric (<75 years), and 612 (64.9%) were geriatric (≥75 years). The population exhibited conduction abnormalities, atrial fibrillation and ischaemic heart disease that progressively deteriorated with age. Among ATTRwt patients, peripheral neuropathy, neurovegetative symptoms, and hearing loss were present across all age groups, but reports of carpal tunnel symptoms or surgery decreased with age. Conversely, among ATTRv patients, reports of extracardiac symptoms increased with age and Val122ILe mutation was highly prevalent among geriatric patients. The 3‐year survival was higher among non‐geriatric ATTR‐CM patients (76%) than geriatric patients (55%) and predictors of 3‐year mortality differed. Notably, predictors identified among geriatric patients were alkaline phosphatase (ALP) (HR = 1.004, 95% CI: [0.001–1.100)], troponin T hs (HR = 1.005, 95% CI: [1.001–1.120)] and tricuspid insufficiency (HR = 1.194, 95% CI: [1.02–1.230)]. Whereas, among non‐geriatric patients, NT‐proBNP (HR = 1.002, 95% CI: [1.02–1.04], global longitudinal strain (HR = 0.95, 95% CI: [0.922–0.989], and glomerular filtration rate (HR = 0.984, 95% CI: [0.968–1.00) were identified. We propose a 3‐stage prognostic staging system combining troponin T hs (≥44 ng/L) and ALP levels (≥119 UI/L). In the geriatric population, this model discriminated survival more precisely than the National Amyloidosis Centre staging, particularly for classifying between stage 1 (82%), stage 2 (50%) and stage 3 (32%) for ATTRv and ATTRwt.

Conclusions

These diagnostic and prognostic indicators, along with ATTR subtype, highlight the distinct characteristics of this important, geriatric ATTR‐CM patient group. Recognizing these mortality markers can be valuable for geriatricians to improve the prognostic quality management of geriatric patients with ATTR‐CM.
Evaluating the influence of working parameters on the efficiency of a solid oxide fuel cell by conducting sensitivity analysis using electrochemical and thermodynamic modeling
Authors: Mouissi Ahmed , Touaibi Rabah , Köten Hasan
Published: July 2024

This research article presents an investigation conducted through a numerical model to analyze the influence of various operational parameters on the performance of solid oxide fuel cells (SOFCs). The parameters studied include operating temperature, current density, pressure, steam‐to‐carbon ratio, and fuel utilization. The electrochemical model employed the Butler‐Volmer equation, Fick's model, and Ohm's law to calculate concentration, activation, and ohmic losses. The primary focus was on evaluating the generated power and electrical efficiency as performance metrics. The study revealed that increasing operating temperature and pressure resulted in higher power generation and specific optimum points were identified for optimal SOFC operation. Notably, the highest power generated was 812 kW, achieved at an operating temperature of 950 K and a current density of 18100 A/m2. Additionally, decreasing the fuel utilization factor to 55% at 15250 A/m2 led to a power output of 706 kW. Similarly, at a current density of 17150 A/m2 and a pressure of 400 kPa, the fuel cell generated about 780 kW of power. Furthermore, the research demonstrated that reducing the steam‐to‐carbon ratio increased power generation, with an optimum power output of 704 kW achieved at a current density of 16000 A/m2 and a low steam‐to‐carbon ratio. Notably, this point also showcased the improved electrical efficiency of the solid oxide fuel cell. Overall, this study underscores the significance of specific operational factors that significantly impact SOFC performance. By comprehending these parameters, it becomes possible to enhance the utilization of solid oxide fuel cells across various applications.