bluuebunny/crossref_metadata_2025 huggingface dataset:
Simultaneously Enhanced Low Temperature Li+ Transport Kinetics and Crystal Stability of Nb1.94Mo0.06O5@C Anode Induced by Distorted NbO6 Octahedron
Authors: Wang Guan , Wang Guixin , Dong Haotian , Li Jiaxin , Zhang Suojiang , Zhang Haitao
Published: October 2024

The electrochemical performances of lithium‐ion batteries (LIBs) will be significantly degraded under low‐temperature conditions, which restricts their wide application in cold environments. Herein, the low‐temperature transport kinetics of a novel Nb1.94Mo0.06O5@C nanocomposite anode is accelerated greatly via engineering the microstructure and NbO6 octahedron. The detailed crystallographic features are characterized by using synchrotron radiation, spherical electron microscope, and density functional theory simulation methods. Both experimental and simulation analysis suggest that Mo6+ preferentially replaces Nb5+ in the regular octahedral location and distorts the NbO6 octahedron, resulting in a widened c‐axis spacing and a lowered ion diffusion barrier. Coupled with the enhanced electronic conductivity derived from surface carbon layer, Nb1.94Mo0.06O5@C anode exhibits an enhanced charge transfer process, improved Li+ diffusion kinetics, pronounced pseudo‐capacitance process, and excellent low temperature capacity. Furthermore, in situ X‐ray diffraction and ex situ electron microscope elucidate that the structural evolution of Nb1.94Mo0.06O5@C is highly reversible, unveiling its excellent cycling stability. The full cell assembled with LiNi0.6Co0.2Mn0.2O2 cathode demonstrates excellent practicality. This study reveals the critical role of distorting NbO6 octahedron and expanding crystal spacing in facilitating rapid Li+ diffusion and enhancing charge storage performance of Nb2O5 at low temperatures.
Scalable Synaptic Transistor Memory from Solution‐Processed Carbon Nanotubes for High‐Speed Neuromorphic Data Processing
Authors: Pei Jingfang , Song Lekai , Liu Pengyu , Liu Songwei , Liang Zihan , Wen Yingyi , Liu Yang , Wang Shengbo , Chen Xiaolong , Ma Teng , Gao Shuo , Hu Guohua
Published: October 2024

Neural networks as a core information processing technology in machine learning and artificial intelligence demand substantial computational resources to deal with the extensive multiply‐accumulate operations. Neuromorphic computing is an emergent solution to address this problem, allowing the computation performed in memory arrays in parallel with high efficiencies conforming to the neural networks. Here, scalable synaptic transistor memories are developed from solution‐sorted carbon nanotubes. The transistors exhibit a large switching ratio of over 105, a significant memory window of ≈12 V arising from charge trapping, and low response delays down to tens of nanoseconds. These device characteristics endow highly stabilized reconfigurable conductance states, successful emulation of synaptic functions, and a high data processing speed. Importantly, the devices exhibit uniform characteristic metrics, e.g., with a 1.8% variation in the memory window, suggesting an industrial‐scale manufacturing capability of the fabrication. Using the memories, a hardware convolution kernel is designed and parallel image processing is demonstrated at a speed of 1 M bit per second per input channel. Given the efficacy of the convolution kernel, a promising prospect of the memories in implementing neuromorphic computing is envisaged. To explore the potential, large‐scale convolution kernels are simulated and high‐speed video processing is realized for autonomous driving.
Solution Processable Metal–Organic Frameworks: Synthesis Strategy and Applications
Authors: Zhang Wanglin , Wu Xuanhao , Peng Xiaoyan , Tian Yefei , Yuan Hongye
Published: October 2024

Metal–organic frameworks (MOFs), constructed by inorganic secondary building units with organic linkers via reticular chemistry, inherently suffer from poor solution processability due to their insoluble nature, resulting from their extensive crystalline networks and structural rigidity. The ubiquitous occurrence of precipitation and agglomeration of MOFs upon formation poses a significant obstacle to the scale‐up production of MOF‐based monolith, aerogels, membranes, and electronic devices, thus restricting their practical applications in various scenarios. To address the previously mentioned challenge, significant strides have been achieved over the past decade in the development of various strategies aimed at preparing solution‐processable MOF systems. In this review, the latest advance in the synthetic strategies for the construction of solution‐processable MOFs, including direct dispersion in ionic liquids, surface modification, controllable calcination, and bottom‐up synthesis, is comprehensively summarized. The respective advantages and disadvantages of each method are discussed. Additionally, the intriguing applications of solution‐processable MOF systems in the fields of liquid adsorbent, molecular capture, sensing, and separation are systematically discussed. Finally, the challenges and opportunities about the continued advancement of solution‐processable MOFs and their potential applications are outlooked.
Organophotocatalyst Enabled Deoxycyclopropanation of Alcohols
Authors: Zhang Yongsheng , Wang Jincheng , He Xiaoyan , Peng Shilin , Yuan Lei , Huang Gang , Guo Yongjin , Lu Xiuhong
Published: October 2024

Cyclopropane fragments, which widely exist in marketed drugs and natural products, can confer special pharmacological properties to small‐molecule drugs. Therefore, developing methods to construct cyclopropanes is of great significance. Nevertheless, the introduction of cyclopropane primarily relies on already‐formed cyclopropyl groups, which significantly restricts the diversity of cyclopropane skeletons. Late‐stage direct cyclopropanation is still a challenging task. Herein, a photo‐induced intermolecular deoxycyclopropanation reaction that employs alcohols as substrates, and 1 mol.% of 2,3,5,6‐tetrakis(carbazol‐9‐yl)‐1,4‐dicyanobenzene (4CzTPN) as organophotocatalyst is reported. This method proceeds with high transformation efficiency (up to 98% yield) and exhibits broad functional group tolerance, such as primary, secondary, and tertiary alcohols as well as various activated β‐halogenated alkenes. This process is mild, easy to operate, and has low equipment requirements. The power of this technology is demonstrated by the late‐stage functionalization of five marketed drugs and five natural products.
The Bitter Taste of Brazil's Temporary Import Ban on Robusta Coffee
Authors: Otgun Hanifi , Beghin John , Maximiliano Fernando
Published: October 2024

Brazil, a leading Robusta coffee producer and exporter, faced a significant drought in 2016–2017, which drastically reduced production and depleted stocks. Consequently, Brazil temporarily permitted the import of one million 60‐kg bags of Robusta coffee in the spring 2017. An import ban was imposed shortly afterward due to lobbying by domestic Robusta farmers. We examine the welfare and trade impacts of the drought and subsequent import ban on stakeholders in the Robusta bean and soluble coffee markets. The import ban improved the welfare of Brazilian Robusta producers by $174.85–$280.26 million, nearly offsetting the drought's effects. However, it increased unit cost for Brazilian soluble processors by 10% and reduced consumer surplus in Brazil by $108.35–$174.44 million. Deadweight losses remained minimal due to the markets' price inelasticity. Major Robusta exporters faced reduced exports to Brazil and up to 9% lower prices, losing 0.3363–0.7564 million 60‐kg bags. Additionally, foreign consumers of Brazilian soluble coffee lost $62–$107 million in welfare from higher prices. without the import ban, global stakeholders would have seen a $12.61/bag higher world bean price. The drought benefitted Robusta sellers outside Brazil but harmed net importers, even with the ban in place.
Neuroimaging to Genotype: Delineating the Spectrum of Disorders With Deficient Myelination in the Indian Population
Authors: Kaur Namanpreet , do Rosario Michelle C. , Majethia Purvi , Mascarenhas Selinda , Rao Lakshmi Priya , Nair Karthik Vijay , Hunakunti Bhagesh , Prasannakumar Adarsh Pooradan , Naik Rohit , Narayanan Dhanya Lakshmi , Nayak Shalini S. , Bhat Vivekananda , Sharma Suvasini , Ramesh Bhat Y. , Yatheesha B. L. , Kulkarni Rajesh , Patil Siddaramappa J. , Nampoothiri Sheela , Siddiqui Shahyan , Girisha Katta Mohan , Bielas Stephanie , Shukla Anju
Published: October 2024

Several genetic disorders are associated with either a permanent deficit or a delay in central nervous system myelination. We investigated 24 unrelated families (25 individuals) with deficient myelination after clinical and radiological evaluation. A combinatorial approach of targeting and/or genomic testing was employed. Molecular diagnosis was achieved in 22 out of 24 families (92%). Four families (4/9, 44%) were diagnosed with targeted testing and 18 families (18/23, 78%) were diagnosed using broad genomic testing. Overall, 14 monogenic disorders were identified. Twenty disease‐causing variants were identified in 14 genes including PLP1, GJC2, POLR1C, TUBB4A, UFM1, NKX6‐2, DEGS1, RNASEH2C, HEXA, ATP7A, SETBP1, GRIN2B, OCLN, and ZBTB18. Among these, nine (45%) variants are novel. Fourteen families (82%, 14/17) were diagnosed using proband‐only exome sequencing (ES) complemented with deep phenotyping, thus highlighting the utility of singleton ES as a valuable diagnostic tool for identifying these disorders in resource‐limited settings.
The collaborative cross mouse for studying the effect of host genetic background on memory impairments due to obesity and diabetes
Authors: Paz Avia , Midlej Kareem , Zohud Osayd , Lone Iqbal M. , Iraqi Fuad A.
Published: October 2024

Background

Over the past few decades, a threefold increase in obesity and type 2 diabetes (T2D) has placed a heavy burden on the health‐care system and society. Previous studies have shown correlations between obesity, T2D, and neurodegenerative diseases, including dementia. It is imperative to further understand the relationship between obesity, T2D, and cognitive deficits.

Methods

This investigation tested and evaluated the cognitive impact of obesity and T2D induced by high‐fat diet (HFD) and the effect of the host genetic background on the severity of cognitive decline caused by obesity and T2D in collaborative cross (CC) mice. The CC mice are a genetically diverse panel derived from eight inbred strains.

Results

Our findings demonstrated significant variations in the recorded phenotypes across different CC lines compared to the reference mouse line, C57BL/6J. CC037 line exhibited a substantial increase in body weight on HFD, whereas line CC005 exhibited differing responses based on sex. Glucose tolerance tests revealed significant variations, with some lines like CC005 showing a marked increase in area under the curve (AUC) values on HFD. Organ weights, including brain, spleen, liver, and kidney, varied significantly among the lines and sexes in response to HFD. Behavioral tests using the Morris water maze indicated that cognitive performance was differentially affected by diet and genetic background.

Conclusions

Our study establishes a foundation for future quantitative trait loci mapping using CC lines and identifying genes underlying the comorbidity of Alzheimer's disease (AD), caused by obesity and T2D. The genetic components may offer new tools for early prediction and prevention.
Semi‐Quantum Signature Protocol Using EPR Steering and Single Photons
Authors: Yang Chun‐Wei
Published: October 2024

This study tackles critical issues in semi‐quantum signature (SQS) protocols to enhance security and efficiency. It revisits Xia et al.’s SQS protocol, which uses EPR steering for security but introduces inconsistencies in a semi‐quantum environment. Xia et al. assume that both the signatory and arbitrator have full quantum capabilities, while the verifier only has partial capabilities, making them a classical participant. However, their protocol requires the verifier to perform eavesdropping checks, necessitating quantum storage, which is not aligned with a semi‐quantum environment. The study proposes a novel SQS protocol using EPR steering and single photons, with pre‐shared keys to determine photon arrangements to address this. This ensures that only the communicating parties know the inspection and message transmission locations, solving the quantum storage issue and enabling efficient eavesdropper detection and identity authentication. This new protocol adheres to semi‐quantum principles and sets a foundation for future advancements in quantum cryptography and secure communication.
Autocatalysis‐Integrated Bioorthogonal (Poly)Catalyst‐Linked Immunosorbent Assay for Living Cell Membrane Antigens
Authors: Feng Xuepu , Tong Guoming , Ran Zengwei , Liu Xiaojuan , Li Liang , Liu Guhuan , Yang Ronghua
Published: October 2024

Immunoassay methods, notably enzyme‐linked immunosorbent assays (ELISAs), renowned for their signal amplification capabilities, are extensively employed in scientific research and clinical diagnostics. However, the instability of enzymes and their sensitivity to cellular environments present significant challenges for the broad application of ELISA in living cells. In this work, we present a bioorthogonal (poly)catalysis‐linked immunosorbent assay (BCLISA) designed for the detection of cell membrane antigens, which involves coupling bioorthogonal catalysts based on small molecules or polymers to antibodies. After screening, we opted for the copper(I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) as the core reaction system. The polymer‐based catalysts exhibit enhanced reactivity at the same molecular concentration due to their multiple catalytic sites. Polytriazoles formed during the CuAAC reaction have the ability to chelate Cu(I), thereby promoting faster catalysis. By harnessing this autocatalytic feature, we successfully increased the signal amplification potential of BCLISA. Ultimately, this autocatalysis‐integrated BCLISA technique was employed for antigen detection and imaging on both in vitro and living cell membranes. This approach offers a new method for the detection and imaging of low‐abundance antigens on living cells.
Single‐Atom Pt Loaded on MOF‐Derived Porous TiO2 with Maxim‐Ized Pt Atom Utilization for Selective Hydrogenation of Halonitro‐benzene
Authors: Guo Mingchun , Meng Qiangqiang , Gao Ming‐Liang , Zheng Lirong , Li Qunxiang , Jiao Long , Jiang Hai‐Long
Published: October 2024

The location control of single atoms relative to supports is challenging for single‐atom catalysts, leading to a large proportion of inaccessible single atoms buried under supports. Herein, a “sequential thermal transition” strategy is developed to afford single‐atom Pt preferentially dispersed on the outer surface of TiO2. Specifically, a Ti‐MOF confining Pt nanoparticles is converted to PtNPs and TiO2 composite coated by carbon (PtNPs&TiO2@C‐800) at 800 °C in N2. Subsequent thermal‐driven atomization of PtNPs at 600 °C in air produce single‐atom Pt decorated TiO2 (Pt1/TiO2‐600). The resulting Pt1/TiO2‐600 exhibits superior p‐chloroaniline (p‐CAN) selectivity (99 %) to PtNPs/TiO2‐400 (45 %) and much better activity than Pt1@TiO2‐600 with randomly dispersed Pt1 both outside and inside TiO2 in the hydrogenation of p‐chloronitrobenzene (p‐CNB). Mechanism investigations reveal that Pt1/TiO2‐600 achieves 100 % accessibility of Pt1 and preferably adsorbs the –NO2 group of p‐CNB while weakly adsorbs –Cl group of p‐CNB and p‐CAN, promoting catalytic activity and selectivity.
Strong Metal‐Support Interaction between Pt and TiO2 over High‐Temperature CO2 Hydrogenation
Authors: Hu Xiaochun , Xu Dan , Jiang Jianchun
Published: October 2024

The catalytic activities and stability of oxide‐supported metal catalysts are significantly affected by metal‐support interactions (MSI) between oxidic supports and supported metals. The surface properties of the support, such as its phase and defects, are crucial in MSI, including both the strong metal‐support interaction (SMSI) and electronic metal‐support interaction (EMSI). In this study, modulation of SMSI was achieved on rutile‐supported Pt nanoparticles (NP) over high‐temperature CO2 hydrogenation. The encapsulation of Pt NP surfaces with TiO2–x overlayers is precisely controlled by the defects. It is found that oxygen vacancy defects significantly enhance the catalytic stability of Pt/rutile under high‐temperature reverse water‐gas shift (RWGS) reaction by inhibiting the occurrence of SMSI. Pt/rutile with oxygen vacancies achieves a 301 molCO ⋅ gM−1 ⋅ h−1 space time yield and considerably catalytic stability (decreased by 8 %) at 800 °C over 100 h time‐on‐stream. Density functional theory (DFT) calculations suggest that the adsorption capacity of Pt NP on the rutile overlayer can be reduced by increasing electron density. Experimental results combined with DFT calculations show that electron transfer from Pt NP to rutile is reduced by the oxygen vacancy defects on Pt/R, preserving the metallic nature of Pt species during CO2 hydrogenation, thereby preventing the formation of SMSI.
Fe2O3 Nano‐Catalyst Mediated Oxidative Decarboxylation CH Acylation/Benzoylation of 3‐Alkylidene‐2‐Oxindoles With α‐Keto Acids
Authors: Rana Soumitra , Bera Aswini , Sarkar Prabhat , Shee Uday , Sinha Goutam , Bera Debasish , Khatua Bhanu Bhusan , Mukhopadhyay Chhanda
Published: October 2024

We successfully employed an environmentally friendly synthesized heterogeneous Fe2O3 nano‐catalyst‐mediated one pot approach to β CH bond acylation of 3‐Alkylidene‐2‐Oxindoles via oxidative decarboxylation of α‐keto acids. This method enabled the activation of Csp2‐H bonds, resulting in the formation of Csp2‐Csp2 single bonds and the generation of highly substituted derivatives of (E)‐2‐(2‐oxoindolin‐3‐ylidene)‐1‐aryl‐3‐substituted‐propane‐1,3‐diones and (E)‐3‐oxo‐2‐(2‐oxoindolin‐3‐ylidene)‐3‐substituted‐propanoates. The synthesized non‐toxic Fe2O3 nano‐material was meticulously characterized through FT‐IR, powdered XRD, HRTEM, EDX, BET, and ICP‐MS analyses. This heterogeneous catalyst can be conveniently recovered with a magnetic field and reused in subsequent reactions. This method offers excellent functional‐group tolerance, efficient substrate yield in less time, simple workup, and a recyclable catalyst.
Optimization of Photocatalytic Degradation of Rhodamine B and Indigo Carmine Dyes Using Eco‐Friendly Kaolinite‐Silver Oxide Quantum Dots Nanocomposite Under Sunlight Irradiation
Authors: Awad Mahmoud E. , Farrag Amr M. , Aboelnga Mohamed M. , El‐Bindary Ashraf A.
Published: October 2024

In this work, we present a simple method for the pyrofabrication of a new kaolinite‐ silver oxide quantum dots nanocomposite (Kao‐Ag2O/QDs) that is used for the degradation of rhodamine B (RhB) and indigo carmine (IC) dyes. A homogenous combination of kaolinite and silver nitrate was sintered up to 350 °C to create the extremely effective photocatalyst (Kao‐Ag2O/QDs). Various analytical techniques were employed to characterize the Kao‐Ag2O/QDs photocatalyst such as XRD, FTIR, XPS, SEM–EDX, TEM, DTA/TGA, ZP, BET, and UV–Vis DRS. The degradation of RhB and IC dyes through the photocatalyst was carried out in aqueous solutions utilizing several pH dye solutions and sustainable solar energy in atmosphere conditions. The nanocomposite that was prepared had shown an enhanced specific surface area of 53.3005 m2/g, a pore size of 8.1197 nm, and a total pore volume of 0.216 cm3/g. It also displayed an optical band gap energy of 2.9 eV. The study creates that employing the ideal dose of 2000 and 1500 mg/L of the Kao‐Ag2O/QDs photocatalyst at neutral conditions (pH = 7) resulted a maximum degradation effectiveness of RhB and IC of 91.06 and 93.46% after 90 min, respectively. RhB and IC dyes degradation followed Langmuir first‐order kinetics with a rate constant of 0.0217 and 0.0216 min−1 at pH = 7, respectively. The photocatalytic degradation activity for RhB dye is based on hydroxyl radicals (˙OH) and superoxide radicals (˙O2−), while the mechanism of IC removal is based on superoxide radicals (˙O2−), as revealed by scavenger‐based radical trapping studies. A triple reusability study found that the Kao‐Ag2O photocatalyst is highly stable with degradation efficiencies of RhB and IC dyes from the initial 91.09 to 90.04, 88.54, and 86.27% and from the initial 93.46 to 92.8, 91.4 and 89.32%, respectively. The optimal situations for the parameters were identified by the Box–Behnken design (BBD), which was well matched with photocatalytic degradation tests.
Novel Nanoparticle‐Sized Cu(II), Ru(III), and Th(IV) Chelates Derived From Quinaldine Azo Dye Ligand: DFT Studies, Molecular Docking, and Applications in Drug Development and Catalysis
Authors: Khedr Abdalla M. , Gaber Mohamed , Elsharkawy Mohsen , Atlam Faten M. , Bakr Eman A.
Published: October 2024

Three novel complexes of copper(II), ruthenium(III), and thorium(IV) ions with quinaldine azo dye ligand HL were synthesized in nanoscale. Applying mass spectroscopy, electronic, infrared, 1H NMR, elemental, and thermal investigations, their structures were examined. By using azo nitrogen and hydroxyl oxygen atoms to coordinate as a monobasic bidentate, it was found that the ligand displayed bicapped square antiprism geometry with thorium(IV) metal ion, square pyramidal arrangement in copper(II) complex and octahedral configuration in ruthenium(III) complex. In order to confirm the complexes' geometrical arrangement, theoretical investigations were carried out using DFT/B3LYP/6–311 + G(d,p)/LANLDZ. The dipole moment, geometrical configuration, energetic parameters, and HOMO–LUMO gap of energy have been calculated. The compounds were formed in nanometric forms, as indicated by the mean particle sizes obtained by applying TEM. Based on TEM images for the complexes of copper(II), ruthenium(III), and thorium(IV), their average particle sizes were 11.04, 3.89, and 1.52 nm, respectively. PANC‐1 and A‐549 cells were used in the tests to evaluate the compounds' anticancer activity against the vinblastine reference. The findings confirm the great cytotoxicity effect of the free ligand and its complexes against the investigated cell lines using different doses of the examined compounds. Ru(III) and Cu(II) complexes exhibited cytotoxic effectiveness greater than that of vinblastine. The azo ligand, HL, exhibited the strongest antibacterial activity that is superior to that of the conventional medicines themselves and greater than that of its metal complexes. The most physiologically active compound's ideal conformation was found using molecular docking research, and the manner in which the Ru(III) complex and the enzyme of Panc‐1 link together was determined. It interacts in three different modes with the target receptor (PANC‐1): hydrophobic force, electrostatic force, and H‐bond. In addition to increasing the candidate activity, these interactions can be used to design and predict new, effective compounds. The capacity of the ligand and its complexes to act as heterogeneous catalysts for the oxidation of methyl violet 2B was examined. The ruthenium(III) and thorium(IV) complexes generated the greatest catalytic efficiencies.
Invasion Dynamics of the Alien Amphibian Xenopus laevis in France: Perspectives for Management
Authors: Pagano Alain , Harmange Clément , Rappoccio Mariastella , Colchen Tatiana , Combet Gabriel , Chouteau Philippe , Picard Damien , Moreau Eléonore , Bartoli Marco , Pays Olivier
Published: October 2024

Background

Invasive alien species (IAS) are recognised as pervasive drivers of global environmental change and pose significant threats to socio‐ecosystems worldwide. Although much attention is focused on prevalent IAS, the oversight of species that are still contained and approaching critical invasion thresholds raises concern. In this context, scientific support to implement effective and spatially informed management strategies is critically needed.

Aims

Our study focuses on the African clawed frog, Xenopus laevis, a concerning IAS projected to undergo a substantial expansion in Europe.

Materials & Methods

Using a comprehensive analysis of three distinct datasets, our study aimed to document newly colonised sites and provide an up‐to‐date overview of the current distribution and invasion dynamics of X. laevis in France.

Results

Our results revealed recent colonisation of new sites within the established range of the species and the continuous progression of the invasion front at a rate of 1.2 km per year. This annual progression currently translates to an expansion of approximately 400 km2 per year in the predicted distribution range of the species.

Discussion

Emphasising the urgent need for proactive management, we recommend measures encompassing prevention, early detection and rapid responses to invasion, delineated across three strategic zoning levels.

Conclusion

Immediate and coordinated efforts are imperative to anticipate and mitigate the considerable socio‐environmental impacts associated with this species in the future.
N‐[4‐(Benzyloxy)‐3‐methoxybenzyl)]adamantane‐1‐amine (DZH2), a dual CCR5 and CXCR4 inhibitor as a potential agent against triple negative breast cancer
Authors: Rostom Monica M. , El‐Zohairy Mariam A. , Marzouk Mohamed A. , Berger Martin R. , Schols Dominique , Assal Reem A. , Mandour Yasmine M. , Adwan Hassan , Zlotos Darius P.
Published: October 2024

DZH2, a dual inhibitor of the chemokine receptors CCR5 and CXCR4, was discovered from virtual screening for CCR5 antagonists. In specific Ca2+ chemokine signaling assays, DZH2 displayed low micromolar IC50 values at both chemokine receptors. Its binding to intracellular allosteric binding sites of CCR5 and CXCR4 was confirmed by MD simulations and binding free‐energy calculations. DZH2 is superior to the CCR5 antagonist maraviroc in terms of its inhibitory activity on the growth of two breast cancer cell lines. In MCF7 and MDA‐MB‐231 cells, DZH2 was a >100‐fold more potent inhibitor of cell viability compared to maraviroc. DZH2 (6.7 µM) reduced migration of MDA‐MB‐231 cells to 4% compared to 50% inhibition of migration caused by maraviroc (780 µM). Also, DZH2 was a significantly more potent inhibitor of colony formation in MDA‐MB‐231 cells than maraviroc. In MCF10 cells, DZH2 caused no alteration in the gene expression with respect to cellular pathways mediating cell death, indicating its selectivity to breast cancer cells.
The carcinogenesis of esophageal squamous cell cancer is positively regulated by USP13 through WISP1 deubiquitination
Authors: Wang An , Wang Youbo , Ma Qinyun , Chen Xiaofeng
Published: October 2024

The objective was to determine whether USP13 stabilizes WISP1 protein and contributes to tumorigenicity and metastasis in ESCC through the Wnt/CTNNB1 signaling pathway. ESCC cell lines (KYSE150 and TE10) were treated with the proteasome inhibitor MG‐132, followed by siRNA screening of deubiquitinases (DUBs) to identify regulators of WISP1. Mass spectrometry, immunoprecipitation, and in vitro functional assays were conducted to explore the interaction between USP13 and WISP1 and to assess the effects of USP13 downregulation on cell proliferation, migration, invasion, epithelial–mesenchymal transition (EMT), and apoptosis. Additionally, in vivo experiments using mouse models were performed to evaluate the impact of USP13 knockdown on tumor growth and metastasis. USP13 was identified as a key regulator of WISP1, stabilizing its protein levels through deubiquitination. Downregulation of USP13 resulted in reduced WISP1 protein stability, decreased cell proliferation, migration, and EMT, and increased apoptosis in vitro. In vivo, USP13 knockdown significantly inhibited tumor growth and lung metastasis. WISP1 overexpression in USP13‐knockdown cells partially rescued these phenotypes, confirming the functional role of the USP13/WISP1 axis. Furthermore, knockdown of USP13 or WISP1 impaired the activation of the Wnt/CTNNB1 signaling pathway and reduced immune checkpoint marker expression, indicating a mechanism by which USP13 promotes immune evasion in ESCC. USP13 stabilizes WISP1 through deubiquitination, enhancing ESCC progression by activating the Wnt/CTNNB1 pathway and promoting immune evasion, making USP13 a potential therapeutic target in ESCC.
Biomimetic synthesis of fluvirosaone A
Authors: Kang Gyumin , Han Sunkyu
Published: October 2024

Over the past century, biomimetic synthesis has significantly enhanced our understanding of the biosynthetic pathways involved in the formation of natural products. In this article, we present a two‐step biomimetic synthesis of fluvirosaone A from 2,3‐dehydroallosecurinine, featuring a Nazarov‐type cyclization as the key step. Based on our synthetic results and computational analysis, we propose an alternative biosynthetic route for fluvirosaone A, identifying pyruvaldehyde as the likely source of the extraneous three carbons incorporated into the securinega skeleton.
Stretchable conducting polymer PEDOT:PSS treated with hard‐cation‐soft‐anion ionic liquid designed from molecular modeling
Authors: Lansac Yves , Choi Changwon , Jang Yun Hee
Published: October 2024

PEDOT:PSS, an ionic polymer mixture of positively‐charged poly‐3,4‐ethylenedioxythiophene (PEDOT+) and negatively‐charged poly‐styrenesulfonate (PSS−), is a water‐processable and environmentally‐benign organic semiconductor and electrochemical transistor, which plays a key role in organic (bio)electronic devices. However, pristine PEDOT:PSS films form 10‐to‐30‐nm granular domains, where conducting‐but‐hydrophobic PEDOT‐rich cores are surrounded by hydrophilic‐but‐insulating PSS‐rich shells. Such morphology makes PEDOT:PSS water‐soluble and thermally stable but very poor in conductivity. A tremendous amount of effort has been made to enhance the conductivity of PEDOT:PSS by restoring the extended conduction network of PEDOT. Recently, remarkable ~5000‐fold improvements of conductivity have been achieved by mixing PEDOT:PSS with proper ionic liquids (ILs). In a series of free energy estimations using density functional theory calculation and molecular dynamics simulation, we have demonstrated that the classic hard‐soft acid–base (or cation‐anion) principle of chemistry plays an important role in such improvements. Ion exchange between PEDOT+:PSS− and A+:X− ILs helps PEDOT+ to decouple from PSS− and to grow into large‐scale conducting domains of π‐stacked PEDOT+ decorated by IL anions X−. Thus, the most spontaneous decoupling between soft (hydrophobic) PEDOT+ and hard (hydrophilic) PSS− would be induced by strong interaction with soft anions X− and hard cations A+, respectively. Such hard‐cation‐soft‐anion principles have led us to design ILs containing extremely hydrophilic (i.e., protic) cations and hydrophobic anions. Not only they indeed improve the conductivity of PEDOT:PSS but also enhance its stretchability as well. In summary, our modeling offered molecular‐level insights on the morphological, electrical, and mechanical properties of PEDOT:PSS and a molecular‐interaction‐based enhancement strategy for intrinsically stretchable conductive polymers.
Enantioseparation strategies for sertraline by instrumental and crystallization‐based techniques: An important issue in quality control
Authors: Kaviani Raha , Jouyban Abolghasem , Javan Mahsa , Seyfinejad Behrouz , Shayanfar Ali
Published: October 2024

Enantiomers of a chiral active pharmaceutical ingredient (API) often exhibit different physicochemical, pharmacokinetic, and biological properties. Therefore, enantioseparation becomes a critical aspect of pharmaceutical development. Sertraline, one of the most widely prescribed antidepressant medications, requires purification from its chiral impurities, and this is recommended and essential for its quality control. This perspective highlights the current established research on the separation and quantification of sertraline's chiral impurities, with a focus on instrumental and crystallization‐based techniques.
Microfoundations of dynamic capabilities enabling scaling pathways of sustainability‐oriented innovation business models
Authors: Mehrabi Sepide , Mahdad Maral , Bijman Jos , Cholez Celia , Mesa Juan Carlos Perez , Giagnocavo Cynthia
Published: October 2024

Using the lens of the microfoundations of dynamic capabilities, this article sheds light on the scaling pathways (scaling up, out, and deep) of sustainability‐oriented innovation business models (SOI BMs). Empirical data from 20 small‐sized agri‐food organizations working on SOI as a core BM value proposition was collected and analyzed. We categorized microfoundations of dynamic capabilities of these organizations through multi‐layered deductive and abductive coding and a two‐level analysis and showed they are interconnected. Our results also highlight that specific microfoundations of dynamic capabilities mutually reinforce each other and collectively result in the realization of each scaling pathway. Our cross‐case analysis shows interdependence amongst scaling pathways, where the success of one is a prerequisite for another. This research offers a framework to unpack scaling pathways and provides important insights into scaling strategies and practices for developing SOI BMs, benefiting researchers, practitioners, and policymakers.
Predictors and Interdependence of Quality of Life in a Random Sample of Long‐Term Young Breast Cancer Survivors and Their Biological Relatives
Authors: Ellis Katrina R. , Koechlin Helen , Rudaz Marion , Gerido Lynette Hammond , Hecht Hillary K. , Jones Carly , Raji Dolapo , Northouse Laurel , Katapodi Maria
Published: October 2024

Purpose

Quality of life (QOL) among young breast cancer survivors (YBCS) is often worse than QOL of older breast cancer survivors or age‐matched peers without a history of cancer. Families commonly support YBCS, particularly during treatment, but little is known about long‐term YBCS and family member QOL. The purpose of this study was to identify demographic, clinical, and psychosocial predictors of physical and mental QOL in YBCS and biological relatives and investigate associations between their QOL (i.e., QOL interdependence).

Methods

This secondary data analysis includes a random sample of long‐term YBCS (≤ 45 years old at diagnosis) and up to two female relatives at baseline (post‐treatment) and 18‐month follow‐up. The sample consists of 189 dyads (YBCS and one relative) and 121 triads (YBCS and two relatives). Actor‐partner interdependence models (APIMs) were used to estimate the influence of YBCS's and relatives' demographic, clinical, and psychosocial factors on their own QOL (actor effects) and the other persons' QOL (partner effects).

Results

For YBCS and relatives, QOL at the baseline was associated with their QOL at 18‐months. YBCS's perceived cancer risk was associated with their own and relatives' QOL. Older relatives' physical QOL at baseline was associated with younger relatives' physical QOL at follow‐up. Age, race, marital status, years since diagnosis, education, out‐of‐pocket costs of care, routine sources of care, income, family support, fear of recurrence, anxiety, and depression were also significant predictors of QOL.

Conclusions

Findings revealed independent and interdependent effects on QOL. These predictors point to potential targets of support for families.

Trial Registration

ClinicalTrials.gov ID: NCT01612338
Does Attitudinal Inoculation Confer Resistance to Violent Extremist Propaganda? Assessing Mechanisms, Long‐Term Effects, and the Advantage of Visuals
Authors: Schumann Sandy , Barton Michael
Published: October 2024

Previous research suggests that attitudinal inoculation can confer resistance to violent extremist propaganda. The present study aimed to strengthen and extend this rather scant evidence base. First, we conceptually replicated Braddock (2022) and investigated whether attitudinal inoculation reduces intentions to support a violent extremist group (VEG) by eliciting higher levels of anger and counter‐arguing. Advancing the literature, we examined as well if the effect of attitudinal inoculation on violent extremist behavioural intentions lasted for up to 1 week and if message‐relevant emotionally evocative visuals enhanced the influence of inoculation stimuli. We conducted a multi‐phase longitudinal online experiment with two waves (Nwave1 = 498; Nwave2 = 399). Participants read the inoculation treatment (or control message) and were then exposed to the propaganda of a fictional VEG. Outcomes were measured immediately and again after 1 week. Partially supporting Braddock (2022), inoculated participants who were less strongly ideologically aligned with the VEG reported (compared to the control condition) lower violent extremist behavioural intentions. Inoculation had no impact on the behavioural tendencies of individuals who were strongly ideologically aligned with the VEG. Crucially, contesting Braddock (2022), inoculated participants felt less (not more) anger towards the violent extremist group. After 1 week, no direct effect of attitudinal inoculation on violent extremist behavioural intentions but an indirect effect mediated by counter‐arguing was confirmed. The modality of the inoculation stimulus did not moderate its influence. In summary, attitudinal inoculation conferred resistance to violent extremist propaganda for a short period and for individuals who are perhaps less at risk of being persuaded by VEGs. Further research is needed to replicate the exploratory findings and to investigate the role of anger as well as means to boost the long‐term influence of attitudinal inoculation treatments. Please refer to the Supplementary Material section to find this article's Community and Social Impact Statement.
Opportunity's Calling: Perceived Inequality and Causal Beliefs About Socioeconomic Status Linked to Civic Engagement
Authors: Im Hohjin , Shane Jacob
Published: October 2024

Although objective states of inequality often stifle civic engagement, subjective perceptions of inequality can stimulate it. Across two studies using a nationally representative US sample (Study 1, n = 1053) and a US university student sample (Study 2, n = 604), we found that the perception of inequality was positively associated with civic engagement. We further explored the mediating pathways linking this association. We found that perceived inequality is positively associated with the belief that socioeconomic status (SES) is attained through opportunity (e.g., social connections). In turn, opportunity belief was negatively associated with acceptance of inequality which was likewise negatively correlated with civic engagement. Our findings suggest opportunity belief may be a key mechanism activated by perceived inequality that links it to civic engagement. Please refer to the Supplementary Material section to find this article's Community and Social Impact Statement.
Isolation, Characterization, and Anti‐Inflammatory Effects of β‐Sitosterol‐β‐D‐Glucoside from Hygrophila auriculata: Experimental Validation, Molecular Docking, and Molecular Dynamics Simulations
Authors: Alghamdi Mashael A. , Azam Faizul , Sarfaraj Hussain Md , Ali Mohamed A. M. , Jamir Anwar Md , Mahmood Danish
Published: October 2024

Hygrophila auriculata (K. Schum) Heine is known to treat various common aliment e. g. rheumatoid arthritis, kidney infections, jaundice, edema, and gout. This study aims to isolate bioactive components from the methanolic extract, assess their anti‐inflammatory effects, and investigate their interactions with drug targets through docking and molecular dynamics simulations. Methanolic extract of H. auriculata furnished stigmast‐5‐en‐3‐ol‐β‐D‐glucopyranoside (HA‐06) which was characterized by using IR, NMR and mass spectral data. HA‐06 alleviated carrageenan‐induced inflammation in rats, while the methanolic extract of H. auriculata produced comparable results. The findings were similar to those of the positive control, indomethacin. The chemical structure of HA‐06 was optimized using DFT at the B3LYP level and subsequently used for molecular docking against anti‐inflammatory drug targets. HA‐06 exhibited strong affinity towards phospholipase A2 and glucocorticoid receptor exhibiting binding energies of −11.25 kcal/mol and −11.07 kcal/mol, respectively. Molecular dynamics simulation was used to assess the dynamical stability of these two complexes and their native co‐crystallized ligands. Principal component analysis, radius of gyration, free energy landscapes, solvent‐accessible‐surface‐area, and root‐mean square deviation/fluctuation all indicated stable interactions. Therefore, HA‐06 could be a promising candidate for development into an effective therapy against inflammatory diseases targeting phospholipase A2 and glucocorticoid receptor.
Skeletal Isomerization of Ergosterol‐5,8‐Peroxide Leading to the Discovery of Unprecedented Ergostanes and Collective Syntheses of 5,6‐Epoxysterols and (+)‐Sarocladione
Authors: Nagayasu Saki , Togo Hinata , Nagai Kaoru , Kobayashi Shoji
Published: October 2024

Skeletal isomerization of ergosterol peroxide, a primary oxidation product of ergosterol, was investigated under thermal and iron(II)‐mediated conditions. Thermal isomerization resulted in not only the isolation of the predicted 7‐hydroxy‐5,6‐epoxides but also the discovery of the unprecedented 7/9/5‐ring‐fused ergostane for the first time. The iron(II)‐mediated isomerization proceeded at ambient temperature, resulting in the formation of the expected 5,6‐epoxysterols and a ring‐opened bicyclic diketone. The diketone was further converted into novel ergostane under thermal conditions and into (+)‐sarocladione under acidic conditions. All transformations from ergosterol to sarocladione, including the isolation of the unstable diketone intermediate, were achieved at ambient temperature, confirming the biosynthetic pathway of sarocladione. Several mushroom ingredients with a 5,6‐epoxy group were synthesized stereoselectively from the isomerization products, leading to the confirmation or revision of the structures of natural products. The β‐amyloid aggregation inhibitory activity of synthetic sterols was evaluated for the first time to gain insights into the potential for dementia prevention. This study is valuable both for supplying rare sterols found in mushrooms for biological studies and for shedding light on the oxidative metabolic pathways of ergosterol.
Heavier Diferrocenylpnictogenium Ions
Authors: Stoian Corina , Olaru Marian , Demeshko Serhiy , Fischer Malte , Mebs Stefan , Hupf Emanuel , Beckmann Jens
Published: October 2024

The synthesis, characterization and reactivity of the diferrocenylphosphenium ion [Fc2P]+ was extended to the heavier diferrocenylpnictogenium ions, [Fc2E]+ (E=As, Sb, Bi). The lighter diferrocenylnitrenium ion, [Fc2N]+, was detected by mass spectrometry, but could not be isolated. The molecular structures of [Fc2E]+ (E=P, As, Sb, Bi) reveal intramolecular coordination of the iron atoms, which counterbalance the electron deficiency of the pnictogens without affecting the strong Lewis acidities, which were determined according to the method of Gutmann and Beckett. The (electro−)chemical oxidation and reduction afforded the dications [Fc2E]2+ (E=P (unstable), As) and the neutral dipnictogens Fc2EEFc2 (E=P, As).
Enantioselective Cascade Reactions of Aminocatalytic Dienamines and Trienamines Initiated by a Cycloaddition Reaction
Authors: Faghtmann Jonas , Pladsbjerg Andresen Signe Sofie , Rask Østergaard Anne , Anker Jørgensen Karl
Published: October 2024

Cycloadditions are widely accepted as a group of reactions that rapidly generate molecular complexity. Being highly atom economic and often predictable, these reactions can generate up to four stereogenic centers and two C−C (or C−X) bonds in one reaction step. During the last two decades, asymmetric aminocatalysis has shown to be a successful strategy for controlling stereoselectivity and enabling reactivity of cycloaddition reactions. By increasing the conjugation of the carbonyl species employed, dienamines and trienamines can be catalytically formed. Not only can these facilitate the cycloaddition, often accompanied by high levels of stereocontrol, but they also leave a residual enamine or carbonyl (by hydrolysis) in the cycloadduct. This residual functionality can engage in further intramolecular reactions generating complex cyclic systems in a one‐pot cascade manner. In this regard, asymmetric aminocatalysis can add another layer of complexity to the already complex nature of cycloadditions. In this review, we will present the general concept of such reactivity patterns of dienamines and trienamines, and hereafter showcase examples in the literature. We aspire that the chemical community can use these concepts to design new enantioselective aminocatalytic cascade reactions to access enantioenriched, complex compounds, and perhaps use these in complex molecule synthesis.
Phenazinium‐ and Malachite Green‐Based Pd(II) Cages: Chiroptical Discrimination of Nucleoside Triphosphates
Authors: Durmisevic Armin , Regeni Irene , Namoro Mark Ely , Baksi Ananya , Clever Guido H.
Published: October 2024

Organic chromophores have been successfully implemented into supramolecular systems to bestow them with distinct photophysical properties for various applications, ranging from solar energy conversion, photochemical reactions or as receptors for guest molecules with optical readout. We had previously introduced first members of the large family of coal‐tar dyes (methylene blue, crystal violet and rhodamine) as integral components of coordination cages. Here, we add two new chromophores, malachite green (MGP) and a purple phenazinium dye (PHP), serving as backbones of bis‐monodentate banana‐shaped ligands with pyridine donors. We show the formation of corresponding green and purple coloured Pd2L4 coordination cages and investigate their interaction with chiral guest molecules via UV‐Vis and CD spectroscopy. The PHP cage can be used to recognize nucleoside triphosphates, based on chirality transfer from the guests to the structurally flexible helicate. In combination with the already known methylene blue cage MBP we could further differentiate between all four canonical NTPs through characteristic changes in the observed CD signatures.
Outcomes following off‐site remote systemic cancer therapy administration
Authors: Arnold Abram S. , Asif Samia , Shostrom Valerie , Krishnan Mridula , Ganti Apar Kishor
Published: October 2024

Background

The Veterans Affairs Nebraska Western Iowa Health Care System (VA‐NWIHCS) uses teleoncology and remote systemic cancer therapy services to expand care to veterans in rural Nebraska via remote sites in Lincoln and Grand Island. This study compares clinical outcomes in patients receiving care at these remote sites to those at the primary site in Omaha.

Methods

Data were retrospectively reviewed for 151 patients who received first‐line systemic therapy at VA sites in Omaha, Lincoln, or Grand Island between January 1, 2018, and December 31, 2020. This included patient demographics, malignancy type and stage, survival, systemic therapy received, treatment intent and toxicities, missed or delayed cycles, and frequency of hospitalizations or emergency department visits. SAS version 9.4 was used for analysis.

Results

The study population included 108 patients who received their systemic therapy in Omaha, whereas 43 received therapy at the remote sites. The demographic of both populations was predominantly male with a median age of 69 years and Eastern Cooperative Oncology Group Performance Status of 0 to 1. The two groups were comparable in terms of comorbidities. Both populations had a similar distribution of cancer types, proportion of patients with stage IV disease, and treatment with curative intent. There was no difference in 1‐ and 2‐year survival, systemic therapy‐related toxicity classification and prevalence, number of delayed/missed cycles, and hospitalization/emergency department visits.

Conclusion

Evaluated outcomes in patients treated in Omaha versus remote sites via teleoncology under the same providers were similar. Effective oncology care, including systemic therapy, can be provided via teleoncology, and this model can help mitigate issues with access to care.