bluuebunny/crossref_metadata_2025 huggingface dataset:
The Midas Touch by Internal Stimuli: Activatable Luminogens with Near‐Infrared Aggregation‐Induced Emission for Potent Bioimaging and Theranostics
Authors: Gao Yiting , Yan Dingyuan , Yang Xinyue , Huang Weigeng , Sun Yan , Zhu Dongxia , Liu Qian , Shan Guogang , Wang Dong , Tang Ben Zhong
Published: September 2024

As a modality of optical imaging, fluorescence imaging of biochemical analytes holds significant potential in the field of disease diagnosis and therapy. However, the non‐responsive fluorophores are not able to selectively and sensitively detect lesions, resulting in a poor signal‐to‐background ratio and compromised accuracy. The utilization of activatable sensors, in contrast, is capable of effectively overcoming these limitations by displaying variations in fluorescence intensity and spectral wavelength in response to physiological parameters. Aggregation‐induced emission luminogens (AIEgens), particularly those emitting fluorescence in the near‐infrared (NIR, 700–1700 nm) window, have practical application prospects in disease theranostics due to their excellent photostability, deeper penetration depth, and enhanced fluorescence intensity in physiological environments. In this review, an overview of the advancements in research on NIR AIEgens for internal stimuli‐activated diagnosis and treatment of diseases is provided. The design principles of responsive NIR AIEgens and their biomedical applications are exemplified with representative examples, categorized based on the type of stimuli. Finally, the review concludes with a brief discussion of the challenges, opportunities, and future prospects of activatable NIR AIEgens in the field of disease photo theranostics.
Ultrahigh Thermal Robustness of High‐Entropy Spectrally Selective Absorbers for Next‐Generation Concentrated Solar Power System
Authors: Zhao Peng , Dong Meng , Liu Xi , Wang Yun‐Feng , Wang Wei‐Ming , Liu Bao‐Hua , Lu Zhong‐Wei , He Cheng‐Yu , Gao Xiang‐Hu
Published: September 2024

Spectrally selective absorbers (SSAs) are a critical component in concentrated solar power (CSP) systems, as they maximize sunlight absorption while suppressing heat radiative loss. Despite various SSAs being demonstrated, the challenges remain on the limitations of thermal instability at elevated operating temperatures especially above 650 °C due to component oxidation and diffusion in the absorption layer. To address these challenges, herein a high‐entropy strategy is resorted. By utilizing high‐entropy nitride film as an absorption layer, a double‐layer SSA is prepared by a facile magnetron sputtering method. High‐entropy engineering intensifies and complicates the localized electronic bands, concurrently exhibiting relatively flat bands around the Fermi level, which can significantly enhance 3d interband transition. The resultant SSA delivers the desired spectral selectivity (α/ɛ82 °C = 92.7%/8.4%). Benefitting from the high‐entropy effect, the SSA maintains outstanding optical properties (α/ɛ82 °C = 93.3%/9.4%) even after a 750 °C vacuum thermal treatment for 120 h. Under 1 kW m−2 simulated illumination, the surface temperature of the absorber can easily rise to 95.3 °C, suggesting its remarkable solar‐thermal performance. Furthermore, its effectiveness in parabolic trough collectors (PTCs) is validated. All these competitive performances make the high‐entropy SSA a potentially promising candidate for PTCs.
Advanced Organic–Inorganic Hybrid Materials for Optoelectronic Applications
Authors: Zhou Kun , Qi Bingyu , Liu Zhongwei , Wang Xinjiang , Sun Yuanhui , Zhang Lijun
Published: September 2024

Research on organic–inorganic hybrid materials (OIHMs) has experienced explosive growth in the past decades. The diversity of organic components allows for the introduction of various spatial scales, functional groups, and polarities, while inorganic components provide higher hardness, heat resistance, and stability, their flexible combination facilitates the formation of diverse structures. Furthermore, simple and cost‐effective synthesis methods, such as room temperature solution processes and mechanochemical techniques, enable precise control over the materials' properties at different scales, thus achieving adjustable structure–performance relationships. This review will discuss the recent research progress of OIHMs within the field of optoelectronics and related optoelectronic device applications. According to the dimension of inorganic components and the nature of organic–inorganic interface, this review divides OIHMs into four structural categories. The ongoing research has revealed diverse applications for OIHMs in the fields of solar cells, light‐emitting devices, detectors, and memristors. As an outlook, the potential of perovskite and 0D metal halide materials, which are currently the most studied, for enhancing optoelectronic performance and stability is discussed.
Nitrogen‐Containing Surface Ligands Lead to False Positives for Photofixation of N2 on Metal Oxide Nanocrystals: An Experimental and Theoretical Study
Authors: Maldonado‐Lopez Daniel , Huang Po‐Wei , Sanchez‐Lievanos Karla R. , Jana Gourhari , Mendoza‐Cortes Jose L. , Knowles Kathryn E. , Hatzell Marta C.
Published: September 2024

Many ligands commonly used to prepare nanoparticle catalysts with precise nanoscale features contain nitrogen (e.g., oleylamine); here, it is found that the use of nitrogen‐containing ligands during the synthesis of metal oxide nanoparticle catalysts substantially impacts product analysis during photocatalytic studies. These experimental results are confirmed via hybrid Density Functional Theory (DFT) computations of the materials’ electronic properties to evaluate their viability as photocatalysts for nitrogen reduction. This nitrogen ligand contamination, and subsequent interference in photocatalytic studies is avoidable through the careful design of synthetic pathways that exclude nitrogen‐containing constituents. This result highlights the urgent need for careful evaluation of catalyst synthesis protocols, as contamination by nitrogen‐containing ligands may go unnoticed since the presence of nitrogen is often not detected or probed.
Synthesis, Structural Analysis, and Degradation Behavior of Potassium Tin Chloride as Chloride‐Ion Batteries Conversion Electrode Material
Authors: Panja Soutam , Miao Yidong , Döhn Johannes , Choi Jaehoon , Fleischmann Simon , Guddehalli Chandrappa Shivaraju , Diemant Thomas , Groß Axel , Karkera Guruprakash , Fichtner Maximilian
Published: September 2024

Chloride–ion batteries (CIBs) offer a compelling alternative to conventional battery systems, particularly in applications demanding cost‐effectiveness and resource sustainability. However, the development of tailored electrode materials remains a critical bottleneck for CIB advancement. In this study, an untapped class of perovskite‐based material, potassium hexachlorostannate (K2SnCl6, denoted as KSC) is synthesized via a facile mechanochemical route for the first time. The prepared KSC is subjected to various characterization techniques to confirm its crystal structure and morphology. Herein, KSC exhibits intriguing electrochemical performance in a non‐aqueous CIB configuration, utilizing a lithium metal counter electrode. Furthermore, ex situ X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS) analysis, reveal a conversion reaction mechanism involving chloride ion shuttling and provide insights into structural evolution during cycling. Moreover, the density functional theory (DFT) studies support additional degradation products that can potentially limit the performance of these materials as potential battery electrodes in CIBs.
Dual‐Core Engineering for Efficient Deep‐Blue Multiple Resonance Thermally Activated Delayed Fluorescent Materials
Authors: Shi Hao‐Nan , Xie Feng‐Ming , Li Hao‐Ze , Tang Jian‐Xin , Li Yan‐Qing
Published: September 2024

Developing narrowband blue multiple resonance (MR) organic emitters with Commission Internationale de L'Eclairage (CIE) y coordinates <0.1 is essential for advanced display technologies. This study proposes a deep‐blue thermally activated delayed fluorescence (TADF) emitter, named 2BNO, which integrates two independent MR cores. Unlike many TADF materials with single‐bonded dual emitting cores, 2BNO utilizes a steric hindrance‐assisted fluorene bridge to achieve an orthorhombic molecular structure. The dual‐core MR‐TADF emitter shows enhanced light absorption and a high photoluminescence quantum yield. Notably, the emission of 2BNO is not significantly redshifted compared to single‐core compounds and maintains a narrow full width at half‐maximum (FWHM) of 24 nm with CIE coordinates of (0.147, 0.041) in 2Me‐THF solution, nearing the BT.2020 blue standard. Organic light‐emitting diodes (OLEDs) incorporating 2BNO as the emitter exhibit deep‐blue emission at 460 nm with a narrow FWHM of 29 nm and CIE coordinates of (0.14, 0.09). The dual emitting core design significantly improves device efficiency, achieving a high external quantum efficiency (EQE) of 19.8%. The dual‐core molecular design strategy in this work is demonstrated to be effective in promoting the efficiency of the TADF emitters while preserving deep‐blue color purity.
Expanding Our Horizons: AIE Materials in Bacterial Research
Authors: Lee Michelle M. S. , Yu Eric Y. , Chau Joe H. C. , Lam Jacky W. Y. , Kwok Ryan T. K. , Tang Ben Zhong
Published: September 2024

Bacteria share a longstanding and complex relationship with humans, playing a role in protecting gut health and sustaining the ecosystem to cause infectious diseases and antibiotic resistance. Luminogenic materials that share aggregation‐induced emission (AIE) characteristics have emerged as a versatile toolbox for bacterial studies through fluorescence visualization. Numerous research efforts highlight the superiority of AIE materials in this field. Recent advances in AIE materials in bacterial studies are categorized into four areas: understanding bacterial interactions, antibacterial strategies, diverse applications, and synergistic applications with bacteria. Initial research focuses on visualizing the unseen bacteria and progresses into developing strategies involving electrostatic interactions, amphiphilic AIE luminogens (AIEgens), and various AIE materials to enhance bacterial affinity. Recent progress in antibacterial strategies includes using photodynamic and photothermal therapies, bacterial toxicity studies, and combined therapies. Diverse applications from environmental disinfection to disease treatment, utilizing AIE materials in antibacterial coatings, bacterial sensors, wound healing materials, etc., are also provided. Finally, synergistic applications combining AIE materials with bacteria to achieve enhanced outcomes are explored. This review summarizes the developmental trend of AIE materials in bacterial studies and is expected to provide future research directions in advancing bacterial methodologies.
Five Volts Lithium Batteries with Advanced Carbonate‐Based Electrolytes: A Rational Design via a Trio‐Functional Addon Materials
Authors: Zhang Fuming , Zhang Peng , Zhang Wenhua , Gonzalez Pedro R. , Tan Daniel Q. , Ein‐Eli Yair
Published: September 2024

Lithium metal batteries paired with high‐voltage LiNi0.5Mn1.5O4 (LNMO) cathodes are a promising energy storage source for achieving enhanced high energy density. Forming durable and robust solid‐electrolyte interphase (SEI) and cathode‐electrolyte interface (CEI) and the ability to withstand oxidation at high potentials are essential for long‐lasting performance. Herein, advanced electrolytes are designed via trio‐functional additives to carbonate‐based electrolytes for 5 V Li||LNMO and graphite||LNMO cells achieving 88.3% capacity retention after 500 charge–discharge cycles. Theoretical calculations reveal that adding adiponitrile facilitates the presence of more hierarchical DFOB− and PF6− dual anion structure in the solvation sheath, leading to a faster de‐solvation of the Li cation. By combining both fluorine and nitrile additives, an efficient synergistic effect is obtained, generating robust thin inorganic SEI and CEI films, respectively. These films enhance microstructural stability; Li dendrite growth on the Li electrode is being suppressed at the anode side and transition‐metals dissolution from the cathode is being mitigated, as evidenced by cryo‐transmission electron microscopy and synchrotron studies.
Tailoring the Surface Properties of ZnO Nanowires by ALD Deposition
Authors: Baratto Camilla , Faglia Guido , Dang Thi Than Le , Ferroni Matteo , Holovanova Viktoria , Nazarchuk Bohdan , Hakola Hanna , Niemi Tapio , Tkachenko Nikolai , Golovanov Viacheslav
Published: September 2024

Innovative research on metal‐oxide gas sensors involves nanostructuring and surface modification as key elements to tailor sensitivity and selectivity. This work addresses a ZnO nanowire‐based sensing device obtained by coupling a lithographically prepared substrate with hydrothermal ZnO growth, to align and interconnect the nanowires between two electrical contacts. Furthermore, conformal coating by atomic layer deposition technique allows functionalization of the surface of the nanowires with sub‐monolayers of Al2O3 and TiO2. A detailed analysis is carried out from a morphological and structural point of view with photoluminescence and Raman spectroscopy and electron microscopy. The material characterization results are analyzed in comparison with the functional characterization in gases toward reducing (NO2) and oxidizing (H2S) gases. Unparalleled sensing enhancement with Atomic Layer Deposition functionalization is obtained for NO2 detection. The passivation role of surface states is discussed combining information from experimental techniques with a proposed model.
Wetting and Dewetting Behaviors of Droplets on the Nanoring Surface
Authors: Cheng Ziyi , Wu Xiao , Zhang Yudong , Peng Wei , Zhu Mingfu , Liang Tianshui , Li Shijiao , Hao Yilin , Zhang Zheyuan , Wei Ronghan
Published: September 2024

This study uses molecular dynamics simulations to investigate the wetting behavior of water droplets on a gold substrate with annular grooves. The research finds that droplet size and substrate hydrophilicity similarly affect wetting behavior. Enhanced hydrophilicity changes the velocity trend of droplet contact line movement, while droplet size impacts the magnitude of velocity change. Contact angle fluctuations are observed and analyzed theoretically based on Young's equation. The results provide insights into the relationship between droplet dynamics and surface structure, contributing to a better understanding of wetting processes at the microscopic level.
Reversible Switching of Light‐Gated Organic Transistors Employing Dihydroazulene/Vinylheptafulvene Photo‐/Thermochromic Molecules
Authors: Gebel Sten , Aiboudi Oumaima , Grigorescu Vladimir , Ling Zhitian , Marszalek Tomasz , Blom Paul W. M. , Ramanan Charusheela , Lissel Franziska , Kraft Ulrike
Published: September 2024

An innovative possibility to introduce additional functionality to organic field‐effect transistors (OFETs) is to employ photochromic molecules, which undergo reversible isomerization under applied stimuli such as irradiation with specific wavelengths. As a result, the transistors not only can be switched on/off by the applied voltages, they can also be programmed by alternate triggers, such as light. Here, reversible switching of OFETs is presented by blending various dihydroazulene/vinylheptafulvene photoswitches into polythiophene‐based conjugated polymers. In result, the transfer characteristics of the transistors are altered significantly through UV irradiation. In contrast to current literature on different photoswitches such as spiropyrans or diarylethenes, the backreaction is induced thermally and not via visible light irradiation and reproducibly yields the pristine transistor characteristics. This reversible switching upon alternating UV irradiation and thermal annealing is quantified by figures of merit such as the magnitude of drain current, threshold voltage, and subthreshold swing. Irradiating the devices with different doses of UV light shows that the magnitude of switching directly depends on the respective UV dose, hence enabling a multi‐level electronic system. Furthermore, long‐term cyclability over 100 steps of repeated UV light exposure and thermal annealing is demonstrated.
Emerging Optoelectronic Devices for Brain‐Inspired Computing
Authors: Hu Lingxiang , Zhuge Xia , Wang Jingrui , Wei Xianhua , Zhang Li , Chai Yang , Xue Xiaoyong , Ye Zhizhen , Zhuge Fei
Published: September 2024

Brain‐inspired neuromorphic computing is recognized as a promising technology for implementing human intelligence in hardware. Neuromorphic devices, including artificial synapses and neurons, are regarded as essential components for the construction of neuromorphic hardware systems. Recently, optoelectronic neuromorphic devices are increasingly highlighted due to their potential applications in next‐generation artificial visual systems, attributed to their integrated sensing, computing, and memory capabilities. In this review, recent advancements in optoelectronic synapses and neurons are examined, with an emphasis on their structural characteristics, operational principles, and the replication of neuromorphic functions. For optoelectronic synaptic devices, such as memristor‐ and transistor‐based ones, attention is given to the two primary weight update modes: the light‐electricity synergistic mode and the all‐optical mode. Optoelectronic neurons are discussed in terms of different device types, including threshold switch neurons and semiconductor laser neurons. Last, the challenges that impede the progress of optoelectronic neuromorphic devices are identified, and potential future directions are suggested.
Electrical Sensing of Molecular Spin State Switching in a Spin Crossover Complex Using an Organic Field‐Effect Transistor
Authors: Zhang Yuteng , Alavi Seyed Ehsan , Soroceanu Ion , Kamau Dennis Wanyoike , Rotaru Aurelian , Séguy Isabelle , Salmon Lionel , Molnár Gábor , Bousseksou Azzedine
Published: September 2024

An organic semiconductor – spin crossover polymer composite heterostructure is fabricated, and it is integrated into an organic field‐effect transistor (OFET) with the aim to achieve electrical sensing of molecular spin state switching events. The OFETs display ≈50–70% increase in drain‐source current intensity when going from the low spin (LS) to the high spin (HS) state. This phenomenon is reversible without apparent fatigue and the application of a gate voltage significantly enhances the sensing sensitivity. Capacitance measurements and finite element calculations allow identifying mechanical stress, induced by the spin state switching, at the origin of the transistor response. These results open up appealing perspectives for the integration of spin crossover molecules into technological applications, such as soft robotics
.
Investigating TNNC1 gene inheritance and clinical outcomes through a comprehensive familial study
Authors: Patsalis Constantinos , Kyriakou Skevi , Georgiadou Michaella , Ioannou Lygia , Constantinou Louisa , Soteriou Valando , Jossif Antonis , Evangelidou Paola , Sismani Carolina , Kypri Elena , Ioannides Marios , Koumbaris George
Published: September 2024

Hypertrophic cardiomyopathy (HCM) and restrictive cardiomyopathy (RCM) have significant phenotypic overlap and a similar genetic background, both caused mainly by variants in sarcomeric genes. HCM is the most common cardiomyopathy, while RCM is a rare and often underdiagnosed heart condition, with a poor prognosis. This study focuses on a large family with four infants diagnosed with fatal RCM associated with biventricular hypertrophy. Affected infants were found to be homozygous for NM_003280.3(TNNC1):c.23C>T(p.Ala8Val) variant. Interestingly, this variant resulted in a low penetrance and mild form of hypertrophic cardiomyopathy (HCM) in relatives carrying a single copy of the variant. Overall, this study underscores the complex nature of genetic inheritance in cardiomyopathies and the wide range of clinical presentations they can exhibit. This emphasizes the vital role of genetic testing in providing essential insights crucial for diagnosis, prognosis, early intervention, and the development of potential treatment strategies.
Oxindolyl‐Based Radicals with Tunable Mechanochromic and Thermochromic Behavior
Authors: Xu Tingting , Han Yi , Ni Yong , Chi Chunyan
Published: September 2024

Organic radicals based dynamic covalent chemistry is promising in preparing stimuli‐responsive chromic materials, due to their simplicity of dissociation/association, accompanied with distinct color changes during the process. However, suitable organic radicals for dynamic covalent chemistry have not been widely explored yet. Herein, a series of oxindolyl‐based mono‐radicals (OxRs) with different substituents were successfully synthesized and studied systematically as potential building blocks for stimuli‐responsive chromic materials. These OxRs would dimerize spontaneously to form their corresponding dimers. The structures of dimers were unambiguously confirmed through low‐temperature 1H NMR and single‐crystal X‐ray diffraction analyses. Dynamic interconversion between monomers and dimers was achieved by reversible cleavage and recovery of the σ‐bond upon soft external stimuli (temperature, pressure, and solvent polarity), accompanied by significant color changes. It is interesting that the stability of the mono‐radical could be tuned through changing different substituents, and consequently altering the bond dissociation energy of the dynamic covalent bond between monomers. These new OxRs characterized by appreciable properties are entitled to more opportunities in developing mechanochromic and thermochromic materials, where their responsiveness to stimuli can be readily controlled by the substituents adhered.
Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones
Authors: Guan Jing , Luo Yicong , Wang Qiyuan , Chen Jianzhong , Zhang Wanbin
Published: September 2024

The asymmetric hydrogenation of benzophenones, catalyzed by low‐activity earth‐abundant metal copper, has hitherto remained a challenge due to the substrates equipped with two indistinguishably similar aryl groups. In this study, we demonstrated that the prochiral carbon of the ortho‐bromine substrate exhibits the highest electrophilicity and high reactivity among the ortho‐halogen substituted benzophenones, as determined by the Fukui function (f+) analysis and hydrogenation reaction. Considering that the enantiodirecting functional bromine group can be easily derivatized and removed in the products, we successfully achieved a green copper‐catalyzed asymmetric hydrogenation of ortho‐bromine substituted benzophenones. This method yielded a series of chiral benzhydrols with excellent results. The utility of this protocol has been validated through a gram‐scale reaction and subsequent product transformations. Independent gradient model based on Hirshfeld partition (IGMH) and energy decomposition analysis (EDA) indicate that the CH⋅⋅⋅HC multiple attractive dispersion interactions (MADI) effect between the catalyst and substrate enhances the catalyst's activity.
Immunoinformatic approach to design an efficient multi‐epitope peptide vaccine against melanoma
Authors: Dehghankhold Mahvash , Nezafat Navid , Farahmandnejad Mitra , Abolmaali Samira Sadat , Tamaddon Ali Mohammad
Published: September 2024

Melanoma is known to be the most hazardous and life‐threatening type of skin cancer. Although numerous treatments have been authorized in recent years, they often result in severe side effects and may not fully cure the disease. To combat this issue, immunotherapy has emerged as a promising approach for the prevention and treatment of melanoma. Specifically, the use of epitope melanoma vaccine, a subset of immunotherapy, has recently gained attention. The aim of this study was to create a multi‐epitope melanoma vaccine using immunoinformatic methods. Two well‐known antigens, NYESO‐1 and MAGE‐C2, were selected due to their strong immunogenicity and high expression in melanoma. To enhance the immunogenicity of the peptide vaccine, Brucella cell‐surface protein 31 (BCSP31), the G5 domain of resuscitation‐promoting factor B (RpfB) adjuvants, and the helper epitope of pan HLADR‐binding epitope (PADRE) were incorporated to vaccine construct. These different segments were connected with suitable linkers and the resulting vaccine structure was evaluated for its physicochemical, structural, and immunological properties using computational tools. The designed vaccine was found to have satisfactory allergenicity, antigenicity, and physicochemical parameters. Additionally, a high‐quality tertiary structure of the vaccine was achieved through modeling, refinement, and validation. Docking and molecular dynamics studies showed that the vaccine had a stable and appropriate interaction with the cognate TLR2 and TLR4 receptors during the simulation period. Finally, in silico immune simulation analysis revealed a significant increase in the levels of helper and cytotoxic T cells, as well as the cytokines interferon‐gamma and interleukin‐2, after repeated exposure to the melanoma vaccine. These results suggest that the designed vaccine has the potential to be an effective therapeutic option for melanoma. However, additional in vitro and in vivo validations are crucial to assess real‐world efficacy and safety.
Glyoxylic‐Acetal‐Based Gel‐Polymer Electrolytes for Lithium‐Ion Batteries
Authors: Leibing Christian , Muench Simon , Gómez Urbano Juan Luis , Schubert Ulrich S. , Balducci Andrea
Published: September 2024

This work focuses on the combination of two strategies to improve the safety of lithium‐ion batteries: The use of a glyoxylic‐acetal, 1,1,2,2‐tetraethoxyethane, in the solvent blend to reduce the flammability of the liquid electrolyte and further its confinement inside of a methacrylate‐based polymer matrix, to prevent electrolyte leakage from the battery cells. Physicochemical characterizations of this novel gel‐polymer electrolyte (GPE) confirm its improved thermal properties and suitable ionic conductivity, as well as electrochemical stability window. Tests in LFP and hard carbon half‐cells vs. lithium metal show that the combination of glyoxylic‐acetal‐based electrolyte and the methacrylate‐based polymer matrix can promote lithium‐ion intercalation and deintercalation with stable capacity values. The application in lithium‐ion battery full cells furthermore shows that the GPE can promote a similar performance compared to the respective liquid electrolyte and can therefore make possible the realization of energy storage devices with improved safety characteristics.
Impact of positive CD4 cells on event‐free survival in follicular lymphoma patients
Authors: Li Cong , Guo Na , Han Shuiyun , Yu Haifeng , Lei Tao , Chen Xi , Peng Shuailing , Yang Haiyan , Wu Meijuan
Published: September 2024

Objective

Previous results about prognostic value of CD4+ T cells in follicular lymphoma (FL) remain controversial.

Methods

Immunohistochemistry was used to examine expression of positive CD4 cells in 103 patients with FL 1‐3A. Early failure was described as failing to achieve event‐free survival (EFS) at 12 or 24 months.

Results

There were 49 (47.6%) male and 54 (52.4%) females, with a median age of 54 years. Compared to patients with <20% of positive CD4 cells, patients with ≥20% of positive CD4 cells exhibited a significant lower risk of early failure (2‐year EFS rate: 56.7% vs 73.5%, p = 0.047). When patients were stratified based on positive CD4 cell combined with FLIPI, the median EFS (p = 0.002) and median OS (p = 0.007) were significantly different.

Conclusions

This study demonstrated that higher expression of positive CD4 cells predicts lower risk of early failure in follicular lymphoma, and combination analysis of CD4 and FLIPI could better predict disease relapse and survival outcome.
Nomograms for predicting recurrence of HER2‐positive breast cancer with different HR status based on ultrasound and clinicopathological characteristics
Authors: Zhang Xudong , Kong Hanqing , Liu Xiaoxue , Li Qingxiang , Fang Xinran , Wang Junjia , Qin Zihao , Hu Nana , Tian Jiawei , Cui Hao , Zhang Lei
Published: September 2024

Purpose

This study aimed to identify ultrasound and clinicopathological characteristics related to recurrence in HER2‐positive (HER2+) breast cancer, and to develop nomograms for predicting recurrence.

Methods

In this dual‐center study, we retrospectively enrolled 570 patients with HER2+ breast cancer. The ultrasound and clinicopathological characteristics of hormone receptor (HR)−/HER2+ patients and HR+/HER2+ patients were analyzed separately according to HR status. Eighty percent of the original samples from HR−/HER2+ and HR+/HER2+ patients were extracted by bootstrap sampling as the training cohorts, while the remaining 20% were used as the external validation cohorts. Informative characteristics were screened through univariate and multivariable Cox regression in the training cohorts and used to develop nomograms for predicting recurrence. The predictive accuracy was calculated using Harrell's C‐index and calibration curves.

Results

Three informative characteristics (axillary nodal status, calcification, and Adler degree) were identified in HR−/HER2+ patients, and another three (histological grade, axillary nodal status, and echogenic halo) in HR+/HER2+ patients. Based on these, two separate nomograms were constructed to assess recurrence risk. In the training cohorts, the C‐index was 0.740 (95% CI: 0.667–0.811) for HR−/HER2+ nomogram, and 0.749 (95% CI: 0.679–0.820) for HR+/HER2+ nomogram. In the validation cohorts, the C‐index was 0.708 (95% CI: 0.540–0.877) for HR−/HER2+ group, and 0.705 (95% CI: 0.557–0.853) for HR+/HER2+ group. The calibration curves also indicated the excellent accuracy of the nomograms.

Conclusions

Ultrasound performance of HER2+ breast cancers with different HR status was significantly different. Nomograms integrating ultrasound and clinicopathological characteristics exhibited favorable performance and have the potential to serve as a reliable method for predicting recurrence in heterogeneous breast cancer.
Activin levels correlate with lymphocytic infiltration in epithelial ovarian cancer
Authors: Evans Elizabeth T. , Page Emily F. , Choi Alex Seok , Shonibare Zainab , Kahn Andrea G. , Arend Rebecca C. , Mythreye Karthikeyan
Published: September 2024

Objective

The TGF‐β superfamily member activin, a dimer of the gene products of INHBA and/or INHBB, has been implicated in immune cell maturation and recruitment, but its immune impact within epithelial ovarian cancer (EOC) is not well characterized. We sought to explore differences in activin (INHBA/ Inhibin‐βA and INHBB/ Inhibin‐βB) between malignant and ovarian tissues at the RNA and protein level and assess the relationship between activin and immune cells in EOC.

Methods

Publicly available RNA sequencing data were accessed from GEO (#GSE143897) with normalization and quantification performed via DESeq2. Immune gene expression profile was further explored within the TCGA‐OV cohort derived from The Cancer Genome Atlas (TCGA). Immunohistochemical analysis was performed to evaluate activin A and T‐cell markers CD8 and FoxP3 at the protein level. ELISA to activin‐A was used to assess levels in the ascites of advanced EOC patients. Kaplan–Meier curves were generated to visualize survival outcomes.

Results

Gene expression levels of components of the activin signaling pathway were elevated within EOC when compared to a benign cohort, with differences in activin type I/II receptor gene profiles identified. Additionally, INHBA gene expression was linked to lymphocytic immune markers in EOC samples. Immunohistochemistry analysis revealed a positive correlation of CD8 and FOXP3 staining with activin A at the protein level in both primary and metastatic epithelial ovarian cancer samples. Furthermore, Activin‐A (inhibin‐βA) is significantly elevated in EOC patient ascites.

Conclusion

INHBA expression is elevated within EOC, correlating with worse survival, with activin protein levels correlating with specific immune infiltration. Our findings suggest that activin‐A may play a role in suppressing anti‐tumor immunity in EOC, highlighting its potential as a therapeutic target.
The Mysterious World of Non‐Canonical Caps – What We Know and Why We Need New Sequencing Techniques
Authors: Mancini Flaminia , Cahova Hana
Published: September 2024

It was long believed that viral and eukaryotic mRNA molecules are capped at their 5′ end solely by the N7‐methylguanosine cap, which regulates various aspects of the RNA life cycle, from its biogenesis to its decay. However, the recent discovery of a variety of non‐canonical RNA caps derived from metabolites and cofactors — such as NAD, FAD, CoA, UDP‐glucose, UDP−N‐acetylglucosamine, and dinucleoside polyphosphates — has expanded the known repertoire of RNA modifications. These non‐canonical caps are found across all domains of life and can impact multiple aspects of RNA metabolism, including stability, translation initiation, and cellular stress responses. The study of these modifications has been facilitated by sophisticated methodologies such as liquid chromatography‐mass spectrometry, which have unveiled their presence in both prokaryotic and eukaryotic organisms. The identification of these novel RNA caps highlights the need for advanced sequencing techniques to characterize the specific RNA types bearing these modifications and understand their roles in cellular processes. Unravelling the biological role of non‐canonical RNA caps will provide insights into their contributions to gene expression, cellular adaptation, and evolutionary diversity. This review emphasizes the importance of these technological advancements in uncovering the complete spectrum of RNA modifications and their implications for living systems.
Naturally Occurring [4+2] Type Terpenoid Dimers Assembled through Unmatched‐electron‐demand Cycloaddition
Authors: Fu Shaomin , Liu Bo
Published: September 2024

Terpenoid dimers of the [4+2] type, which are naturally occurring compounds biosynthetically derived from the [4+2] cycloaddition of two precursors, have garnered considerable attention due to their complex molecular structures, diverse biological activities, and intriguing biosynthetic pathways. We have previously summarized the advancements in three types of [4+2] terpenoid dimers. In this review, we will focus on the lesser‐explored class of [4+2] terpenoid dimers which assembled from two electron‐deficient precursors via the unmatched‐electron‐demand Diels‐Alder reaction (UMEDDA). We will summarize their sources, biological activities, proposed biosynthesis, and chemical syntheses. Finally, a summary and outlook for this fascinating class of compounds will be presented.
Polyoxometalate Derived Materials as Laccase‐Mimic Nanozyme and Reduction Catalyst for p‐Nitrophenol Remediation in Water
Authors: Sun Ping , Xu Xinxin , Chen Jin
Published: September 2024

p‐Nitrophenol (PNP), a highly toxic water pollutant, poses significant risks to human health and the environment. For detecting PNP, a colorimetric method utilizing a nanozyme that mimics laccase activity presents a viable approach. In this study, PV14@MIL‐88A, a robust nanozyme with superior laccase‐mimic capabilities, was synthesized by incorporating Na7H2[PV14O42] (PV14) into MIL‐88A, a metal‐organic framework (MOF). This nanozyme demonstrates optimal laccase‐mimicking activity, enabling effective PNP detection via colorimetry and digital image colorimetry using smartphones. Theoretical analyses suggest that the outstanding laccase‐mimic activity of PV14@MIL‐88A is derived from the optimized d‐band center in PV14. Upon calcination with dicyandiamide (DCDA), PV14@MIL‐88A transforms into Fe2O3/VO2@NCNF. In the presence of NaBH4, Fe2O3/VO2@NCNF facilitates the conversion of PNP to p‐aminophenol (PAP), an essential precursor in paracetamol synthesis. The interaction between Fe2O3 and VO2 in Fe2O3/VO2@NCNF enhances adsorption and subsequent reduction of PNP. The saturation magnetization of Fe2O3/VO2@NCNF reaches 25 emu g−1, which supports efficient magnetic separation in the reduction process. This study not only advances an effective method for PNP detection but also facilitates its transformation from a hazardous pollutant into a valuable chemical precursor.
Quantum Effects Explain the Twist Angle in the Helical Structure of DNA
Authors: Jerbi Jihène , Fink Reinhold F. , Peña‐García Jorge , Arias‐Olivares David , Contreras‐García Julia , Cerón‐Carrasco José P.
Published: September 2024

Why are DNA bases stacked in a double helix structure? We combined three theoretical approaches to demonstrate how one core concept derived from quantum mechanics (Pauli repulsion) annihilates the contribution of dispersion to the π–π stacking. The helical architecture is governed by a combination of exchange and electrostatic forces, a result that is interpreted from both a computational and a biological perspective.
Cyclic Oxothiomolybdates: Building Blocks for Cyclodextrin‐Based Open Frameworks
Authors: Lion Maxence , Marrot Jérôme , Shepard William , Leclerc Nathalie , Haouas Mohamed , Cadot Emmanuel , Falaise Clément
Published: September 2024

Desolvation processes, though common in self‐assembled biological structures, are rarely evidenced and utilized in the design of crystalline architectures. In this study, we introduce a novel approach using the [Mo8S8O8(OH)8(guest)]2− complex, formed by the self‐condensation of four [MoV2O2S2]2− fragments around a guest unit (MoVIO6H4 or oxalate), as a chaotropic scaffold for crystallizing hybrid organic‐inorganic systems with natural cyclodextrins. Our findings reveal that β‐cyclodextrin (β‐CD) facilitates the formation of host‐guest complexes, while α‐cyclodextrin (α‐CD) induces the formation of a Kagome‐type structure with significant voids. These new compounds were thoroughly characterized using X‐ray diffraction (both powder and single‐crystal), N2 adsorption, elemental and thermogravimetric analysis. Additionally, solution studies using 1H NMR titration and small‐angle X‐ray scattering (SAXS) demonstrated pre‐association of the building units in solution. These results enhance our understanding of the design principles for supramolecular structures composed of inorganic polyanions and cyclodextrins.
A User‐Driven Framework for Dose Selection in Pregnancy: Proof of Concept for Sertraline
Authors: Koldeweij Charlotte , Dibbets Caroline , Franklin Bryony D. , Scheepers Hubertina C. J. , de Wildt Saskia N.
Published: September 2024

Despite growing knowledge of pregnancy‐induced changes in physiology that may alter maternal and fetal pharmacokinetics, evidence‐based antenatal doses are lacking for most drugs. Pharmacokinetic modeling and expanding clinical data in pregnancy may support antenatal doses. We aimed to develop and pilot a comprehensive and user‐driven Framework for Dose Selection in Pregnancy to support the clinical implementation of a best‐evidence antenatal dose for sertraline. After initial development and evaluation by experts, the framework prototype was piloted to formulate an antenatal dosing strategy for sertraline in depression and anxiety disorders. Next, the framework was reviewed and assessed for usability by a multidisciplinary working committee of end‐users comprising healthcare practitioners, experts from other disciplines including pharmacometrics, reproductive toxicology and medical ethics, alongside pregnant women and a partner. The resulting framework encompasses the following: rationale for drug selection, a comprehensive analysis of pharmacokinetic and dose‐related efficacy and safety data, and implementation aspects including feasibility and desirability of the recommended antenatal dose based on a structured maternal and fetal benefit–risk assessment. An antenatal dose recommendation for sertraline, as a case study, was formulated using this approach and endorsed for clinical use by the working committee. Future applications of the framework for other drugs can further demonstrate its suitability for developing best evidence, acceptable and clinically feasible antenatal doses.
Assessing the economic impacts of eco‐innovation strategies across contexts shaped by different institutional and structural pressures
Authors: Forés Beatriz
Published: September 2024

In the face of escalating environmental challenges, eco‐innovation (EI) has emerged as a crucial strategy for businesses aiming to balance ecological responsibility with economic and social performance. This study explores the impact of various EI strategies on the economic performance of firms, analyzing the contingent effect of both institutional and structural factors in dirty and clean industries. Using data from the Spanish Technological Innovation Panel (PITEC) spanning the period 2009–2016, our findings reveal that context matters for the effectiveness of EI strategies in enhancing economic performance. In stable environments with low institutional pressures, dirty industries benefit from R&D‐centric strategies, whereas in clean industries only efficiency‐centric and ambidextrous strategies yield economic gains. Similarly, in moderate institutional environments, the advantages offered by EI strategies hold for clean and dirty industries; however, ambidextrous EI strategies yield more economic advantages in both industry types. In dynamic environments, proactive strategies such as R&D‐centric and ambidextrous approaches are crucial for both dirty and clean industries. Firms in this situation should thus invest in assets and practices that enhance R&D for EI, as efficiency‐centric strategies are less effective in dynamic contexts. The findings have interesting implications for managers and policymakers, underlining the need for a nuanced approach to supporting and implementing EI initiatives.
Electrochemical Hydrodimerization of Lignocellulose‐Derived Carbonyls in Aqueous Electrolytes for Biobased Polymer and Long‐chained Synfuel Production: A Review
Authors: Kunkel Robin , Schmidt Volkmar M.
Published: September 2024

The transformation from fossil resources, crude oil and natural gas to biomass‐derived feedstocks is an urgent and major challenge for the chemical industry. The valorization of lignocellulose as renewable resource is a promising pathway offering access to a wide range of platform chemicals, such as vanillin, furfural and 5‐HMF. The subsequent conversion of such platform chemicals is one crucial step in the value‐added chain. The electrochemical hydrodimerization (EHD) is a sustainable tool for C−C coupling of these chemicals to their corresponding hydrodimers hydrovanilloin, hydrofuroin and 5,5′‐bis(hydroxymethyl)hydrofuroin (BHH). This review covers the current state of art concerning the mechanism of the electrochemical reduction of biobased aldehydes and studies targeting the electrochemical production of these hydrodimers in aqueous media. Moreover, the subsequent conversion of these hydrodimers to valuable additives, polymers and long carbon chain synfuels will be summarized offering a broad scope for their application in the chemical industry.
Boosting the O2‐to‐H2O2 Selectivity Using Sn‐Doped Carbon Electrocatalysts: Towards Highly Efficient Cathodes for Actual Water Decontamination
Authors: Zhao Lele , Mazzucato Marco , Lanzalaco Sonia , Parnigotto Mattia , Khan Anastassiya , Zitolo Andrea , Cabot Pere L. , Durante Christian , Sirés Ignasi
Published: September 2024

The high cost and often complex synthesis procedure of new highly selective electrocatalysts (particularly those based on noble metals) for H2O2 production are daunting obstacles to penetration of this technology into the wastewater treatment market. In this work, a simple direct thermal method has been employed to synthesize Sn‐doped carbon electrocatalysts, which showed an electron transfer number of 2.04 and outstanding two‐electron oxygen reduction reaction (ORR) selectivity of up to 98.0 %. Physicochemical characterization revealed that this material contains 1.53 % pyrrolic nitrogen, which is beneficial for the production of H2O2, and ‐C≡N functional group, which is advantageous for H+ transport. Moreover, the high volume ratio of mesopores to micropores is known to favor the quick escape of H2O2 from the electrode surface, thus minimizing its further oxidation. A purpose‐made gas‐diffusion electrode (GDE) was prepared, yielding 20.4 mM H2O2 under optimal electrolysis conditions. The drug diphenhydramine was selected for the first time as model organic pollutant to evaluate the performance of an electrochemical advanced oxidation process. In conventional electro‐Fenton process (pH 3), complete degradation was achieved in only 15 min at 10 mA cm−2, whereas at natural pH 5.9 and 33.3 mA cm−2, almost overall drug removal was reached in 120 min.
Electrooxidative Thiocyanation of Hydroxy‐ and Alkoxybenzenes
Authors: Moiseeva Natalia V. , Sokolov Aleksey E. , Andreev Ivan A. , Ratmanova Nina K. , Trushkov Igor V. , Kokorekin Vladimir A.
Published: September 2024

We developed an original method for thiocyanation of hydroxy‐ and alkoxy‐substituted benzenes (including naturally occurring compounds) using electrogenerated thiocyanogen, (SCN)₂. The presence of zinc chloride as a Lewis acid significantly enhances reaction efficiency by activating thiocyanogen. Cyclic voltammetry of the reactants and their combinations was employed to optimize reaction conditions and investigate the proposed mechanisms. This method demonstrated broad synthetic utility, leading to mono‐ and bis‐thiocyanated arenes and various heterocycles with yields 36–97 %. Notable products include the neuroprotective drug riluzole and precursors for the antiprotozoal drugs toltrazuril and ponazuril.
Preoperative measures of pain at rest and movement‐evoked pain in knee arthroplasty: Associations with pain and function outcome trajectories from a prospective multicentre longitudinal cohort study
Authors: Riddle Daniel L. , Dumenci Levent
Published: September 2024

Background

The study of pain at rest (PAR) and movement‐evoked pain (MEP) in persons with musculoskeletal pain has received substantial attention. Despite strong interest, relatively little attention has been directed to the psychometric development of these constructs. Our purpose was to explore the relationship between PAR and MEP and to examine the prognostic utility of these measures in persons with knee arthroplasty.

Methods

We used prospectively collected data from persons scheduled for knee arthroplasty who had moderate to high levels of pain catastrophizing. Preoperative latent variables for PAR and MEP were developed and used to determine if they were associated with a binary latent variable of good versus poor pain and function outcome trajectories. Factor correlations were used to determine the extent to which the variance for PAR and MEP was overlapping.

Results

PAR and MEP are significant predictors of good versus poor pain and function classes. Odds ratios ranged from 1.21 to 1.64 (p < 0.001) indicating a significant increase in the likelihood of poor outcome. Correlation between PAR and MEP latent variables was high (r = 0.89; 95% CI: 0.86–0.92) indicating substantially overlapping variance.

Conclusions

PAR and MEP, as defined in our study, can be used to make prognostic judgements regarding risk of poor postoperative outcome trajectory following knee arthroplasty. However, PAR and MEP showed substantially overlapping variance indicating that measurements of both are not necessary when making prognostic assessments.

Significance Statement

Preoperative PAR and MEP latent variables, as defined in our study, had prognostic significance for 1 year pain and function outcome trajectories. PAR and MEP latent variables had substantially overlapping variance which suggested that only one is needed to make prognostic judgements. The prognostic significance of PAR and MEP as well as their substantially overlapping variance is new to the field prognostic research in knee arthroplasty.