bluuebunny/crossref_metadata_2025_split huggingface dataset:
Blockade of CCR5+ T Cell Accumulation in the Tumor Microenvironment Optimizes Anti‐TGF‐β/PD‐L1 Bispecific Antibody
Authors: Yi Ming , Li Tianye , Niu Mengke , Wu Yuze , Zhao Bin , Shen Zhuoyang , Hu Shengtao , Zhang Chaomei , Zhang Xiaojun , Zhang Jing , Yan Yongxiang , Zhou Pengfei , Chu Qian , Dai Zhijun , Wu Kongming 
Published: September 2024

AbstractIn the previous studies, anti‐TGF‐β/PD‐L1 bispecific antibody YM101 is demonstrated, with superior efficacy to anti‐PD‐L1 monotherapy in multiple tumor models. However, YM101 therapy can not achieve complete regression in most tumor‐bearing mice, suggesting the presence of other immunosuppressive elements in the tumor microenvironment (TME) beyond TGF‐β and PD‐L1. Thoroughly exploring the TME is imperative to pave the way for the successful translation of anti‐TGF‐β/PD‐L1 BsAb into clinical practice. In this work, scRNA‐seq is employed to comprehensively profile the TME changes induced by YM101. The scRNA‐seq analysis reveals an increase in immune cell populations associated with antitumor immunity and enhances cell‐killing pathways. However, the analysis also uncovers the presence of immunosuppressive CCR5+ T cells in the TME after YM101 treatment. To overcome this hurdle, YM101 is combined with Maraviroc, a widely used CCR5 antagonist for treating HIV infection, suppressing CCR5+ T cell accumulation, and optimizing the immune response. Mechanistically, YM101‐induced neutrophil activation recruits immunosuppressive CCR5+ T cells via CCR5 ligand secretion, creating a feedback loop that diminishes the antitumor response. Maraviroc then cleared these infiltrating cells and offset YM101‐mediated immunosuppressive effects, further unleashing the antitumor immunity. These findings suggest selectively targeting CCR5 signaling with Maraviroc represents a promising and strategic approach to enhance YM101 efficacy.
Synthesis of 1,2,3‐Triphospholenes, 1,2‐Diphosphetes, and Unsymmetric Phospholes by Rhodium‐catalyzed Cleavage of P−P Bonds and Addition to Alkynes
Authors: Arisawa Mieko , Otsuka Hiiro , Idogawa Tomoko , Sawahata Kyosuke , Kawai Yasutaka 
Published: September 2024

AbstractThe rhodium‐catalyzed addition reaction of cyclo‐(PPh)5 to alkynes in refluxing THF efficiently provide 1,2,3‐triphospholenes, in which the –PPh–PPh–PPh– group is transferred from cyclo‐(PPh)5 by the cleavage of P−P bonds. In refluxing chlorobenzene, the reactions are accompanied by the formation of 1,2‐diphosphetes. When the triphospholenes containing P−P bonds are reacted with reactive alkynes under rhodium‐catalyzed conditions, unsymmetric phospholes are obtained. The rhodium‐catalyzed reactions can be used to synthesize various phosphorus‐containing heterocycles with different numbers of phosphorus atoms.
Indole N‐Linked Hydroperoxyl Adduct of Protein‐Derived Cofactor Modulating Catalase‐Peroxidase Functions
Authors: Li Jiasong , Duan Ran , Traore Ephrahime S. , Nguyen Romie C. , Davis Ian , Griffth Wendell P. , Goodwin Douglas C. , Jarzecki Andrzej A. , Liu Aimin 
Published: September 2024

AbstractBifunctional catalase‐peroxidase (KatG) features a posttranslational methionine‐tyrosine‐tryptophan (MYW) crosslinked cofactor crucial for its catalase function, enabling pathogens to neutralize hydrogen peroxide during infection. We discovered the presence of indole nitrogen‐linked hydroperoxyl adduct (MYW‐OOH) in Mycobacterium tuberculosis KatG in the solution state under ambient conditions, suggesting its natural occurrence. By isolating predominantly MYW‐OOH‐containing KatG protein, we investigated the chemical stability and functional impact of MYW‐OOH. We discovered that MYW‐OOH inhibits catalase activity, presenting a unique temporary lock. Exposure to peroxide or increased temperature removes the hydroperoxyl adduct from the protein cofactor, converting MYW‐OOH to MYW and restoring the detoxifying ability of the enzyme against hydrogen peroxide. Thus, the N‐linked hydroperoxyl group is releasable. KatG with MYW‐OOH represents a catalase dormant, but primed, state of the enzyme. These findings provide insight into chemical strategies targeting the bifunctional enzyme KatG in pathogens, highlighting the role of N‐linked hydroperoxyl modifications in enzymatic function.
Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO2 Reduction to CnH2n+1OH (n=1, 2)
Authors: Li Pengyan , Qi Zhenhong , Yan Dongpeng 
Published: September 2024

AbstractEfficient synthesis of CnH2n+1OH (n=1, 2) via photochemical CO2 reduction holds promise for achieving carbon neutrality but remains challenging. Here, we present rare earth dual single atoms (SAs) catalysts containing ErN6 and NdN6 moieties, fabricated via an atom‐confinement and coordination method. The dual Er−Nd SAs catalysts exhibit unprecedented generation rates of 1761.4 μmol g−1 h−1 and 987.7 μmol g−1 h−1 for CH3CH2OH and CH3OH, respectively. Through a combination of theoretical calculation, XAFS analysis, aberration‐corrected HAADF‐STEM, and in‐situ FTIR spectroscopy, we demonstrate that the Er SAs facilitate charge transfer, serving as active centers for C−C bond formation, while Nd SAs provide the necessary *CO for C−C coupling in C2H5OH synthesis under visible light. Furthermore, the experiment and DFT calculation elucidate that the variety of electronic states induced by 4 f orbitals of the Er SAs and the p−f orbital hybridization of Er−N moieties enable the formation of charge‐transfer channel. Therefore, this study sheds light on the pivotal role of *CO adsorption in achieving efficient conversion from CO2 to CnH2n+1OH (n=1, 2) via a novel rare earth‐based dual SAs photocatalysis approach.
How Can Materials Chemists Contribute to Food Supply Security in the Age of AI and Robotics?
Authors: Cademartiri Ludovico 
Published: September 2024

AbstractGlobal factors are compromising the security of the food supply. Many of us in our community might be unsure about how to help with our seemingly inapplicable expertise. In this piece, I describe how materials chemistry and materials chemists will be essential in addressing this problem, but not only in the way we might think. There is a gigantic and largely unexplored opportunity for real societal impact if we accept a broader view of what academic materials chemistry can be.
Coupling Photocatalytic Hydrogen Production with Key Oxidation Reactions
Authors: Teng Jiayan , Li Wenlu , Wei Zhen , Hao Derek , Jing Lin , Liu Yuxi , Dai Hongxing , Zhu Yongfa , Ma Tianyi , Deng Jiguang 
Published: September 2024

AbstractHydrogen represents a clean and sustainable energy source with wide applications in fuel cells and hydrogen energy storage systems. Photocatalytic strategies emerge as a green and promising solution for hydrogen production, which still reveals several critical challenges in enhancing the efficiency and stability and improving the whole value. This review systematically elaborates on various coupling approaches for photocatalytic hydrogen production, aiming to improve both efficiency and value through different oxidation half‐reactions. Firstly, the fundamental mechanism is discussed for photocatalytic hydrogen production. Then, the advances, challenges, and opportunities are expanded for the coupling of photocatalytic hydrogen production, which focuses on the integration of value‐added reactions including O2 production, H2O2 production, biomass conversion, alcohol oxidation, and pollutants treatment. Finally, the challenges and outlook of photocatalytic H2 production technology are analyzed from the aspects of coupling hydrogen production value, photocatalyst design and reaction system construction. This work presents a holistic view of the field, emphasizing the synergistic benefits of coupled reactions and their practical application potential, rather than focusing on catalysts or single reaction systems. This review provides valuable references for the development and application of photocatalytic hydrogen production in energy conversion and environmental conservation through sustainable, eco‐friendly and economic pathways.
The effect of the modification mechanism of SiO2 in resin‐based friction materials on the mechanical and tribological performance
Authors: Zhao Yuncai , Gu Yanglang , Jiang Bingchun , Zou Yaoping , Wan Shaochen 
Published: September 2024

AbstractThis study aimed to address the thermal degradation of resin‐based friction materials in the mid‐temperature stage (200–250°C), as well as the resulting instability of the friction coefficient and decrease in the mechanical properties. To investigate the impact on the toughening and wear resistance properties, this study employed nanosilica‐modified resin‐based friction materials. The mechanical, friction, and wear properties of the modified samples were tested using a Rockwell hardness tester, hydraulic universal testing machine, and constant speed friction tester. The phase composition and microstructure of the samples were analyzed by scanning electron microscope, energy‐dispersive x‐ray spectroscopy, x‐ray diffraction. When the mass fraction of nanosilica was 3%, modified sample S3 exhibited excellent mechanical properties, with shear strength and compressive strength reaching 40.3 and 171.7 MPa, respectively, which were increased by 30% and 9% compared to unmodified sample S1. Moreover, the density and hardness of sample S3 showed minimal variation compared to those of unmodified sample S1. In the temperature range of 100–250°C, the wear rate of modified sample S3 remained within the range of 0.22 × 10−7–0.38 × 10−7 N−1 m−1, with a friction coefficient of 0.38 at 200°C, demonstrating excellent wear resistance.
Creation of Excitation‐Driven Hypervalent Tin(IV) Compounds For Aggregation‐Induced Emission and Application to Thermoresponsive Luminescent Films Below Freezing Point
Authors: Gon Masayuki , Shibahara Keisuke , Tanimura Kazuya , Tanaka Kazuo 
Published: September 2024

AbstractAlthough many researchers have devoted their much effort to establish the strategy for developing a stimuli‐responsive molecule and tuning of their properties according to the preprogrammed design, it is still challenging to create desired molecules from the scratch. We recently demonstrated that the molecules with a large structural difference between the theoretically optimized structures in the ground and excited states have a potential to exhibit stimuli‐responsive luminescent properties. We defined these molecules as an excitation‐driven molecule and have shown that they are a versatile platform for designing stimuli‐responsive luminescent molecules. Herein, based on the concept of excitation‐driven molecules, we show that the hypervalent tin‐fused azomethine (TAm) compounds possessing aggregation‐induced emission (AIE) properties can be obtained by simple chemical modification with a methyl group although conventional TAm derivatives are well known to be highly luminescent compounds in solution. Furthermore, by combining the solid‐state luminescence property of AIE and the coordination number shifts of the hypervalent tin atom, the thermoresponsive films operating below the freezing point are fabricated with the polymer. In this study, we apply the concept of excitation‐driven molecules to the hypervalent compounds and demonstrate to obtain the novel functional materials.
Computertomografie versus Optoanalytik: Bestimmung der Faserverteilung und ‐orientierung in stahlfaserbewehrtem UHFB
Authors: Heck Lennart , Schleiting Maximilian , Leutbecher Torsten 
Published: September 2024

AbstractFaserverteilung und ‐orientierung beeinflussen die Nachrisszugfestigkeit von stahlfaserbewehrtem ultrahochfestem Beton. Zu ihrer Bestimmung stehen verschiedene Verfahren zur Verfügung, darunter das optoanalytische Verfahren an Schnittflächen und die dreidimensionale Mikro‐Computertomografie (μCT). Mit beiden Verfahren können Einzelfasern in Querschnitten bzw. Volumen detektiert und daraus Lage und Ausrichtung der Fasern berechnet werden. Für den vorliegenden Beitrag wurden beide Verfahren vergleichend an drei Probenvolumen angewendet, bei denen der Größtkorndurchmesser und die Herstellmethode variierten. Ermittelt wurden die Faseranzahl, der Fasergehalt und die Faserorientierung durch Schnittflächenanalyse sowie in virtuellen Schnitten der rekonstruierten Volumenstruktur. Die μCT‐Analyse zeigte, dass sich der Fasergehalt für verschiedene Schnitte innerhalb eines Probenvolumens bereits auf kurzer Distanz deutlich unterscheiden kann. Des Weiteren wurden mittels μCT Effekte sichtbar, die auf einen Zusammenhang mit dem Größtkorndurchmesser schließen lassen. Der Vergleich der Ergebnisse beider Analyseverfahren ergab eine insgesamt gute Übereinstimmung. Für Fasern, die annähernd normal zur betrachteten Schnittebene orientiert waren, lieferte die optische Analyse tendenziell etwas zu niedrige Faserorientierungsbeiwerte, da der Querschnitt der in der Schnittfläche detektierten Faser als stärker elliptisch erkannt wurde.
Linking secretion and cytoskeleton in immunity– a case for Arabidopsis TGNap1
Authors: Bhandari Deepak D. , Brandizzi Federica 
Published: September 2024

AbstractIn plants, robust defense depends on the efficient and resilient trafficking supply chains to the site of pathogen attack. Though the importance of intracellular trafficking in plant immunity has been well established, a lack of clarity remains regarding the contribution of the various trafficking pathways in transporting immune‐related proteins. We have recently identified a trans‐Golgi network protein, TGN‐ASSOCIATED PROTEIN 1 (TGNap1), which functionally links post‐Golgi vesicles with the cytoskeleton to transport immunity‐related proteins in the model plant species Arabidopsis thaliana. We propose new hypotheses on the various functional implications of TGNap1 and then elaborate on the surprising heterogeneity of TGN vesicles during immunity revealed by the discovery of TGNap1 and other TGN‐associated proteins in recent years.
Identification and characterization of two new oxidation degradation impurities in cinnarizine through LC‐HRMS/MS and 1H NMR, along with in silico toxicity predictions of its degradation products
Authors: Jain Mohit , Khan Shahnawaz 
Published: September 2024

AbstractCinnarizine (CIN) drug substance is a US FDA and EMA approved antihistaminic drug, There is no report available on CIN for the identification of degradation products and their degradation pathway. Herein, we report a stability‐indicating assay method for CIN, the formation and characterization of its major degradation products using LC‐HRMS/MS and 1H‐NMR techniques. CIN was subjected to oxidation, acid, base, thermal and photolytic degradation conditions. Two unknown degradation products (DP‐1 and DP‐2) of CIN were formed under oxidative conditions. We successfully separated these degradants using gradient elution on an Inertsil ODS 3 V column (150 × 4.6 mm, 5 μm) using mobile phase A consisting of 0.1% formic acid and the mobile phase B consisting of 0.1% formic acid/acetonitrile (20/80, v/v). CIN was labile to oxidative conditions and stable to acidic, alkaline hydrolytic, photolytic and thermal conditions. The degradation pathways were derived from the nature of the product formed under oxidative degradation conditions and available reports for confirmation of the mechanism. Since the stability‐indicating assay method can be utilized for stability studies and routine quality control of CIN in both the pharmaceutical industry and research laboratories. This method has been validated in compliance with the guidelines set forth by the ICH.
Uncommon presentation of transitional cell carcinoma: A case report of hand involvement
Authors: Sanei‐Far Zahra , Gharib Masoumeh 
Published: September 2024

Key Clinical MessageIt is uncommon to see bladder cancer metastases in the hand. A 65‐year‐old man had bladder cancer surgery 3 years ago. His axilla and wrist swelled after surgery. Final amputation was necessary as the cancer had spread to hand. Transitional cell carcinoma was detected by immunohistochemistry with GATA‐3, CK7, CK20, and p63 positivity.
Ultrasound guided pulsed radiofrequency neuromodulation of sphenopalatine ganglion treatment for allergic rhinitis in childern: A case report
Authors: Geng Zeyang , Wang Chenyang , Wang Ruilin , Zhang Aimin 
Published: September 2024

Key Clinical MessageAllergic rhinitis (AR) is a chronic noninfectious inflammation of the nasal mucosa mediated primarily by allergen‐specific immunoglobulin E (IgE) in atopic individuals after exposure to allergens, with the involvement of non‐IgE‐mediated mechanisms and neuroimmune dysregulation. Conservative treatment of AR is ineffective in children who lack compliance, and traditional surgical procedures are risky, making treatment of this community challenging. The sphenopalatine ganglion (SPG), aka pterygopalatine ganglion, is the largest of the four parasympathetic ganglia located within the head region, existing as a bilateral pair. The fibers that arise from the SPG regulate secretomotor functions and provide sensation from various structures, including the lacrimal glands, the mucous membranes of the oropharynx, nasopharynx, nasal cavity, and upper portion of the oral cavity. Previous studies suggest that SPG plays a much crucial role in the neuro‐related pathophysiological mechanisms of AR. Pulsed radiofrequency (PRF) is a commonly used technique in pain management to produce neuromodulatory effects without damaging nerve tissue. Previous research suggests that SPG dysfunction is one of the important pathophysiological mechanisms of trigeminal autonomic cephalalgia, and PRF targeting SPG can effectively exert neuromodulatory effects to improve its symptoms. We thus predicted that the application of PRF for neuromodulation of SPG would be beneficial for symptom remission in AR. We report the first case of AR successfully treated with PRF targeting the SPG, symptoms did ameliorate during the 24‐week follow‐up period, as manifested by the disappearance of nocturnal open‐mouth breathing and its murmur and a significant reduction in the frequency and severity of daily episodes of nasal congestion, tearing, and conjunctival congestion, which diversifies clinical interventions for AR.
The Fabrication of ZIF‐L Derived Zns/Mos2@NC Anode Materials for Remarkable Lithium‐Ion Storage
Authors: Wang Jian , Zhang Baixue , Kang Kai , Li Peihua , Zhang Wanggang , Liu Yiming 
Published: September 2024

AbstractThe enhancement of electrochemical performance in lithium‐ion batteries can be achieved through the incorporation of MoS2 with carbon materials and various metal sulfides. In this study, a ZnS/MoS2 heterostructure was developed, featuring a two‐dimensional nitrogen‐doped carbon nanosheet (NC) backbone. The synthesis of ZnMoZIF−L precursors was accomplished by introducing a Mo source in a 1 : 1 molar ratio during the ZIF−L synthesis process. Following high‐temperature carbonization and vulcanization treatment, ZnS/MoS2@NC composite materials were successfully synthesized. Compared to the unvulcanized ZnO/MoO3@NC and MoS2 samples, the ZnS/MoS2@NC composite exhibits remarkable lithium storage performance. At a current density of 500 mA g−1, the initial reversible capacity capacity is still as high as 1674 mAh g−1. Furthermore, this composite material demonstrates optimal rate capabilities and a significant contribution to pseudocapacitance. The nitrogen‐doped carbon framework effectively mitigates volume changes, while the heterostructural design provides more active sites for lithium‐ions, thereby enhancing lithium storage performance.
3,3‐Difluorooxetane–A Versatile Functional Group for Bioisosteric Replacements in Drug Discovery
Authors: Liashuk Oleksandr S. , Fedinchyk Anastasiya , Melnykov Kostiantyn P. , Herasymchuk Maksym , Alieksieieva Diana , Lesyk Dmytro , Bas Yuliia P. , Keda Tetiana Ye. , Yatsymyrskiy Andriy V. , Holota Yuliia , Borysko Petro , Yarmolchuk Volodymyr S. , Grygorenko Oleksandr O. 
Published: September 2024

AbstractFunctional group (FG) is one of the cornerstone concepts in organic chemistry and related areas. The wide spread of bioisosterism ideas in medicinal chemistry and beyond caused a striking rise in demand for novel FGs with a defined impact on the developed compound properties. In this work, the evaluation of the 3,3‐difluorooxetane unit (3,3‐diFox) as a functional group for bioisosteric replacements is disclosed. A comprehensive experimental study (including multigram building block synthesis, quantification of steric and electronic properties, measurements of pKa, LogP, chemical stability, and biological evaluation of the 3,3‐diFox‐derived bioisostere of a drug candidate) revealed a prominent behavior of the 3,3‐diFox fragment as a versatile substituent for early drug discovery programs.
Evaluation of a Radioiodinated G‐Quadruplex Binder in Cervical Cancer Models
Authors: Cristina Oliveira ]Maria , Campello Maria Paula Cabral , Gano Lurdes , Raposinho Paula , Belchior Ana , Mendes Edgar , Silva Catarina D. , Lopes‐Nunes Jéssica , Cruz Carla , Paulo António 
Published: September 2024

AbstractWe herein describe the radiosynthesis of a 125I‐labeled acridine orange derivative ([125I]‐C8), acting as a G‐quadruplex binder, and its biological evaluation in cervical cancer models, aiming to enlighten its potential as a radioligand for Auger Electron Radiopharmaceutical Therapy (AE‐RPT) of cancer. [125I]‐C8 was synthesized with a moderate radiochemical yield (ca. 60 %) by a [125I]iodo‐destannylation reaction. Its evaluation in cervical cancer HeLa cells demonstrated that the radiocompound has a significant cellular internalization with a notorious accumulation in the cell nucleus. In line with these results, [125I]‐C8 strongly compromised the viability of HeLa cells in a dose‐dependent manner, inducing non‐repairable DNA lesions that are most probably due to the AEs emitted by 125I in close proximity to the DNA molecule. Biodistribution studies in a murine HeLa xenograft model showed that [125I]‐C8 has fast blood clearance and high in vivo stability but poor tumor uptake, after systemic administration. The respective supramolecular conjugate with the AS1411 aptamer ([125I]‐C8/AS1411) led to a slower blood clearance in the same animal tumor model, although without improving the tumor uptake. To take advantage of the radiotoxicity of [125I]‐C8 against cervical cancer cells other strategies need to be studied, based namely on alternative nanodelivery carriers and/or intratumoral injection approaches.
Elementary Steps of Catalytic Reactions Occurring on Metallic Alloy Nanoparticles
Authors: Zhdanov Vladimir P. 
Published: September 2024

AbstractCatalytic reactions running in an adsorbed overlayer on metallic alloy nanoparticles are of high interest in the context of applications in the chemical industry. The understanding of the corresponding kinetics is, however, still limited. One of the reasons of this state of the art is the interplay between adsorption and adsorbate‐influenced segregation of metal atoms inside alloy nanoparticles. I scrutinize this interplay by using a generic field model of segregation and the mean‐field approximation in order to describe adsorption, desorption, and elementary catalytic reactions. Under steady‐state conditions, the segregation is demonstrated to be manifested in the change of the dependence of the activation energies of desorption or elementary reactions on coverage, and the sign of this change is positive. The effect of this change on the apparent reaction orders is briefly discussed as well.