bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reactive Intermediate Confinement in Beta Zeolites for the Efficient Aerobic Epoxidation of α‐Olefins
Authors: Zhou Ziyu , Zhang Kun , He Peng , Chang Hongying , Zhang Min , Yan Tao , Zhang Xiangjie , Li Yongwang , Cao Zhi 
Published: December 2024

AbstractThe efficient conversion of long‐chain linear α‐olefins (LAOs) into industrially useful epoxides is of pivotal importance. Mukaiyama epoxidation based on the use of molecular oxygen as the sole oxidant and aldehyde as the cosubstrate offers a promising route for LAOs epoxidation. However, challenges associated with epoxide forming selectivity and aldehyde coupling efficiency have long impeded the adoption of Mukaiyama epoxidation in large‐scale applications. Herein, we show that confinement of key intermediates involved in the parallel epoxidation pathways within a Beta zeolite unlocks a selectivity of greater than 95 % towards the epoxides at the expense of minimal consumption of only 1.5 equivalents of the aldehyde, achieving an efficiency better than the state‐of‐the‐art homogeneous and heterogeneous catalysts. Moreover, the incorporation of Sn sites into the Beta zeolite framework further facilitates the adsorption activation process of the aldehyde cosubstrate, thereby increasing the concentration of acylperoxy radicals and accelerating the kinetic process of the epoxidation step. Consequently, this work not only provides an efficient and green epoxidation route over zeolite catalysts with easily available O2 as the oxidant, but also systematically reveals the fundamental understanding of the zeolite confinement effects on steering the reaction pathway, which benefits the further development of valorization of LAOs.
Gold‐Catalysed Intramolecular Reaction of Alkynes with Sulfoximines Acting as N‐ and O‐Transfer Reagents
Authors: Mackenroth Alexandra V. , Antoni Patrick W. , Shiri Farshad , Bendel Christoph , Mayer Christian , Gross Jürgen H. , Rominger Frank , Rudolph Matthias , Ariafard Alireza , Hashmi A. Stephen K. 
Published: December 2024

AbstractAmong the nucleophilic oxidants employed in the gold‐catalysed oxidation of alkynes, sulphur‐based reagents have played a substantial role since the beginning, granting access to the respective gold carbene intermediates. Herein, we describe the first example of the substance class of sulfoximines being used as atom transfer reagents to alkynes in gold catalysis. Based on the transformation of N‐(2‐alkynylphenyl) sulfoximines to 3H‐indol‐3‐ones, it is demonstrated that the sulfoximine functionality is capable of selectively transferring first its nitrogen moiety to the alkyne, forming the α‐imino gold carbene, which is then oxidised by the released sulfoxide moiety in a second step via a pseudo‐intramolecular mechanism—a distinctive feature that differentiates this work mechanistically from earlier studies. A combination of extensive experimental and theoretical studies provides evidence for this mechanistic rationale. As no external reagents for the 1,2‐difunctionalisation of the alkyne unit are required, a wide variety of functional groups are tolerated in the transformation, affording the desired 3H‐indol‐3‐ones in mostly good yields. It was further also showcased that it is possible to combine our methodology with additional transformations of the 3H‐indol‐3‐one core in one‐pot procedures, allowing facile access to C2‐quaternary indolin‐3‐one structures.
Palladium‐Imidazole Nanoparticles' Cytotoxic Effects on Colon Cancer Cells: Induction of Cell Cycle Arrest and Apoptosis Mediated via Mitochondria
Authors: Ismail Khaled M. , Hassan Safaa S. , Hanna Demiana H. 
Published: December 2024

ABSTRACTThe present study emphasized the potential antitumor activity of compound A; [Pd (Im)2Cl2], a nano‐sized coordination compound with a size of 23.76 nm. Characterization was performed using elemental analysis, molar conductance, magnetic measurement, FTIR, Ultraviolet–visible (UV–vis) spectroscopy, thermal analysis, mass spectrometry, and NMR. The complex showed stability up to 300°C. Furthermore, the compound's formation spontaneity was supported by activation parameters calculated from TGA. The di‐aqua form of the separated solid complex, compound B [Pd (Im)2(H2O)2]2+, was successfully prepared. The geometry optimization of imidazole and its complexes showed that both complexes were more stable than free imidazole. The cis di‐aqua form of [Pd (Im)2(H2O)2]2+ exhibits superior stability with a more potent IC50 value of 5.72±0.68 μg/mL. This form demonstrates greater inhibitory impacts on Caco‐2 cancer cell proliferation compared to [Pd (Im)2Cl2]. Moreover, the cytoxicity of [Pd (Im)2(H2O)2]2+ against Caco‐2 cells was confirmed by a significant increase in LDH levels in treated Caco‐2 cells compared to untreated ones. Treatment with [Pd (Im)2(H2O)2]2+ in Caco‐2 cells markedly raised the percentage of early and late apoptotic cells, accompanied by Go/G1 phase arrest with a more intense comet nucleus. Apoptosis induction in [Pd (Im)2(H2O)2]2+ treated cells was mediated through increased reactive oxygen species (ROS) production. Moreover, [Pd (Im)2(H2O)2]2+ markedly raised the expression levels of cleaved Caspase‐3, Bax, and P53 in treated Caco‐2 cells, while concurrently dropping the levels of Bcl‐2, cyclin D1, and CDK4. Overall, these findings indicate that [Pd (Im)2(H2O)2]2+ triggers significant cytotoxicity in Caco‐2 cancer cells in a dose‐dependent manner, primarily via ROS‐mediated cell death, possibly via the mitochondrial pathway. Additionally, the active species in selected proteins related to apoptosis and cell cycle arrest were explored and compared with theoretical molecular docking results. The outcomes also validated the safety of using [Pd (Im)2(H2O)2]2+ against healthy cells, suggesting it as a promising treatment option for colon cancer in humans.
Adsorption Optimization of VNi‐Layered Double Hydroxide Encapsulated With Chitosan and Carboxymethyl Cellulose for Rhodamine B Dye Removal From Aqueous Solutions: Adsorption Isotherm, Kinetics, and Thermodynamics
Authors: Abu‐Melha Sraa 
Published: December 2024

ABSTRACTIndustrial dye–contaminated wastewater needs creative techniques to effectively remove these contaminants. An easy co‐precipitation technique was used in this work to create the VNi‐layered double hydroxide (VNi‐LDH) adsorbent. VNi‐LDH was encapsulated with chitosan (CS) and carboxymethyl cellulose (CMC) that cross‐linked with itaconic acid as the cross linker via chemical crosslinking to form VNi‐LDH/CS‐CMC hydrogel beads. FT‐IR, SEM, XPS, BET, XRD, BET, and point of zero charge (pHzpc) were employed to characterize the prepared material. Examining VNi‐LDH/CS‐CMC's ability to remove rhodamine B (RB) from water waste as an adsorbent was the aim of the study. The highest adsorption capacity of RB on VNi‐LDH/CS‐CMC was found to be 653.8 mg/g. The research findings designated that the Langmuir isotherm models provided the most accurate representation of the RB adsorption procedure for VNi‐LDH/CS‐CMC. At a dosage of 0.8 g/L for the adsorbent and an equilibrium time of 100 min, it was established that the RB adsorption of VNi‐LDH/CS‐CMC hydrogel beads occurred at a pH of 8. The model of pseudo‐second order, demonstrating chemisorption with an adsorption energy of 30.34 kJ/mol along with a diffusion‐limited adsorption process, was most appropriate for the RB adsorption kinetics on VNi‐LDH/CS‐CMC hydrogel beads. The impact of temperature was also investigated, with an analysis of the thermodynamic variables (∆H°, ∆S°, and ∆G°) revealing a spontaneous increase in positive enthalpy and entropy charge, along with a decrease in ΔG°, as the temperature rose. The adsorption process outcomes were further optimized using response surface methodology (RSM) and the Box–Behnken design (BBD). It was proposed that the elimination of RB through VNi‐LDH/CS‐CMC may occur through different potential mechanisms, such as chemisorption, pore‐filling, π‐π bonding, electrostatic interactions, and hydrogen bonding. Given that the adsorbent was made of reusable materials and could be reused more than six times with high efficiency, the VNi‐LDH/CS‐CMC hydrogel beads offer a viable low‐cost option for removing RB dye from wastewater streams.
Two Stable Zn (II) Coordination Polymers as Dual‐Functional Luminescent Sensors for Efficient Detection of Nitrofurazone, Pefloxacin, and Cr2O72− in Water
Authors: Fan Xiao‐Fei , Cui Jia‐Ning , Cui Guang‐Hua 
Published: December 2024

ABSTRACTTwo new Zn (II) coordination polymers, {[Zn (OBA)(L)]·H2O}n (1) and {[Zn2(TCPA)2(L)2]·H2O}n (2), were synthesized under hydrothermal condition. Here, L = 2‐(1H‐imidazol‐1‐yl)methyl)‐5,6‐dimethyl‐1H‐benzo[d]imidazole, H2OBA = 4,4′‐dicarboxydiphenyl ether, H2TCPA = tetrachloroterephthalic acid. Structural analyses revealed that 1 exhibits a 2D hcb topology of {63} while 2 displays a four‐connected 2D sql layer with the point symbol of {44.62}. Both 1 and 2 are extended to 3D supramolecular frameworks through hydrogen bonding interactions. These CPs demonstrate remarkable thermal and chemical stability across a wide pH range of 3 to 12. Notably, they can serve as dual‐functional luminescent sensors for the sensitive, selective, and recyclable detection of nitrofurazone (NFZ)/Cr2O72− ions (for 1) and pefloxacin (PEF)/Cr2O72− ions (for 2) in aqueous solutions. The limits of detection (LODs) of 1 towards NFZ and Cr2O72− ions are 2.20 × 10−7 and 4.90 × 10−7 mol·L−1, respectively. For 2, the LOD is 5.42 × 10−8 mol·L−1 for PEF and 3.40 × 10−7 mol·L−1 for Cr2O72− ions. It is worth noting that this is the first report of luminescent Zn (II)‐CPs based on L ligands for the sensing of NFZ, PEF, and Cr2O72− ions. And the quenching mechanism was deeply investigated.
The MOF‐Derived Ag@M‐N/Al‐O Catalyst for Highly Selective Electrocatalytic Reduction of CO2 to CO
Authors: Liu Yichen , Zhao Zhongqin , Zhu Yanyan , Xiang Ruifang , Dong Xiuyan , Parvez Mohammad Khalid , Al‐Dosari Mohammed S. , Pan Ying 
Published: December 2024

ABSTRACTFor ensuring the economic feasibility of the electrochemical carbon dioxide reduction reaction (CO2RR), which can be used to reduce the catalyst load and increase the catalytic activity of CO2RR by using carrier materials. Here, we report the systematic alteration of metal chloride on bipyridine groups in MOF‐253(Al) using modified metal–organic frameworks (MOFs) as precursors and the introduction of Ag nanoparticles to prepare catalysts Ag@M‐N/Al‐O (M = Co, Ni, Zn, Cu). EDS spectra showed the uniform dispersion of Ag nanoparticles. In addition, the chemical structure of the catalyst was analyzed by XPS and PXRD, which proved the existence of M‐N and Al‐O bonds. The interaction with Ag nanoparticles leads to electron density reconstruction, and the stable *COOH intermediates with electron delocalization enhanced by polymetallic electron configuration modulation are conducive to CO production. The results show that Ag@Co‐N/Al‐O can achieve 85.6% FE for CO and has good stability within 12 h. This work provides a new idea for CO2RR material design using MOFs as a precursor catalyst.
Semi‐Stable Active Region Around the Co‐Rotation Latitude of Low‐Mass Close Binary KIC 7671594
Authors: Kaya N. Ö. , Dal H. A. 
Published: December 2024

ABSTRACTWe present the new findings from the light variation of KIC 7671594. We have analyzed the light curve of the system, which is likely a low‐mass eclipsing close binary. We have detected a spotted active region migration on the active component. This spotted active region on the stellar surface appears to be stable during the first 2.70 years, but it exhibits rapid migration during the last 0.85 years of the observing season. The OPEA model was derived using 1128 flares and their corresponding parameters. In the model, the value was found to be 2.46703 ± 0.25234 s, and the was calculated as 7332.28 s. The flare frequency was determined to be 0.03719 , while was found to be 0.00028. We have concluded that KIC 7671594 is likely a low‐mass eclipsing binary system with a main sequence component that possesses an active region covered by some cool spots around its co‐rotation latitude.
Nucleic acid‐templated chemical reactions for nucleic acid detection
Authors: Ryu Ji Young , Park Ha Yeong , Shin Hayeong , Kim Ki Tae 
Published: December 2024

AbstractNucleic acid‐templated reactions are chemical processes driven by the increased effective concentration of reactants on nucleic acids through the sequence‐specific hybridization of nucleic acids. Because these reactions translate the signals of target nucleic acids to detectable specific outputs, such as fluorescence, they can be applied for nucleic acid sensing and imaging. Owing to their advantageous features, such as signal amplification, isothermal nonenzymatic operation, and diverse reaction outputs and designs, the templated reactions have considerable potential for designing next‐generation nucleic acid sensors with high sensitivity, selectivity, rapidity, and user‐friendliness. Thus, over the past two decades, numerous templated reactions have been developed for more efficient nucleic acid detection. This review highlights recent advances in nucleic acid‐templated reactions since 2020, focusing on the newly developed reactions and strategies for designing highly sensitive, selective, and accurate nucleic acid sensing systems. We also summarize templated reaction research since 2015 and explore how integrating these reactions with other signal amplification systems and readout methods has led to the development of practical nucleic acid sensors with improved properties. According to the analysis of each type of templated reactions (ligation, releasing, and transformation), design trends are discussed that inform the outlook for the future development of nucleic acid sensors utilizing templated reactions.
Cancer situation in China: an analysis based on the global epidemiological data released in 2024
Authors: Diao Xiayao , Guo Chao , Jin Yukai , Li Bowen , Gao Xuehan , Du Xin , Chen Zhenchong , Jo Minju , Zeng Yi , Ding Chao , Liu Wenwu , Guo Jianrong , Li Shanqing , Qiu Haibo 
Published: December 2024

AbstractBackgroundCancer remains a major cause of mortality and a significant economic burden in China. Exploring the disparities in cancer patterns and control strategies between China and developed countries may offer valuable insights for policy formulation and enhance cancer management efforts. This study examined the incidence, mortality, and disability‐adjusted life year (DALY) burden of cancer in China, and compared these metrics with those observed in the United States (US) and the United Kingdom (UK).MethodsData on cancer incidence, mortality, and DALYs for China, the US, and the UK were sourced from the GLOBOCAN 2022 online database and the Global Burden of Disease 2021 study (GBD 2021). We utilized Joinpoint regression models to analyze trends in cancer incidence and mortality across these countries, calculating annual percent changes (APCs) and determining the optimal joinpoints.ResultsIn 2022, China recorded around 4,824,703 new cancer cases and 2,574,176 cancer‐related deaths, contributing to 71,037,170 DALYs. China exhibited a lower cancer incidence rate compared to the US and the UK. Although cancer‐related mortality in China is slightly lower than that in the UK, it is significantly higher than that in the US. Additionally, China experienced significantly higher DALY rates compared to both the US and UK. The cancer landscape in China was also undergoing significant changes, with a rapid rise in the incidence and burden of lung, colorectal, breast, cervical, and prostate cancers. Meanwhile, the incidence and burden of stomach cancer continued to decline. Although the incidence of liver and esophageal cancers was decreasing, the burden of liver cancer was increasing, while the burden of esophageal cancer remained largely unchanged.ConclusionsThe cancer profile of China is shifting from that of a developing country to one more typical of a developed country. The ongoing population aging and the rise in unhealthy lifestyles are expected to further escalate the cancer burden in China. Consequently, it is crucial for Chinese authorities to revise the national cancer control program, drawing on successful strategies from developed countries, while also accounting for the regional diversity in cancer types across China.
Fibroblast Growth Factor Receptor 4 Promotes Triple‐Negative Breast Cancer Progression via Regulating Fatty Acid Metabolism Through the AKT/RYR2 Signaling
Authors: Ye Jinhui , Wu Song , Quan Qiang , Ye Feng , Zhang Jinhui , Song Cailu , Fan Yidan , Cao Huijiao , Tang Hailin , Zhao Jianfu 
Published: December 2024

ABSTRACTBackgroundTriple‐negative breast cancer (TNBC) is the most aggressive subtype of breast cancer. Previous studies have found that fibroblast growth factor receptor 4 (FGFR4) plays a crucial role in tumor development and metastasis. However, the potential role and underlying mechanisms of FGFR4 in the progression of TNBC remain unclear.MethodsStatistical analysis of FGFR4 expression data in public databases was used to reveal its role in TNBC. qRT‐PCR was used to detect FGFR4 expression levels. The impact of FGFR4 level changes on TNBC cell proliferation was assessed using CCK‐8 and colony formation assays, while Transwell invasion assays and JC‐1 staining were employed to analyze the effects of FGFR4 level changes on the invasiveness and survival capability of TNBC cells. Differentially expressed genes were subjected to Gene Ontology, KEGG, and GSEA enrichment analyses to identify associated signaling pathways. Additionally, Oil Red O staining, fatty acid metabolite detection, and Western blot analysis were used to investigate the impact of FGFR4 and its inhibitor fisogatinib, as well as the AKT activator SC79, on the metabolic reprogramming of fatty acids in TNBC cells.ResultsFGFR4 was found to be upregulated in breast cancer and correlated with poorer patient outcomes. Inhibition of FGFR4 resulted in reduced cell growth and invasion in TNBC cells. It also led to increased lipid accumulation, upregulated lipid biosynthesis‐related genes, and downregulated lipolysis‐related genes. Mechanistically, FGFR4 inhibition suppressed the activation of the AKT/RYR2 signaling pathway. Reactivating the AKT pathway reversed the suppressive effects of FGFR4 inhibition on TNBC progression.ConclusionDysregulated FGFR4 activates the AKT/RYR2 axis, leading to tumor proliferation, invasion, and altered lipid metabolism in TNBC. FGFR4 inhibition could potentially serve as a novel therapeutic strategy for TNBC treatment.
Effective Antiviral Therapy Improves Immunosuppressive Activities in the Immune Microenvironment of Hepatocellular Carcinoma by Alleviating Inflammation and Fibrosis
Authors: Wang Zhu‐tao , Guan Ruo‐yu , Gan Wei , Yang Zhang‐fu , Sun Bao‐ye , Wu Jing‐fang , Zhang Dai , Sun Guo‐qiang , Gao Xu‐kang , Huang Jin‐long , Liu Gao , Zhou Cheng , Zhou Jian , Fan Jia , Yi Yong , Hu Bo , Qiu Shuang‐Jian 
Published: December 2024

ABSTRACTBackground and AimsThe immune microenvironment (IME) plays a crucial role in the progression of hepatocellular carcinoma (HCC). In HCC, the IME is often compromised by hepatitis B virus (HBV) infection, chronic inflammation, and fibrosis. Both antiviral therapy (AVT) and the alleviation of inflammation and fibrosis (AIF) have been shown to improve prognosis. However, the relationship among the IME of HCC, AVT, and AIF remains unclear.MethodsA total of 140 and 110 primary HBV‐related HCC patients were enrolled as training and validation sets, respectively, to establish a HCC‐immune microenvironment score (H‐IME score). Immunohistochemistry was performed to assess the number of granzyme B+ (GrB+) and Foxp3+ cells, as well as the expression of CTLA‐4, PD‐1, LAG3, TIGIT, TIM3, and VISTA. Another cohort consisting of 114 recurrent HBV‐related HCC patients with paired primary and recurrent tissues was used to study the relationship among the IME of HCC, AVT, and AIF.ResultsThe H‐IME score, including GrB, Foxp3, CTLA‐4, PD‐1, LAG3, and TIGIT, was established to evaluate the IME. A higher H‐IME score indicates stronger immunosuppressive activities. Both AVT and AIF were found to inhibit immunosuppressive activities in the IME. Compared to primary tumors, the H‐IME scores of recurrent tumors in the effective AVT group (e‐AVT, classified by HBV DNA) with AIF decreased, while the scores increased in the non‐AVT group without AIF.ConclusionsThe IME of HCC is closely related to AVT and AIF. e‐AVT can enhance anti‐tumor activities in the IME by alleviating inflammation and fibrosis.
Associations Between Oncology Outreach and Patient‐Sharing Measures of Care Coordination
Authors: Scodari Bruno T. , Schaefer Andrew P. , Kapadia Nirav S. , O'Malley A. James , Moen Erika L. 
Published: December 2024

ABSTRACTBackgroundOncology outreach is a common strategy for addressing cancer workforce shortages, where traveling oncologists commute across clinical settings to extend their services. Despite its known benefits specifically for rural patients, oncology outreach reallocates physician resources to satellite clinics and may negatively impact the coordination of cancer care.MethodsIn this retrospective study, we identified patients with incident breast, colorectal, and lung cancers from 2016–2019 nationwide Medicare claims and linked them to oncologists using Part B. We considered encounters occurring outside the physician's primary hospital service area as “outreach visits” and calculated the proportion of outreach visits by oncology specialty for contiguous US hospital referral regions (HRRs) using 2016–2017 claims. We constructed a nationwide physician patient‐sharing network from 2018–2019 claims and computed median care density—a measure of physician team familiarity—and local transitivity—a measure of physician cohesion/clustering—for each HRR as proxies for care coordination. Generalized linear models were used to explore the associations between oncology outreach and care coordination measures at the HRR level.ResultsWe found that HRRs with high medical oncology outreach were associated with 16% decreases in care density (95% CI: 5–25) and 4% decreases in local transitivity (95% CI: 1–8) compared to HRRs with low medical oncology outreach. HRRs with high radiation and surgical oncology outreach were not associated with network‐based measures of care coordination.ConclusionsWhile medical oncology outreach increases access for underserved patient populations, it potentially fragments care delivery across clinical settings. Health systems may consider this trade‐off to inform decisions concerning the implementation of outreach programs or policies aimed at hedging against fragmentation in markets with active outreach arrangements.