bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis and Properties of Covalently Linked Terpyridine‐BODIPY and Terpyridine‐3‐Pyrrolyl BODIPY Conjugates
Authors: Charan Behera Kanhu , Ravikanth Mangalampalli 
Published: December 2024

AbstractA series of covalently linked terpyridine‐BODIPY and terpyridine‐3‐pyrrolyl BODIPY conjugates were synthesized by strategically tuning the position of the terpyridine moiety at the α and/or meso positions of the BODIPY (3–4) and 3‐pyrrolyl BODIPY cores (5–7). These compounds were synthesized over a sequence of synthetic steps and their identities were confirmed by HR‐MS, 1D, 2D NMR, and X‐ray crystallography of one of the conjugates and studied by various spectroscopic, electrochemical, and theoretical techniques. The presence of terpyridine moieties on BODIPY and 3‐pyrrolyl BODIPY cores significantly alters their electronic properties and these conjugates absorb strongly in the 505–640 nm region. Furthermore, the α‐terpyridinyl 3‐pyrrolyl BODIPY conjugate was used as a ligand to form heteroleptic ruthenium(II/III) complexes. The Ru(II)/Ru(III) complexes exhibit weak fluorescence with significantly reduced quantum yield and single‐state lifetime due to the presence of a heavy Ru(II)/Ru(III) ion, which enhances spin‐orbit coupling and increases the rate of intersystem crossing (ISC), leading to non‐radiative relaxation. DFT and TD‐DFT studies corroborated our experimental findings, providing deeper insights into the structural, photophysical, and electronic properties of these conjugates.
Where and How: Stone Tool Sites of the Endangered Sapajus flavius in a Caatinga Environment in Northeastern Brazil
Authors: Rufino Maria Gabriella , da Silva José Jucimário , Souza‐Alves João Pedro 
Published: December 2024

ABSTRACTThe blonde capuchin monkey (Sapajus flavius) was, until a few years ago, an endemic primate of the Atlantic Forest. Today, populations inhabit the Caatinga dry forest and these have been documented using stone tools to access encased foods. It is important to know the distribution of these sites and the characteristics of the stone tools to inform conservation actions for this primate in the Caatinga. To this end, we identified and characterized stone tool sites used by a group of blonde capuchin monkeys in the Caatinga dry forest of northeastern Brazil. For 8 months, we walked two pre‐existing trails to georeference the stone tool use sites, to measure the dimensions and weight of the anvils and hammerstones, and to identify the food items processed at the sites. A total of 215 anvils and 247 hammerstones were mapped. The anvils were significantly longer than the hammerstones, while there was no difference in width. Most food remains found on the anvils were old (n = 101; 91%). Cnidoscolus quercifolius (n = 85; 77.3%) and Prunus dulcis (n = 25; 22.7%) were most common among the plant species found on the anvils. The width, thickness, and weight of hammerstones used to crack fruits of P. dulcis were significantly greater than those used to crack C. quercifolius. These results should be used as a baseline for the development of conservation actions for the species and habitat.
Atlas of Cerebrospinal Fluid Immune Cells Across Neurological Diseases
Authors: Heming Michael , Börsch Anna‐Lena , Melnik Simone , Gmahl Noemi , Müller‐Miny Louisa , Dambietz Christine , Fisch Lukas , Kühnel Timm , Brix Tobias J. , Janssen Alice , Schumann Eva , Gross Catharina C. , Varghese Julian , Hahn Tim , Wiendl Heinz , Meyer zu Hörste Gerd 
Published: December 2024

ObjectiveCerebrospinal fluid (CSF) provides unique insights into the brain and neurological diseases. However, the potential of CSF flow cytometry applied on a large scale remains unknown.MethodsWe used data‐driven approaches to analyze paired CSF and blood flow cytometry measurements from 8,790 patients (discovery cohort) and CSF only data from 3,201 patients (validation cohort) collected across neurological diseases in a real‐world setting.ResultsIn somatoform controls (n = 788), activation of T cells increased with age in both CSF and blood, whereas double negative blood T cells (CD3+CD4−CD8−) decreased with age. A machine learning model of CSF and blood immune cells defined immune age, which correlated strongly with true biological age (r = 0.71). Classifying all diseases solely based on the CSF/blood parameters in 8,790 patients resulted in clusters of 4 disease categories: healthy, autoimmune, meningoencephalitis, and neurodegenerative. This clustering was validated in an analytically independent test dataset (8,790 patients) and in a temporally independent cohort (3,201 patients). Patients with multiple sclerosis were more likely to have progressive disease when assigned to the neurodegeneration cluster and to have lower disability in the autoimmune cluster. Patients with dementia in the neurodegeneration cluster showed more severe disease progression. Flow cytometry helped differentiate dementia from controls, thereby enhancing the diagnostic power of routine CSF diagnostics.InterpretationFlow cytometry of CSF and blood thus identifies site‐specific aging patterns and disease‐overarching patterns of neurodegeneration. ANN NEUROL 2024
Spiro‐Fused vs 575‐Ringed Boron‐Doped Polycyclic π‐Systems: Selective Synthesis, Reactivity and Properties
Authors: Liu Yujia , Tian Xinyu , Li Zeyi , Zhang Tianyu , Yuan Liuzhong , Wang Yue , Dou Chuandong 
Published: December 2024

AbstractIncorporation of heteroatoms and/or non‐hexagonal rings into polycyclic aromatic hydrocarbons (PAHs) can alter their intrinsic structures and physical properties. However, it is challenging to construct PAHs featuring boron/carbon composition and non‐hexagonal combination. Herein, we disclose the selective synthesis of spiro‐type and pentagon/heptagon‐containing boron‐doped polycyclic π‐systems by the Scholl reaction. Two spiro‐fused organoboranes 1 and 2 and one 575‐ringed boron‐doped nanographene 3 were synthesized. The key point is that the boron‐edged π‐system enabled unexpected spiro‐formation via dearomatization, whereas the boron‐centered π‐system enabled desired 575‐ringed π‐extension via cyclodehydrogenation. The thus‐obtained molecules exhibit the intriguing but fully distinct reactivity, electronic structures and properties, for instance, while 2 may react with Brønsted acid to display reversible chemochromism and further convert into 1, 3 possesses very broad absorption, short excited‐state lifetime and no fluorescence nature. As disclosed, the boron atom together with the spirocycle region or 575‐ringed structural motif significantly contribute to their characteristic properties. Thus, this study sheds light on control over the Scholl reaction using organoborane π‐systems and will promote the exploration of more sophisticated polycyclic π‐systems as organic reactive and optical scaffolds.
3,6‐Bis(methylthio)‐9H‐carbazole Based Self‐Assembled Monolayer for Highly Efficient and Stable Inverted Perovskite Solar Cells
Authors: Ameen Shahid , Lee Dongmin , Faheem Abdullah Bin , Son Jung Geon , Lee Youngwan , Yoo Hyunjoon , Park Sujung , Shin Yun Seop , Lee Jaehwi , Seo Jongdeuk , Jang Hyungsu , Roe Jina , Song Ji Won , Cho Shinuk , Park Yongsup , Lee Kyung‐Koo , Kim Jin Young , Kim Dong Suk , Kim BongSoo 
Published: December 2024

AbstractThe photovoltaic performance of inverted perovskite solar cells (PSCs) relies on effectively managing the interface between the hole extraction layer and the light‐absorbing perovskite layer. In this study, we have synthesised (4‐(3,6‐bis(methylthio)‐9H‐carbazol‐9‐yl)butyl)phosphonic acid (MeS‐4PACz), which forms a self‐assembled monolayer (SAM) on the fluorine‐doped tin oxide (FTO) electrode. The molecule‘s methylthio substituents generate a favourable interfacial dipole moment and interact with the perovskite layer. This interaction results in well‐aligned energy levels among the FTO/SAM/perovskite layers, promoting efficient hole extraction and significantly reducing carrier recombination losses. Additionally, the methylthio groups passivate iodide vacancies and interact with Pb2+ ions of the perovskite, reducing defect‐induced trap states and enhancing the crystalline growth of the perovskite layer. Consequently, inverted PSCs incorporating MeS‐4PACz achieve a power conversion efficiency of 25.13 %, along with outstanding photostability.
Iridium(III) and Rhodium(III) Complexes With Imidazo[1,5‐a]pyridine‐Based Cyclometalating Ligands: Synthesis, Photophysical and Electrochemical Properties, and Catalytic Activities Toward the [4 + 2] Cycloaddition Reactions of Tertiary Anilines and Maleimides
Authors: Yang Xiaohan , Wang Biqin , Li Yahong 
Published: December 2024

ABSTRACTEighteen cationic iridium(III) (PC1–PC9) and rhodium(III) (PC10–PC18) complexes with a general formula [M(ppy)2(N^N)]+ (ppy = 2‐phenylpyridine; N^N = imidazo[1,5‐a]pyridine‐based ancillary ligands bearing different halogen atoms) were synthesized and characterized. The photophysical and electrochemical properties and catalytic activities of these complexes were investigated, and their properties were supported by density functional theory (DFT) calculations. The aims of this work were to study the influences of changes in the metal centers, the replacement of the pyridine ring by the pyrazine ring, the extension of the conjugation systems, and the attachment of different halogen atoms at the backbone of imidazo[1,5‐a]pyridine on the photophysical, electrochemical, and catalytic properties of PC1–PC18. It is found that the variation in the metal centers affected these properties the most. The experimental and calculated results revealed that the photophysical and electrochemical behaviors of iridium(III) complexes and rhodium(III) compounds are different. Upon photoexcitation, the iridium(III) complexes exhibited intense and long‐lived (6.96–13.03 μs) green to orange–red luminescence in acetonitrile at 298 K, and the emissions originated from 3ILCT transitions. The rhodium(III) complexes showed blue to green emissions with shorter excited‐state lifetimes (2.87–4.94 μs) than those of the iridium(III) complexes in acetonitrile. The emissions of the rhodium(III) complexes were attributed to 3MLCT or mixed 3MLCT/3ILCT/3LLCT transitions. All the complexes are catalytically active for the [4 + 2] cycloaddition reactions of tertiary anilines with maleimides, producing a series of tetrahydroquinoline derivatives.
Assessing the Reaction Kinetics and Solid Viscoelastic Behavior of Limonene Dioxide Epoxy Resin
Authors: Xavier Maurício Carpe Diem Ferreira , da Silva Fonseca Cristiane , Romanzini Daiane , Amico Sandro Campos , Petzhold Cesar Liberato , Bianchi Otávio 
Published: December 2024

ABSTRACTThis study examines the relationship between limonene dioxide's (LDO) curing degree and glass transition temperature with methyltetrahydrophthalic anhydride (MTHPA) and triethylamine. Using isothermal and non‐isothermal differential scanning calorimetry (DSC) analyses, the curing behavior and degree of conversion were mapped on a time–temperature‐transformation (TTT) diagram. At 50°C, the isothermal curing required approximately 1000 min to reach a significant conversion level, indicating a slow reaction rate for LDO. The curing process likely progresses in multiple stages. The initial stage, within 50°C–100°C, is a first‐order reaction with an activation energy of 63.3 kJ/mol. Subsequent stages involve reactions associated with the reactivity of cis‐LDO and trans‐LDO isomers, acting as parallel autocatalytic reactions with activation energies around 60 kJ/mol, increasing to 80 kJ/mol due to diffusion limitations. Viscosity and dynamic‐mechanical analyses were used to assess the viscoelastic properties of the cured polymer. The isomer mixture formed a resin with low crosslink density and thermoplastic behavior, limiting high‐temperature applications but aiding recyclability. This aligns with previous findings, noting the resin's low reactivity in its oxirane ring to nucleophilic opening.
Assessing Manufacturing‐Performance Correlation On LiMn0.7Fe0.3PO4 Electrodes For Application In Upscaled Li‐Ion Battery Cells
Authors: Minnetti Luca , Maddar Faduma M. , Haridas Anupriya K. , Capener Matthew , Nobili Francesco , Hasa Ivana 
Published: December 2024

AbstractOlivine LiMnxFe1−xPO4 (LMFP) cathodes are gaining attention as a promising alternative to LiFePO4 (LFP) for lithium‐ion batteries (LIBs), offering higher energy density while maintaining lower costs and improved safety compared to traditional layered oxide cathodes. However, their low electronic conductivity remains a challenge. One effective strategy to enhance electrode kinetics is incorporating carbon additives during fabrication. This study examines the role of conductive additive optimization in LiMn0.7Fe0.3PO4 (LMFP73) electrodes and evaluates the impact of refining the electrode manufacturing to improve performance under practical conditions. Electrodes with 0.5 % single‐walled carbon nanotubes (SWCNTs) dispersion demonstrated improved performance. Optimization of mixing protocol, solid content, and coating speed, significantly enhanced the electrode's microstructure, mechanical integrity, and electrochemical response, producing thick electrodes suitable for industrial use. Upscaling to Graphite|LMFP73 single‐layer pouch (SLP) cells with 200 g m−2 cathode loading resulted in 110 mAh g−1 at C/2, retaining 93 % of the initial capacity after 100 cycles. This work provides practical process parameters to reduce the gap between academic and industrial perspectives in electrode performance assessment under realistic conditions, tackling challenges in performance improvement while taking into account high areal loadings, mechanical properties of the coatings, practical electrode balancing, and electrolyte amount in the cell fabrication process.
Melatonin Attenuates PFOS‐Induced Reproductive Toxicity of Pregnant Mice due to Placental Damage Via Antioxidant, Anti‐Aging and Anti‐Inflammatory Pathways
Authors: Han Jianqiu , Lu Zhikai , Qi Yalei , Liu Tengfei , Li Yongmei , Han Honghui , Zhao Chen , Ma Xueyun 
Published: December 2024

ABSTRACTBackgroundPerfluorooctane sulfonate (PFOS), an industrially synthesized persistent organic pollutant (POP), is intricately intertwined with human production and daily life. It has been discovered that PFOS is related to an elevated incidence of birth defects in fetuses. In contrast, melatonin (MLT), a hormone secreted by the pineal gland, has been demonstrated to exert a protective effect on reproductive development.MethodsThis paper investigates the protective effect of MLT against PFOS‐induced reproductive toxicity by simultaneously orally administering MLT to pregnant mice exposed to PFOS. The therapeutic effect was evaluated through the monitoring of pregnancy outcomes, histological changes in the placenta, apoptosis and proliferation of placental spongiotrophoblast, as well as the expression of antioxidant enzyme genes, anti‐aging genes, anti‐inflammatory genes and other relevant genes.ResultsThe results of the study demonstrated that MLT treatment reversed the adverse pregnancy outcomes caused by toxic PFOS, including a low number of implanted fetuses, low neonatal fetal weight, and an increased number of resorbed fetuses. MLT treatment decreased the levels of MDA, an oxidation product generated by PFOS in the placenta of pregnant mice, and increased the levels of the antioxidant enzyme SOD. Additionally, MLT was able to maintain the normalization of placental structure, reduce apoptosis and sustain the proliferation of placental spongiotrophoblast by upregulating the expression of antioxidant genes (Nrf2, CAT) and anti‐aging gene (Klotho), anti‐inflammatory gene (Hsd11b2), thereby counteracting the oxidative stress caused by PFOS in the placenta, moreover, it also reduced the expression of inflammatory genes (Pycard) in the placenta.ConclusionsThe findings firmly establish the effectiveness of MLT in mitigating the harmful impacts of tainted PFOS on reproductive development during pregnancy. This provides a novel therapeutic approach for addressing PFOS‐induced birth defects in fetuses.
Observed Prevalence of Congenital Situs Inversus in the United States Before and During the SARS‐CoV‐2 Pandemic, 2017–2022
Authors: Cragan Janet D. , Cho Sook‐Ja , Forestieri Nina , Hort Michele , Nestoridi Eirini , Moore Cynthia A. , Stallings Erin , Gray Elizabeth B. , Reefhuis Jennita 
Published: December 2024

ABSTRACTBackgroundReports from China describe an increase in the frequency of fetal situs inversus in 2023 after the country's “zero‐Covid” policy was lifted, suggesting an association with maternal SARS‐CoV‐2 infection. However, a report of birth defects surveillance data from Scandinavia observed no sustained increase during the SARS‐CoV‐2 pandemic (2020–2022 vs. 2018–2019). We examined birth defects surveillance data to assess any increase in situs inversus in the U.S. during the SARS‐CoV‐2 pandemic.MethodsWe combined data from four population‐based birth defects programs in Massachusetts, Minnesota, North Carolina, and Atlanta, Georgia, to compare the prevalence of situs inversus among infants and fetuses delivered before (2017–2019) and during (2021–2022) the SARS‐CoV‐2 pandemic. We defined situs inversus as mirror‐image transposition of the heart and/or other organs, or primary ciliary dyskinesis with situs inversus, excluding isolated dextrocardia. The programs varied in the pregnancy outcomes included (live births ± non‐live births); all included both prenatal and postnatal diagnoses.ResultsWe identified 294 infants and fetuses with situs inversus (6.8% non‐live births). We estimated the combined prevalence per 10,000 live births as 1.72 during the pandemic versus 1.71 before the pandemic (OR = 1.005; 95% CI: 0.778–1.297). The estimated annual prevalence ranged from 1.41 in 2017 to 2.21 in 2019 with no significant trend across the study period (p = 0.39).ConclusionsWe did not observe an increase in situs inversus during the SARS‐CoV‐2 pandemic. Because information about SARS‐CoV‐2 infection among individual pregnancies was not available from all programs, we could not assess a specific association with maternal infection.
Combination of UHPLC‐QE‐MS and Network Pharmacology to Reveal the Mechanism of Fufang‐Duzhong‐Jiangu Granules for Treating Knee Osteoarthritis
Authors: Wang Weixiang , Luan Fei , Shi Yajun , Zhang Xiaofei , Guo Dongyan , Sun Jing , Zou Junbo , Yuan Puwei 
Published: December 2024

ABSTRACTUHPLC‐QE‐MS technology and network pharmacology are used to comprehensively analyze and validate the potential mechanism of Fufang‐Duzhong‐Jiangu granules (FFDZ) in treating knee osteoarthritis (KOA). UHPLC‐QE‐MS technology and content‐weighted construction of databases and screening conditions are used to obtain key component targets. CTD, Gene Cards, and DisGeNET databases are used to define KOA‐related targets. Target pathways are selected through GO enrichment analysis and KEGG enrichment analysis. Additionally, a KOA rat model was established using the type II collagenase injection method. The efficacy of FFDZ on type II collagenase‐induced KOA rats was evaluated through behavioral, biochemical, and histopathological assessments, and the predicted pathways were confirmed through Western blot. These results show that the rats significantly increased in knee joint diameter, decreased weight‐bearing capacity of the right leg, and elevated levels of IL‐6 and IL‐1β in serum, all with a significance level of p < 0.05. Through CT and HE staining, it was shown that KOA rats exhibit distinct pathological structures. These results show that FFDZ exerts its anti‐KOA effects by regulating the RAS pathway. This study found that FFDZ improves KOA in rats by inhibiting the expression of proteins related to the RAS pathway.
Mendelian Randomization Study Investigating the Causal Relationship Between Thyroid Dysfunction and Cerebral Infarction
Authors: Li Letai , Leng Jiajie , Xiong Haibing , Deng Zishan , Ye Meng , Wang Haiyan , Guo Xin , Zeng Shi , Xiong Haofeng , Huo Jianhong 
Published: December 2024

ABSTRACTBACKGROUNDThere is an association between thyroid dysfunction and cerebral infarction (CI), but the causality cannot be determined. A two‐sample two‐way Mendelian randomization (MR) study was conducted to assess the causal relationship between thyroid function and CI.METHODSWe selected single‐nucleotide polymorphisms (SNPs) associated with five phenotypes, including CI from the UK Biobank (n = 361,194), hyperthyroidism from the IEU Open GWAS database (n = 484,598), hypothyroidism from the IEU Open GWAS database (n = 473,703), normal thyroid‐stimulating hormone (TSH) (n = 271,040), and normal free thyroxine (FT4) (n = 119,120) from the Thyroidomics Consortium database. For the forward MR analysis, the exposures were hyperthyroidism, hypothyroidism, TSH, and FT4. The inverse variance weighted (IVW) method, weighted median (WM), and MR‐Egger revealed the causality with CI. For the reverse MR analysis, CI was regarded as the exposure, and four thyroid function phenotypes were the outcomes. The sensitivity and heterogeneity test was assessed using Cochran's Q test, MR‐Egger regression, and leave‐one‐out analysis.RESULTSThe MR analysis indicated that genetic susceptibility to hyperthyroidism increased the risk of CI (IVW‐OR = 1.070; 95% CI: 1.015–1.128; p = 0.003). In reverse MR, genetic susceptibility to RA is not associated with hyperthyroidism (IVW‐OR = 1.001; 95% CI: 1.000–1.001; p = 0.144). Any positive or reverse causal relationship between hypothyroidism, FT4, and TSH with CI could not be established. Sensitivity and heterogeneity test consolidated our findings.CONCLUSIONThe causality between CI and hyperthyroidism demonstrated patients with hyperthyroidism have a risk of genetic variants for CI. In the future, further studies are needed to fully explore their mechanisms of action.
lncRNA TCONS_00251376 promotes the proliferation and migration of gastric cancer cell through upregulating ETV1
Authors: Ren Dengfeng , Zhao Fuxing , Li Jinming , Guo Xinjian , Ma Xinfu , Zheng Yonghui , Shen Guoshuang , Zhao Jiuda 
Published: December 2024

AbstractBackgroundAlthough there have been significant advancements in the treatment modalities for gastric cancer (GC) in recent years, the overall prognosis remains poor, particularly for individuals in advanced stages. The absence of a sensitive tumor marker in GC is a crucial factor contributing to this challenge.MethodsOur study focused on investigating a newly discovered long noncoding RNA (lncRNA) known as TCONS_00251376, which has been confirmed to exhibit differential expression in GC compared to adjacent tissues. To further validate these expression differences, we collected 22 pairs of GC and adjacent noncancerous tissues. Subsequent cell function experiments and animal studies were conducted to elucidate the role and underlying mechanisms of lncRNA TCONS_00251376 in the development of GC.ResultsThe study revealed a significant upregulation of lncRNA TCONS_00251376 in cancer tissues (p < 0.01) and a consistent upregulation in GC cell lines (AGS, MKN45, BGC‐823, and MGC‐803). Furthermore, it was observed that lncRNA TCONS_00251376 played a promotive role in the proliferation, migration, and invasion of GC cells. Subsequent analysis indicated that lncRNA TCONS_00251376 could upregulate the expression of ETV1, a factor associated with the prognosis of GC.ConclusionsTherefore, our findings suggest that lncRNA TCONS_00251376 functions as an oncogenic lncRNA, promoting tumorigenesis and progression by regulating the expression of ETV1 gene. This highlights its potential as an effective target for treating GC.