bluuebunny/crossref_metadata_2025_split huggingface dataset:
Methanesulfonic Acid‐Catalyzed Friedel‐Crafts Alkylation: Towards Sustainable Synthesis of Arylalkanes from Donor–Acceptor Cyclopropane Ketones
Authors: Goswami Lakshmi , Paul Sayantan , Mamale Ajay G. , Gonnade Rajesh G. , Bhattacharya Asish K. 
Published: April 2024

AbstractWe present herein Brønsted acid‐catalyzed Friedel‐Crafts alkylation of phenols with Donor–Acceptor cyclopropane ketones. The presence of the 1,4‐diphenyl butan‐1‐one and 1,3‐diphenyl propane‐1‐one motifs in various naturally occurring biologically significant molecules inspired us to pursue the direct synthesis of these structural frameworks. Utilizing methanesulfonic acid (MeSO3H) as a catalyst, we achieved a more environmentally friendly and high‐yielding synthesis, owing to its cost‐effectiveness, biodegradability, transition–metal and additives free conditions. Furthermore, we have successfully extended our developed methodology to thiophenols, resulting in the production of sulfur–based butan‐1‐one derivatives in good yields.
Racial discrimination during middle age predicts higher serum phosphorylated tau and neurofilament light chain levels a decade later: A study of aging black Americans
Authors: Simons Ronald L. , Ong Mei Ling , Lei Man‐Kit , Beach Steven R. H. , Zhang Yue , Philibert Robert , Mielke Michelle M. 
Published: April 2024

AbstractINTRODUCTIONRecent evidence suggests that exposure to the stress of racism may increase the risk of dementia for Black Americans.METHODSThe present study used 17 years of data from a sample of 255 Black Americans to investigate the extent to which exposure to racial discrimination predicts subsequent changes in serum Alzheimer's Disease Research Center (ADRC) biomarkers: serum phosphorylated tau181(p‐tau181), neurofilament light (NfL), and glial fibrillary acidic protein (GFAP). We hypothesized that racial discrimination assessed during middle age would predict increases in these serum biomarkers as the participants aged into their 60s.RESULTSOur findings indicate that exposure to various forms of racial discrimination during a person's 40s and early 50s predicts an 11‐year increase in both serum p‐tau181 and NfL. Racial discrimination was not associated with subsequent levels of GFAP.DISCUSSIONThese findings suggest that racial discrimination in midlife may contribute to increased AD pathology and neurodegeneration later in life.Highlights
A 17‐year longitudinal study of Black Americans.
Assessments of change in serum p‐tau181, neurofilament light, and glial fibrillary acidic protein.
Exposure to racial discrimination during middle age predicted increases in p‐tau181 and neurofilament light.
Education was positively related to both p‐tau181 and exposure to racial discrimination.
Controllable Skeletal and Peripheral Editing of Pyrroles with Vinylcarbenes
Authors: Yang Yong , Song Qingmin , Sivaguru Paramasivam , Liu Zhaohong , Shi Dan , Tian Tian , de Ruiter Graham , Bi Xihe 
Published: April 2024

AbstractThe skeletal editing of azaarenes through insertion, deletion, or swapping of single atoms has recently gained considerable momentum in chemical synthesis. Here, we describe a practical skeletal editing strategy using vinylcarbenes in situ generated from trifluoromethyl vinyl N‐triftosylhydrazones, leading to the first dearomative skeletal editing of pyrroles through carbon‐atom insertion. Furthermore, depending on the used catalyst and substrate, three types of peripheral editing reactions of pyrroles are also disclosed: α‐ or γ‐selective C−H insertion, and [3+2] cycloaddition. These controllable molecular editing reactions provide a powerful platform for accessing medicinally relevant CF3‐containing N‐heterocyclic frameworks, such as 2,5‐dihydropyridines, piperidines, azabicyclo[3.3.0]octadienes, and allylated pyrroles from readily available pyrroles. Mechanistic insights from experiments and density functional theory (DFT) calculations shed light on the origin of substrate‐ or catalyst‐controlled chemo‐ and regioselectivity as well as the reaction mechanism.
An Artificial Enzyme for Asymmetric Nitrocyclopropanation of α,β‐Unsaturated Aldehydes—Design and Evolution
Authors: Yu Ming‐Zhu , Yuan Ye , Li Zhen‐Jie , Kunthic Thittaya , Wang He‐Xiang , Xu Chen , Xiang Zheng 
Published: April 2024

AbstractThe introduction of an abiological catalytic group into the binding pocket of a protein host allows for the expansion of enzyme chemistries. Here, we report the generation of an artificial enzyme by genetic encoding of a non‐canonical amino acid that contains a secondary amine side chain. The non‐canonical amino acid and the binding pocket function synergistically to catalyze the asymmetric nitrocyclopropanation of α,β‐unsaturated aldehydes by the iminium activation mechanism. The designer enzyme was evolved to an optimal variant that catalyzes the reaction at high conversions with high diastereo‐ and enantioselectivity. This work demonstrates the application of genetic code expansion in enzyme design and expands the scope of enzyme‐catalyzed abiological reactions.
Anisotropic Semicrystalline Homopolymer Dielectrics for High‐Temperature Capacitive Energy Storage
Authors: Xu Wenhan , Zhou Chenyi , Ji Wenhai , Zhang Yunhe , Jiang Zhenhua , Bertram Florian , Shang Yingshuang , Zhang Haibo , Shen Chen 
Published: April 2024

AbstractHigh‐temperature dielectric polymers are in high demand for powering applications in extreme environments. Here, we have developed high‐temperature homopolymer dielectrics with anisotropy by leveraging the hierarchical structure in semicrystalline polymers. The lamellae have been aligned parallel to the surface in the dielectric films. This structural arrangement resembles the horizontal alignment of nanosheet fillers in polymer nanocomposites and nanosheet‐like lamellae in block copolymers, which has been proven to provide the optimal topological structure for electrical energy storage. The unique ordering of lamellae in our dielectric films endue a significantly increased breakdown strength and a reduced leakage current compared to amorphous films. This novel approach of enhancing the capacitive energy storage properties by controlled orientation of lamellae in homopolymer offers a new perspective for the design of high‐temperature polymer dielectrics.
Strategies for Achieving Ultra‐Long ORR Durability—Rh Activates Interatomic Interactions in Alloys
Authors: Li Xiaoke , Duan Xiao , Zhang Siao , Wang Chuanjie , Hua Kang , Wang Zejin , Wu Yongkang , Li Jia , Liu Jianguo 
Published: April 2024

AbstractThe stability of platinum‐based alloy catalysts is crucial for the future development of proton exchange membrane fuel cells, considering the potential dissolution of transition metals under complex operating conditions. Here, we report on a Rh‐doped Pt3Co alloy that exhibits strong interatomic interactions, thereby enhancing the durability of fuel cells. The Rh−Pt3Co/C catalyst demonstrates exceptional catalytic activity for oxygen reduction reactions (ORR) (1.31 A mgPt−1 at 0.9 V vs. the reversible hydrogen electrode (RHE) and maintaining 92 % of its mass activity after 170,000 potential cycles). Long‐term testing has shown direct inhibition of Co dissolution in Rh−Pt3Co/C. Furthermore, tests on proton exchange membrane fuel cells (PEMFC) have shown excellent performance and long‐term durability with low Pt loading. After 50,000 cycles, there was no voltage loss at 0.8 A cm−2 for Rh−Pt3Co/C, while Pt3Co/C experienced a loss of 200 mV. Theoretical calculations suggest that introducing transition metal atoms through doping creates a stronger compressive strain, which in turn leads to increased catalytic activity. Additionally, Rh doping increases the energy barrier for Co diffusion in the bulk phase, while also raising the vacancy formation energy of the surface Pt. This ensures the long‐term stability of the alloy over the course of the cycle.
Enhanced mechanical qualities of sericin‐removed silk by direct feeding of silkworms with cellulose nanofiber
Authors: Kobayashi Genki , Kurita Hiroki , Nagasawa Atsuhiko , Hori Masatoshi , Narita Fumio 
Published: April 2024

AbstractRecently, the modification of silkworm silk fibers (SFs) by adding fillers has been investigated. Previously, we have reported that SFs obtained from silkworms fed diets supplemented with 5 wt.% cellulose nanofiber (CNF) and whose surface was covered with sericin exhibited excellent tensile properties. On the other hand, to use SF in silk products, the sericin must be removed, and it is necessary to ensure that CNF‐enriched silkworm SFs with the sericin removed (i.e., fibroin) exhibit high tensile properties. Therefore, this study evaluated the tensile properties of sericin‐removed SF obtained from silkworms fed a CNF diet. The results showed that the average CNF with SF—near 7.5 wt.% exhibited high mechanical properties. Adding CNF to the silkworm diet did not affect their growth and cocoon yield. The analysis of the SF microstructure confirmed that CNF is a fibrous material on the surface of fibroin. Kelly‐Tyson's equation suggested that almost all of the CNF in fibroin contributed to the increased tensile strength.
Flame retardant polyurethane microbubble elastomer based on ionic liquid/ammonium polyphosphate/aluminum hypophosphite ternary flame retardant system
Authors: Liu Kai , Gao Xingtong , Liu Zhiyuan , Hu Wenjin , Li Aixiang , Xu Yanjun , Zhang Wenjie 
Published: April 2024

AbstractTo develop a highly efficient flame retardant system for polyurethane microbubble elastomer (PME), a phosphate‐based ionic liquid (IL) 1‐methyl‐3‐(dioxyphosphoryl)‐propyl imidazole bromide was synthesized, and then combined with ammonium polyphosphate (APP) and aluminum hypophosphate (ALHP) to form a ternary flame retardant system, which shows excellent synergistic flame retardancy and plays an important role in both gas phase and condensed phase flame retardancy. Compared with pure PME, the limiting oxygen index of flame retardant PME with 6 wt% IL and 15 wt% APP/ALHP increased from 20.25% to 29.25%, the char yields is increased by 13 times, and the heat release rate, total heat release rate, mass loss rate, and smoke production rate are reduced by 74%, 19%, 67%, and 22%, respectively. Ignition time increased from 9 s to 19 s, and extinguishing time increased from 295 s to 573 s. At the same time, the addition of IL promoted the dispersion and compatibility of APP/ALHP in the PME matrix and improved the mechanical properties. In addition, IL also shows potential in antistatic modification, providing the possibility for materials to meet both flame retardant and antistatic requirements.
Effect of polyphenylene sulfide sulfone sizing agent on interfacial, thermal, and mechanical properties of carbon fiber
Authors: Zhuang Yifan , Liu Haibin , Zhou Shaoyang , Jia Zhehao , Sun Ying 
Published: April 2024

AbstractPolyphenylene sulfide sulfone (PPSS) was synthesized by one‐step method and utilized as a sizing agent for carbon fibers. The effects of various monomer ratios, reaction time, and reaction temperature were investigated on the molecular weight of PPSS. The thermal analysis revealed that the product PPSS exhibited a glass transition temperature exceeding 215.5°C, indicating exceptional thermal stability. After PPSS sizing treatment, the grooves on the surface of carbon fibers were filled, resulting in a substantial enhancement of the microinterface properties. The surface energy was increased by 8.2%, while the maximum weight loss temperature was 27.8% higher than that of the commercial carbon fiber. The tensile strength of the carbon fiber after heat treatment reached 2196 MPa, representing a 45.9% increase over that of the commercial carbon fiber.
Ambient Temperature Metal‐Free Thiomethylation of Chloroheteroarenes and Chloropurines
Authors: Patel Manisha A. , Vora Raj K. , Sanghvi Yogesh S. , Kapdi Anant R. 
Published: April 2024

AbstractHerein, we report an in‐situ mild and metal‐free protocol for thiomethylation of heteroarenes in high yields. The thiomethylation of various chloropurines, nucleosides, and chloroheteroarenes has been accomplished offering easy access to agrochemicals and synthetic molecules useful for drug discovery.
Novel definition of textbook outcome in biliary system cancers and its influence on patients' survival and quality of life
Authors: Atyah Manar Mikhail , Xu Li , Yang Zhiying 
Published: April 2024

AbstractBackgroundThe definition of textbook outcome in biliary system cancers is a developing concept in need of expansion and investigation of its association with survival and quality of life.MethodsIn this original research, we developed a novel “all or none” textbook outcome definition which addresses the rapid recovery of post‐surgical indexes, in addition to short‐term mortality, hospital re‐admission, prolonged stay, surgical margin and postoperative complications. Based on the fulfillment of relevant criteria, patients were divided into textbook outcome and non‐textbook outcome groups and their characteristics and survival data were analyzed. A customized “quality of life” questionnaire was developed to address short‐term recovery and post‐discharge life quality of patients. Association with quality of life improvement was then investigated.ResultsA total of 129 patients were included. Textbook outcome was achieved in 25.58% of patients (37.04% of gallbladder cancer patients and 17.8% of cholangiocarcinoma patients). Compared to non‐textbook outcome group, patients with textbook outcome had lower rate of pre‐operative biliary drainage (p = 0.026), higher rate of normal preoperative liver function (p < 0.001) and tumor markers (p = 0.001), reduced perioperative bleeding (p = 0.006) and blood transfusion (p = 0.005), and higher rate of N0 stage cases (p = 0.008). Textbook outcome was also associated with enhanced survival, significantly in older patients (<65 years) (1‐year survival rate: 100% vs. 78.57% (p = 0.108), 2‐year survival rate: 87.5% vs. 44% (p = 0.046)). Finally, textbook outcome was significantly associated with enhanced basic daily performance (p < 0.001), social life performance (p = 0.033), and personal evaluation (p < 0.001), and thus improved quality of life (p < 0.001).ConclusionsThe novel definition of textbook outcome was able to address the specific nature of recovery after resection of biliary system cancers. Expanding the scope of textbook outcome and addressing the influence on survival and quality of life provides a comprehensive concept able to reflect physical, psychological and functioning enhancements in patients recovery.
A Rhodanese‐Like Enzyme that Catalyzes Desulfination of Ergothioneine Sulfinic Acid
Authors: Nalivaiko Egor Y. , Seebeck Florian P. 
Published: April 2024

AbstractMany actinobacterial species contain structural genes for iron‐dependent enzymes that consume ergothioneine by way of O2‐dependent dioxygenation. The resulting product ergothioneine sulfinic acid is stable under physiological conditions unless cleavage to sulfur dioxide and trimethyl histidine is catalyzed by a dedicated desulfinase. This report documents that two types of ergothioneine sulfinic desulfinases have evolved by convergent evolution. One type is related to metal‐dependent decarboxylases while the other belongs to the superfamily of rhodanese‐like enzymes. Pairs of ergothioneine dioxygenases (ETDO) and ergothioneine sulfinic acid desulfinase (ETSD) occur in thousands of sequenced actinobacteria, suggesting that oxidative ergothioneine degradation is a common activity in this phylum.
In‐Situ Investigations of Polyoxometalate‐Catalysed Biomass Oxidation to Formic Acid by Using Multinuclear High Resolution Flow NMR Spectroscopy
Authors: Krueger Jan‐Dominik H. , Poller Maximilian J. , Lyall Catherine , Lowe John , Hintermair Ulrich , Albert Jakob 
Published: April 2024

AbstractBiomass valorisation over polyoxometalate‐based (POM) catalysts is a promising strategy for green and sustainable chemistry. In order to further improve such processes e. g. by using different additives, a better understanding of the chemical influence of various additives on the catalyst is paramount. The main objective of this study is to gain a deeper understanding of the effects caused by various additives on the catalytically active vanadium species in the selective aerobic oxidation of carbohydrates to formic acid (esters). After carefully choosing a suitable model system, the oxidation of glycolaldehyde using the heteropolyacid H5PV2Mo10O40 (HPA‐2) as a catalyst was studied in situ by Flow Nuclear magnetic resonance (FlowNMR) spectroscopy. These measurements allowed to identify the catalytically active isomer of the HPA‐2‐catalyst and to observe the influence of additives on the reaction kinetics in situ. These findings provide a good basis for further improving POM‐based catalytic aerobic oxidation of biomass.
A Fluorination Strategy and Low‐Acidity Anchoring Group in Self‐Assembled Molecules for Efficient and Stable Inverted Perovskite Solar Cells
Authors: Sun Xiaowen , Fan Hua , Xu Xiaowei , Li Gongqiang , Gu Xiaoyu , Luo Dou , Shan Chengwei , Yang Qiong , Dong Shixing , Miao Chunyang , Xie Zheng , Lu Gang , Wang Dong Hwan , Sun Ping‐Ping , Kyaw Aung Ko Ko 
Published: April 2024

AbstractHerein, we synthesized two donor‐acceptor (D‐A) type small organic molecules with self‐assembly properties, namely MPA‐BT‐BA and MPA‐2FBT‐BA, both containing a low acidity anchoring group, benzoic acid. After systematically investigation, it is found that, with the fluorination, the MPA‐2FBT‐BA demonstrates a lower highest occupied molecular orbital (HOMO) energy level, higher hole mobility, higher hydrophobicity and stronger interaction with the perovskite layer than that of MPA‐BT‐BA. As a result, the device based‐on MPA‐2FBT‐BA displays a better crystallization and morphology of perovskite layer with larger grain size and less non‐radiative recombination. Consequently, the device using MPA‐2FBT‐BA as hole transport material achieved the power conversion efficiency (PCE) of 20.32 % and remarkable stability. After being kept in an N2 glove box for 116 days, the unsealed PSCs’ device retained 93 % of its initial PCE. Even exposed to air with a relative humidity range of 30±5 % for 43 days, its PCE remained above 91 % of its initial condition. This study highlights the vital importance of the fluorination strategy combined with a low acidity anchoring group in SAMs, offering a pathway to achieve efficient and stable PSCs.
Protocol: Interventions aimed at preventing out‐of‐home placement of children: A systematic review
Authors: Dalgaard Nina Thorup , Bondebjerg Anja , Bengtsen Elizabeth , Dietrichson Jens , Bach‐Mortensen Anders 
Published: April 2024

AbstractThis is the protocol for a Campbell systematic review. The objectives are as follows. The aim of the present review is to synthesize evidence on the effectiveness of interventions for at‐risk families aimed at preventing the out‐of‐home placement of children or increasing the likelihood that children are reunited with their birth families following temporary care arrangements. The review has two objectives: (1) To assess the effectiveness of interventions for at‐risk families with children aged between 0 and 17 years old on measures of out‐of‐home placement and on secondary outcomes. (2) To identify factors that modify intervention effectiveness (e.g., prior placements, parental risk factors such as substance abuse, mental health issues, age, minority status, child risk factors such as disabilities, age, and gender).
Chemical Derivatization Leads to the Discovery Of Novel Analogs of Azotochelin, a Natural Siderophore, as Promising Anticancer Agents
Authors: Karadkhelkar Nishant M. , Gupta Pranav , Barasa Leonard , Chilamakuri Rameswari , Hlordzi Christopher K. , Acharekar Nikita , Agarwal Saurabh , Chen Zhe‐Sheng , Yoganathan Sabesan 
Published: April 2024

AbstractSiderophores are structurally unique medicinal natural products and exhibit considerable therapeutic potential. Herein, we report the design and synthesis of azotochelin, a natural siderophore, and an extensive library of azotochelin analogs and their anticancer properties. We modified the carboxylic acid and the aromatic ring of azotochelin using various chemical motifs. We evaluated the cytotoxicity of the compounds against six different cancer cell lines (KB‐3‐1, SNB‐19, MCF‐7, K‐562, SW‐620, and NCI−H460) and a non‐cancerous cell line (HEK‐293). Among the twenty compounds tested, the IC50 values of nine compounds (14, 32, 35–40, and 54) were between 0.7 and 2.0 μM against a lung cancer cell line (NCI−H460). Moreover, several compounds showed good cytotoxicity profile (IC50 <10 μM) against the tested cancer cell lines. The flow cytometry analysis showed that compounds 36 and 38 induced apoptosis in NCI−H460 in a dose‐dependent manner. The cell cycle analysis indicated that compounds 36 and 38 significantly arrested the cell cycle at the S phase to block cancer cell proliferation in the NCI−H460 cell line. The study has produced various novel azotochelin analogs that are potentially effective anticancer agents and lead compounds for further synthetic and medicinal chemistry exploration.
How the Milan System for Reporting Salivary Gland Cytopathology works in cytopathology practice: Meta‐analysis of prospective studies and comparison with retrospective studies
Authors: Lagerstam Henri , Kalfert David , Maleki Zahra , Kholová Ivana 
Published: April 2024

AbstractBackgroundThe Milan System for Reporting Salivary Gland Cytopathology (MSRSGC) is widely accepted and endorsed by professional societies. Although several studies focusing on the MSRSGC have been published, few have been prospective studies. The objective of this study was to evaluate the effectiveness of the MSRSGC in cytopathology practice.MethodsA comprehensive literature search was conducted to identify all prospective studies on the MSRSGC. The risk of malignancy (ROM), risk of neoplasm, and diagnostic accuracy for each diagnostic category were calculated. Data were tabulated in Microsoft Excel, and analyses were performed with the Open Meta‐Analyst program.ResultsSeven prospective and seven retrospective studies were identified. The total number of fine‐needle aspirations (FNAs) was 1587 in the prospective studies and 1764 in the retrospective studies. The ROM values for the nondiagnostic, nonneoplastic, atypia of undetermined significance, benign neoplasm, salivary gland neoplasm of uncertain malignant potential, suspicious for malignancy, and malignant categories in prospective versus retrospective studies were 21.0% versus 26.6%, 9.4% versus 8.1%, 34.9% versus 39.6%, 2.4% versus 2.1%, 36.6% versus 31.2%, 86.0% versus 66.0%, and 97.0% versus 96.7%, respectively. Sensitivities, specificities, and diagnostic odds ratios were 83.1% (95% confidence interval [CI], 71.1%–90.8%) versus 89.1% (95% CI, 83.6%–92.9%), 98.4% (95% CI, 96.6%–99.3%) versus 94.9% (95% CI, 91.9%–96.9%), and 310.7 (95% CI, 121.2–796.6) versus 218.8 (95% CI, 107.3–438.1).ConclusionsThis meta‐analysis indicated that the MSRSGC works well in FNA cytopathology practice and improves diagnostic accuracy in all diagnostic categories. The ROMs of prospective studies were in concordance with the MSRSGC reference values.