bluuebunny/crossref_metadata_2025_split huggingface dataset:
The decrease in zinc‐finger E‐box‐binding homeobox‐1 could accelerate steroid‐induced osteonecrosis of the femoral head by repressing type‐H vessel formation via Wnt/β‐catenin pathway
Authors: Zhang Guangyang , Cai Yuanqing , Liang Jialin , Jing Zhaopu , Wei Wang , Lv Leifeng , Dang Xiaoqian , Song Qichun 
Published: December 2024

AbstractBackgroundZinc‐finger E‐box‐binding homeobox‐1 (ZEB1) is predominantly found in type‐H vessels. However, the roles of ZEB1 and type‐H vessels in steroid‐induced osteonecrosis of the femoral head (SONFH) are unclear.MethodsHuman femoral heads were collected to detect the expression of ZEB1 and the levels of type‐H vessels. Then, the SONFH model was developed by injecting C57BL/6 mice with lipopolysaccharide and methylprednisolone. Micro‐computed tomography, angiography, double calcein labeling, immunofluorescence, immunohistochemistry, quantitative real‐time polymerase chain reaction, and Western blotting were performed to detect the expression of ZEB1, the Wnt/β‐catenin pathway, type‐H vessels, and the extent to which ZEB1 mediates angiogenesis and osteogenesis. Human umbilical vein endothelial cells were also used to explore the relationship between ZEB1 and the Wnt/β‐catenin pathway.ResultsWe found that ZEB1 expression and the formation of type‐H vessels decreased in SONFH patients and in a mouse model. The number of vascular endothelial growth factors in the femoral heads also decreased. Moreover, the bone mineral density, trabecular number, mineral apposition rate, and expression of genes related to osteogenesis decreased. After ZEB1 knockdown, angiogenesis and osteogenesis decreased. However, the numbers of type‐H vessels and the extent of angiogenesis and osteogenesis improved after activation of the Wnt/β‐catenin pathway.ConclusionsThe ZEB1 expression decreased in SONFH, causing a decrease in type‐H vessel, and it mediated angiogenesis and osteogenesis by regulating the Wnt/β‐catenin pathway, ultimately accelerating the process of SONFH.
Self‐Immolative Polymers Derived from Renewable Resources via Thiol–Ene Chemistry**
Authors: Deng Zhengyu , Gillies Elizabeth R. 
Published: December 2024

AbstractThe development of polymers from renewable resources is a promising approach to reduce reliance on petrochemicals. In addition, depolymerization is attracting significant attention for the breakdown of polymers at their end‐of‐life or to achieve specific stimuli‐responsive functions. However, the design of polymers incorporating both of these features remains a challenge. Herein, we report a new class of self‐immolative polymers based on lignin‐derived aldehydes via a simple thiol‐ene polymerization. These self‐immolative polymers undergo cascade degradation in response to specific stimuli through alternating 1,6‐elimination and cyclization reactions. The two methoxy substituents on the syringaldehyde monomer accelerated the desired depolymerization reaction, while enhancing stability against undesired backbone hydrolysis. Moreover, diverse responsive end‐caps could be introduced through post‐polymerization functionalization from a single polymer precursor.
Hydroalkylation of Vinylarenes by Transition‐Metal‐Free In Situ Generation of Benzylic Nucleophiles Using Tetramethyldisiloxane and Potassium tert‐Butoxide
Authors: Onge Piers St. , Nugraha Hana , Newman Stephen G. 
Published: December 2024

AbstractHydrosilanes and Lewis bases are known to promote various reductive defunctionalizations, rearrangements, and silylation reactions, facilitated by enigmatic silicon/Lewis base‐derived reactive intermediates. Despite the wide variety of transformations enabled by this reagent combination, no examples of intermolecular C(sp3)−C(sp3) forming reactions have been reported. In this work, we've identified 1,1,3,3‐tetramethyldisiloxane (TMDSO) and KOtBu as a unique reagent combination capable of generating benzylic nucleophiles in situ from styrene derivatives, which can subsequently react with alkyl halides to give a new C(sp3)−C(sp3) linkage via formal hydroalkylation. Mechanistic experiments suggest that the reaction proceeds through a key hydrogen atom transfer (HAT) step from a hydrosilane reducing agent to styrene, affording a benzylic radical that undergoes reductive radical polar crossover (RRPC) and subsequent SN2 alkylation.
Chemical Upcycling of Thermoplastics Towards Thermosets Based on Dynamic Dimethylglyoxime‐Urethane Moiety
Authors: Sun Qiao , Liu Ling , Zhang Jianye , Chang Xiaohua , Chen Jianwen , Liu Zenghe , Zhu Yutian 
Published: December 2024

AbstractHuge annual consumption of thermoplastics results in the generation of large amounts of waste after their service life. Currently, the most popular recycling method based on mechanically melt‐reprocessing deteriorates the material performance and is economically unattractive, which makes it unviable to be implemented in large scale. Herein, we present a chemical upcycling strategy that can transform dimethylglyoxime‐urethane based thermoplastic waste into thermoset product with superior mechanical properties and higher economic values than the initial one. It is found that the dimethylglyoxime‐urethane moiety has dynamic nature, endowing the material with open‐loop upcycling ability. By removing the dimethylglyoxime segment via a simple sublimation process, the material structure is transformed from linear molecular into crosslinked network. More interestingly, the transformation is reversible, and the regenerated crosslinked network can be transformed back to linear molecule by returning the removed dimethylglyoxime segment to the material, which means the upcycled product can be recycled again after its service life. Our linear/crosslinked transformation strategy provide a new option for recycling thermoplastic waste.
Solvent‐Dependent Divergent Cyclization of Bicyclo[1.1.0]butanes
Authors: Zhang Fuhao , Dutta Subhabrata , Petti Alessia , Rana Debanjan , Daniliuc Constantin G. , Glorius Frank 
Published: December 2024

AbstractBicyclo[1.1.0]butanes (BCBs) have recently garnered significant research interest as versatile precursors for synthesizing potential [n.1.1] bioisosteres and multi‐functionalized cyclobutanes in a straightforward and atom‐economical manner. Here, we report a solvent‐dependent divergent cyclization of BCBs that provides highly diastereospecific decorated cyclobutanes and oxygen‐containing bicyclo[3.1.1]heptanes (BCHeps), which serve as bioisosteres of meta‐substituted arenes. Additionally, an unprecedented 1,2‐difunctionalization reaction mode for BCBs was explored, thus expanding the chemical space of arene bioisosteres and highly functionalized cyclobutanes.
Copper‐Catalyzed Enantioselective Skeletal Editing through a Formal Nitrogen Insertion into Indoles to Synthesize Atropisomeric Aminoaryl Quinoxalines
Authors: Zhang Xu , Zhang Jin‐Qi , Sun Ze‐Hua , Shan Hui‐Mei , Su Jun‐Cheng , Ma Xiao‐Pan , Su Gui‐Fa , Xu Li‐Ping , Mo Dong‐Liang 
Published: December 2024

AbstractSkeletal editing represents an attractive strategy for adding complexity to a given molecular scaffold in chemical synthesis. Isodesmic reactions provide a complementary skeletal editing approach for the redistribution of chemical bonds in chemical synthesis. However, catalytic enantioselective isodesmic reaction is extremely scarce and enantioselective isodesmic reaction to synthesize atropisomeric compounds is unknown. Herein, we report a facile method to synthesize axially chiral aminoaryl quinoxalines through Cu(I)‐catalyzed dearomatization and sequential chiral phosphoric acid (CPA) catalyzed enantioselective isodesmic C−N bond formation and cleavage from indoles and 1,2‐diaminoarenes under mild reaction conditions. In this process, the five‐membered ring of the indole scaffold was broken and a novel quinoxaline skeleton was constructed. This method allows the practical and atom‐economical synthesis of valuable axially chiral aminoaryl quinoxalines in high yields (up to 95 %) and generally excellent enantioselectivities (up to 99 % ee). Notably, this novel type of quinoxaline atropisomers has promising applications in developing axially chiral ligand in asymmetric catalysis. This strategy represents the first example of CPA‐catalyzed enantioselective isodesmic reaction to form axially chiral compounds.
New Thermoplastic Elastomers based on Ethylene‐Butadiene‐Rubber (EBR) by Switching from Anionic to Coordinative Chain Transfer Polymerization
Authors: Alioui Samy , Langlais Marvin , Ngo Robert , Habhab Karima , Dronet Séverin , Jean‐Baptiste‐dit‐Dominique François , Albertini David , D'Agosto Franck , Boisson Christophe , Montarnal Damien 
Published: December 2024

AbstractOlefin triblock copolymers based on glassy polystyrene (PS), ethylene butadiene rubber (EBR) and highly crystalline polyethylene (PE) segments were prepared for the first time using a switch strategy from anionic polymerization to coordinative chain transfer (co)polymerization (CCT(co)P). PS chains obtained by anionic polymerization were transmetalated with mesitylmagnesium bromide (BrMgMes) to act as macromolecular chain transfer agents (macro‐CTA, PS‐MgMes) in the CCTcoP of ethylene and butadiene using {Me2Si(C13H8)2Nd(BH4)2Li(THF)}2 complex (1). Further chain extension by CCTP using pure ethylene in the monomer feed afforded well‐defined PS‐b‐EBR‐b‐PE triblock copolymers. The structural, rheological and mechanical properties of these materials demonstrate excellent balance between properties and easy processability at moderate temperatures (>150 °C). We demonstrate that such triblock copolymers behave effectively as low‐viscosity PS‐b‐EBR diblock copolymers above the melting point of PE domains and high performance thermoplastic elastomers (TPEs) upon crystallization of PE segments.
Mechanically Strong and Fast‐Curing Kraft Lignin‐Based Polyurethane Foam
Authors: Husna Naurotul , Ismayati Maya , Syafii Wasrin , Fatriasari Widya , Solihat Nissa Nurfajrin 
Published: December 2024

ABSTRACTThe creation of biobased rigid polyurethane from nonfood resources such as lignin has garnered significant interest, especially concerning the biorefinery concept. However, few studies have investigated virgin lignin as a polyol source for polyurethane foam and the effects of single factors, such as the lignin solvent, lignin concentration, and lignin:isocyanate ratio, on the properties of polyurethane. High‐density rigid foam (~500 kg/m3) was successfully formed by all the solvents except sodium hydroxide, which was confirmed via Fourier transform infrared (FTIR) spectroscopy and pyrolysis‐gas chromatography–mass spectrometry (Py‐GCMS). The highest to lowest modulus of elasticity (MOE) and modulus of rupture (MOR) values for the different lignin solvents were as follows: tetrahydrofuran (THF) (402.25 and 13.24 N/mm2) > dimethyl formamide (DMF) (46 and 1.69 N/mm2) > dimethyl sulfoxide (DMSO) (29 and 1.39 N/mm2). DMSO was selected as the optimal solvent because of the considerable curing time (26.67 s) needed to produce rigid foam. A higher lignin concentration resulted in better physical, mechanical, and thermal properties of the foam to some extent. Moreover, the opposite occurred with increasing isocyanate ratio in the system. These findings can serve as a basis for optimizing the utilization of lignin as a bioresource in the manufacture of rigid polyurethane foam with more specific uses.
Water Ageing of Epoxies: Effect of Thermal Oxidation
Authors: Tahraoui Nawfel , Delannoy Romain , Derue Isabelle , Richaud Emmanuel 
Published: December 2024

ABSTRACTEpoxy samples obtained by curing bisphenol A diglycidyl ether with triethylenetetramine are thermally oxidized at 160°C under air. The impact on water sorption is investigated by water uptake recorded by Dynamic Vapor Sorption and the gravimetric method. Experimental data mainly showed that water solubility in epoxies increases due to oxidative degradation, meanwhile, the formation of clustering remains limited. In the investigated ageing conditions, water diffusion obeys Fick's law. Despite a significant chain scission process, water diffusivity in polymer remains constant, possibly in line with the fact that hydroxypropylethers are the driving force of water diffusion and are not degraded during thermal ageing.
Reassessment of Xenodens calminechari with a discussion of tooth morphology in mosasaurs
Authors: Sharpe Henry S. , Powers Mark J. , Caldwell Michael W. 
Published: December 2024

AbstractXenodens calminechari is a mosasaurid taxon named by Longrich et al. (2021) based on the holotype MHNM.KH.331, a left maxilla with several teeth. This holotype was obtained nonscientifically (without technical supervision) from an area in Morocco that yields many manipulated or forged specimens. Examination of Longrich et al. (2021) reveals four tooth crowns occupy what appear to be two alveoli in MHNM.KH.331, and there is potential adhesive connecting the tooth crowns to the maxilla on their lateral sides. We argue that the articulated tooth crowns of this taxon were artificially placed in the maxilla, rendering at least two apomorphies of this taxon the product of forgery. Longrich et al. (2021)'s claims of fused tooth ‘roots' in MNHM.KH.331 are instead calcified periodontal ligament and alveolar bone that have ankylosed, resembling the typical mosasaurid condition. Differing tooth crown morphology does not preclude the referral of the teeth of this specimen to a younger ontogenetic stage of another mosasaur (possibly Carinodens) because many extant lizard species show drastic ontogenetic changes in the dentition. We argue that Xenodens calminechari represents a nomen dubium. This specimen constitutes a confluence of two persistent problems in vertebrate paleontology: material sourced from commercial excavations that has not been adequately tested for forgery, and taxa named from tooth‐based holotypes that ignore the potential for intraspecific dental variation and interspecific convergence in dental characters, as are common in squamates. We suggest that Longrich et al. CT scan MHNM.KH.331, and we supply CT examples for identifying artificially added tooth crowns to Moroccan mosasaur jaws. Finally, we provide recommendations for the designation of mosasaurid holotypes.
Endogenous Retroelement Activation is Implicated in Interferon‐α Production and Anti–Cyclic Citrullinated Peptide Autoantibody Generation in Early Rheumatoid Arthritis
Authors: Cooles Faye A. H. , Vidal Pedrola Gemma , Naamane Najib , Pratt Arthur G. , Barron‐Millar Ben , Anderson Amy E. , Hilkens Catharien M. U. , Casement John , Bondet Vincent , Duffy Darragh , Zhang Fan , Shukla Ruchi , Isaacs John D. 
Published: December 2024

ObjectiveEndogenous retroelements (EREs) stimulate type 1 interferon (IFN‐I) production but have not been explored as potential interferonogenic triggers in rheumatoid arthritis (RA). We investigated ERE expression in early RA (eRA), a period in which IFN‐I levels are increased.MethodsERE expression (long terminal repeat [LTR] 5, long interspersed nuclear element 1 [LINE‐1], and short interspersed nuclear element [SINE]) in disease‐modifying treatment‐naïve eRA whole‐blood and bulk synovial tissue samples was examined by reverse transcription–polymerase chain reaction and NanoString alongside IFN‐α activity. Circulating lymphocyte subsets, including B cell subsets, from patients with eRA and early psoriatic arthritis (ePsA) were flow cytometrically sorted and similarly examined. Existing established RA and osteoarthritis (OA) synovial single‐cell sequencing data were reinterrogated to identify repeat elements, and associations were explored.ResultsThere was significant coexpression of all ERE classes and IFNA in eRA synovial tissue samples (n = 22, P < 0.0001) and significant positive associations between whole‐blood LINE‐1 expression (n = 56) and circulating IFN‐α protein (P = 0.018) and anti–cyclic citrullinated peptide (anti‐CCP) titers (P < 0.0001). ERE expression was highest in circulating eRA B cells, particularly naïve B cells compared with ePsA, with possible ERE regulation by SAM and HD Domain Containing Deoxynucleoside Triphosphate Triphosphohydrolase 1 transcription (SAMDH1) implicated and associations with IFNA again observed. Finally, in established RA synovium, LTRs, particularly human endogenous retroviral sequence K (HERVK), were most increased in RA compared with OA, in which, for all synovial subsets (monocytes, B cells, T cells, and fibroblasts), ERE expression associated with increased IFN‐I signaling (P < 0.001).ConclusionPeripheral blood and synovial ERE expression is examined for the first time in eRA, highlighting both a potential causal relationship between ERE and IFN‐I production and an intriguing association with anti‐CCP autoantibodies. This suggests EREs may contribute to RA pathophysiology with implications for future novel therapeutic strategies.
Evaluating the sustainability of biohydrogen, biogas, and biohythane generation from agricultural, industrial, and municipal waste sources
Authors: Meena Pradeep Kumar , Kumar Deepak , Singh Lokesh , Sharma Sumit , Didwania Mukesh 
Published: December 2024

AbstractBiofuel production from waste materials offers an effective solution for generating renewable energy in biohydrogen, biogas, and biohythane while reducing waste and recycling valuable nutrients. This review examines recent advances in biohydrogen and biogas production from renewable resources, focusing on the environmental impacts of different production techniques. It emphasizes life cycle analysis (LCA) as an important tool for assessing these impacts and discusses key production pathways and processes. The variability in LCA methodologies – including differences in software, impact categories, system boundaries, functional units, and analytical approaches – poses challenges for direct comparisons of studies. Despite these challenges, fermentation‐based production methods show substantial environmental advantages, such as reduced CO2 emissions, diminished ozone depletion potential, improved human health outcomes, lower ecotoxicity, and reduced fossil fuel use. Combining biohydrogen production with anaerobic digestion for biohythane generation demonstrates even greater energy efficiency and greenhouse gas reduction. Adopting waste‐to‐energy strategies grounded in life cycle principles could advance renewable energy system implementation and sustainability significantly.
Test Statistics and Statistical Inference for Data With Informative Cluster Sizes
Authors: Kim Soyoung , Martens Michael J. , Ahn Kwang Woo 
Published: December 2024

ABSTRACTIn biomedical studies, investigators often encounter clustered data. The cluster sizes are said to be informative if the outcome depends on the cluster size. Ignoring informative cluster sizes in the analysis leads to biased parameter estimation in marginal and mixed‐effect regression models. Several methods to analyze data with informative cluster sizes have been proposed; however, methods to test the informativeness of the cluster sizes are limited, particularly for the marginal model. In this paper, we propose a score test and a Wald test to examine the informativeness of the cluster sizes for a generalized linear model, a Cox model, and a proportional subdistribution hazards model. Statistical inference can be conducted through weighted estimating equations. The simulation results show that both tests control Type I error rates well, but the score test has higher power than the Wald test for right‐censored data while the power of the Wald test is generally higher than the score test for the binary outcome. We apply the Wald and score tests to hematopoietic cell transplant data and compare regression analysis results with/without adjusting for informative cluster sizes.
Edaravone's Safety Profile in Acute Ischemic Stroke
Authors: Batino Laurence K. J. , Escabillas Cyrus G. , Navarro Jose C. 
Published: December 2024

ABSTRACTBackgroundWe aimed to evaluate the safety of intravenous edaravone for the treatment of acute ischemic stroke among Filipino patients. The study, categorized as Phase IV, spans from December 2022 to November 2023. The primary objective is to document side effects and serious adverse events during the 14‐day edaravone infusion period.MethodsThe protocol gained approval from the Institutional Review Board, and participants provided written consent. Inclusion criteria involved patients aged 18–70 with acute ischemic stroke within 24 h. Exclusion criteria included extremes of age, pregnancy, severe hepatic impairment, and participation in other clinical trials. Edaravone was administered for 14 days, underwent continuous monitoring, and adverse events were actively recorded.FindingsOut of 64 enrolled patients, 58 completed the treatment, while 4 did not finish, and 2 dropped out. The majority were male (n = 35), median age of 53.5 years, and 81.03% exhibited moderate stroke severity. Two patients reported headaches, and one reported dizziness. No serious adverse events or other untoward effects were documented. Dropouts, attributed to a low ejection fraction, showed normal laboratory results and no side effects during edaravone infusion. Thrombolytic therapy was given to 37.93% of patients.DiscussionOur study contributes insights into edaravone's safety, revealing a favorable profile with mild side effects, aligning with existing literature. Notably, no serious adverse events occurred, emphasizing edaravone's tolerability. Headache and dizziness, which were the common side effects in our case, did not lead to treatment discontinuation. The findings support the growing evidence of edaravone's safety in acute ischemic stroke treatment. Overall, edaravone demonstrates promise in stroke management, necessitating vigilant monitoring, especially considering individual cardiovascular health.
Teachers' Discursive Constructions of Adolescent Sexting, Consent and Gender
Authors: Rousaki Anastasia , Seymour‐Smith Sarah , Kitson‐Boyce Rosie , Marriott Mike 
Published: December 2024

ABSTRACTSexting is the exchange of sexually suggestive content through technological means. Despite being tasked with addressing such incidents in schools, teachers are underrepresented in sexting research. The present study explores teachers' discursive constructions of sexting, consent and gender using Critical Discursive Psychology, analysing 30 interviews with educators and safeguarding staff. The first key finding uncovers the interpretative repertoire of ‘Sexting as a threat’. This repertoire showcases the gendered positions teachers assign adolescents to, positioning ‘Boys as oppressors; girls as victims of sexting’, with girls being simultaneously constructed as sexting to attract boys' attention through the ‘Girls as the validation‐seeking Other’ position. Regarding consent, we explicate three repertoires: ‘Consent as an oxymoron in relation to non‐consensual distribution’, ‘Consent as illegal’ and ‘Coercion as a power imbalance’. We contextualise and discuss these findings within the socio‐political discursive terrain. We highlight their ideological implications and the need to initiate emancipatory positions and discussions regarding inclusive sexting education. Please refer to the Supplementary Material section to find this article's .