bluuebunny/crossref_metadata_2025_split huggingface dataset:
Listening to Hong Kong children's perspectives through pretend play
Authors: Leung Suzannie K. Y. 
Published: February 2024

AbstractQuality in early childhood education and care (ECEC) has become an increasing concern in recent years. The issue has been regularly discussed by different stakeholders. However, the rising concern regarding quality in ECEC has not seriously taken into account children's perspectives. Hong Kong, with its academic‐driven education system, is no exception. Children's perspectives have been neglected under the impact of neoliberalism on education in Chinese society. Engaging with children's perspectives has thus become an important matter in Hong Kong society. In April 2019, a children's pretend‐play project was started in an open playground in Hong Kong. This project aimed to help children regain their subjectivities and share their thoughts through the process of pretend play. Children in this project were invited to create, pretend and imagine themselves in the role of superheroes so that they could express their perspectives. This alternative practice opened a space for children to liberate themselves through pretend‐play activities, while reworking the conventional pedagogies found in the neoliberal education system. The findings offer critical reflections on how to improve quality in ECEC by redeveloping trust and respect among adults and children through listening to children's perspectives.
How green human resource management can promote green competitive advantage: The role of green innovation
Authors: Zhang Shujie , Chen Mengyuan , Tang Guiyao 
Published: February 2024

AbstractWith growing public concerns about ecological issues, it has been increasingly critical for corporations to enhance their green competitive advantages. Utilizing a natural‐resource‐based view of firm and human resource management (HRM) perspective, we propose that green HRM (GHRM) promotes firms' green competitive advantages by facilitating two kinds of green innovation (i.e., green product/process innovation). Via a two‐wave survey study of chief human resources officers (CHOs) and chief financial officers (CFOs) from 69 companies in China, we find support that GHRM positively links to green product and process innovations, each of which will, in turn, have a positive correlation with a green competitive advantage. Moreover, an indirectly positive linkage between GHRM and green competitive advantage via two types of green innovation is also proved. Our study expands current research by demonstrating a positive effect of GHRM in building green competitive advantage and by revealing two parallel mechanisms of such effect.
New Azo Derivative of β‐Diketones and Its Cu(II), Co(II) Complexes: Synthesis, Theoretical Study and Biological Activity
Authors: Tahirli Shahla , Sadeghian Nastaran , Aliyeva Farqana , Sujayev Afsun , Günay Sevilay , Erden Yavuz , Shikhaliyev Namig , Kaya Savaş , Mehtap Özden Eda , Chiragov Famil , Berisha Avni , Taslimi Parham 
Published: February 2024

AbstractThe paper is focused on biological activity and theoretical study of the structure and properties of a new azo derivative of β‐diketones and its complexes with some metals. The aim of our work was to study the structure and properties of the newly synthesized compound as well as to theoretically determine the possibility of complex formation with the Cu(II) or Co(II) ions. A compound with the same substituents R1=R2=CH3 was chosen for the study. A synthesized azo compound based on 4‐amino antipyrine and its complexes with Cu(II), Co(II) in solution and solid phase is reported. The structures of these compounds have been testified by X‐ray, IR and NMR spectroscopy. The combined experimental and theoretical approach was used. To study the structure and properties of the synthesized compound, as well as its possible complex formation with the Cu(II), quantum‐chemical calculations were carried out the 6‐31G basis set and the electron density functional theory (DFT) method. These 3‐(1‐phenyl‐2,3‐dimethyl‐pyrazolone‐5) azopentadione‐2,4 (PDPA) with Cu(II) and Co(II) complexes had effective inhibition against butyrylcholinesterase and acetylcholinesterase. IC50 values were found as 19.03, 3.64 μM for AChE and 28.47, 8.01 μM for BChE, respectively. Cholinesterase inhibitors work to slow down the acetylcholine‘s deterioration.
Bioactive 5/5/5/6 Four–Ring System Iridoids from Plumeria alba L.
Authors: Zhou Xin , Meng Xin‐Bin , Zhou Xue‐Ming , Zhu Zheng‐Tian , Yang Jing , Chen Hong‐Jie , Song Xin‐Ming 
Published: February 2024

AbstractTwo rare 5/5/5/6 four–ring system iridoids, allamancins A and B (1 and 2) together with one known biogenetically related iridoid derivative, 3‐O‐methyallamancin (3) were isolated from the flowers of Plumeria alba L. The structures of these iridoid derivatives were determined by comprehensive spectroscopic analyses. The absolute configuration of 1 was confirmed by X‐ray crystallographic analysis. The inhibitory activities of compounds 1–3 against nitric oxide (NO) production induced and three cancer cell lines were evaluated in vitro. Compounds 1 and 3 showed inhibitory activities on NO production with IC50 values of 18.3±0.12 and 22.1±0.14 μM, respectively. Compounds 1–3 showed moderate inhibitory activities against cancer cell lines of A549, Hela and MCF‐7.
A Facile Access to Green Fluorescent Albumin Derivatives
Authors: Saletti Mario , Paolino Marco , Venditti Jacopo , Bonechi Claudia , Giuliani Germano , Lamponi Stefania , Tassone Giusy , Boccia Antonella , Botta Chiara , Blancafort Lluís , Poggialini Federica , Vagaggini Chiara , Cappelli Andrea 
Published: February 2024

AbstractA Morita‐Baylis‐Hillman Adduct (MBHA) derivative bearing a triphenylamine moiety was found to react with human serum albumin (HSA) shifting its emission from the blue to the green‐yellow thus leading to green fluorescent albumin (GFA) derivatives and enlarging the platform of probes for aggregation‐induced fluorescent‐based detection techniques. A possible interaction of MBHA derivative 7 with a lipophilic pocket within the HSA structure was suggested by docking studies. DLS experiments showed that the reaction with HSA induce a conformational change of the protein contributing to the aggregation process of GFA derivatives. The results of investigations on the biological properties suggested that GFA retained the ability of binding drug molecules such as warfarin and diazepam. Finally, cytotoxicity evaluation studies suggested that, although the MBHA derivative 7 at 0.1 μg/mL affected the percentage of cell viability in comparison to the negative control, it cannot be considered cytotoxic, whereas at all the other concentrations≥0.5 μg/mL resulted cytotoxic at different extent.
Functional and Mechanistic Characterization of the 4,5‐diepi‐Isoishwarane Synthase from the Liverwort Radula lindenbergiana
Authors: Xu Houchao , Köllner Tobias G. , Chen Feng , Dickschat Jeroen S. 
Published: February 2024

AbstractThe microbial type sesquiterpene synthase RlMTPSL4 from the liverwort Radula lindenbergiana was investigated for its products, showing the formation of several sesquiterpene hydrocarbons. The main product was structurally characterized as the new compound 4,5‐diepi‐isoishwarane, while the side products included the known hydrocarbons germacrene A, α‐selinene, eremophilene and 4,5‐diepi‐aristolochene. The cyclization mechanism towards 4,5‐diepi‐isoishwarane catalyzed by RlMTPSL4 was investigated through isotopic labeling experiments, revealing the stereochemical course for the deprotonation step to the neutral intermediate germacrene A, a reprotonation for its further cyclization, and a 1,2‐hydride shift along the cascade. The absolute configuration of 4,5‐diepi‐isoishwarane was determined using a stereoselective deuteration approach, revealing an absolute configuration typically observed for a microbial type sesquiterpene.
Strategies to Improve the Activity of Silver–loaded Calcium Titanate Crystal Photocatalyst for Photocatalytic Reduction of Carbon Dioxide with Water
Authors: Qiu Hongxuan , Yamamoto Akira , Yoshida Hisao 
Published: February 2024

AbstractThe rapid increase of carbon dioxide (CO2) in the atmosphere has sparked a global enthusiasm for carbon recycling. Photocatalytic CO2 reduction with water into carbon–containing products has attracted much attention since it can convert solar energy to the chemical potential of the products and CO2 to valuable compounds at the same time. One of the main products in the photocatalytic reaction system is carbon monoxide (CO), a useful compound for the one‐carbon chemistry and related ones. The current shortage of this system is the low production efficiency, demanding us to improve the activity of the photocatalyst. In this perspective article, by taking a calcium titanate (CaTiO3, CTO) photocatalyst with silver cocatalyst (Ag/CTO) and so on as examples that can promote the selective photocatalytic CO2 reduction with water, we shortly review some strategies to improve the photocatalytic activity such as fabrication of well–structured crystal photocatalysts, development of the surface property and cocatalyst, improvement of surface CO2 adsorption, and improvement of photoabsorption. These concepts will be widely applied and contribute to further development of photocatalytic systems.
The Resorcinarene Hexameric Capsule as a Supramolecular Photoacid to Trigger Olefin Hydroarylation in Confined Space
Authors: Ferrino Giuseppina , De Rosa Margherita , Della Sala Paolo , Gaeta Carmine , Talotta Carmen , Soriente Annunziata , Cao Zhen , Maity Bholanath , Cavallo Luigi , Neri Placido 
Published: February 2024

AbstractThe self‐assembled resorcinarene capsule C6 shows remarkable photoacidity upon light irradiation, which is here exploited to catalyze olefin hydroarylation reactions in confined space. An experimental pKa* value range of −3.3–−2.8 was estimated for the photo‐excited hexameric capsule C6*, and consequently an increase in acidity of 8.8 log units was observed with respect to its ground state (pKa=5.5–6.0). This makes the hexameric capsule the first example of a self‐assembled supramolecular photoacid. The photoacid C6* can catalyze hydroarylation reaction of olefins with aromatic substrates inside its cavity, while no reaction occurred between them in the absence of irradiation and/or capsule. DFT calculations corroborated a mechanism in which the photoacidity of C6* plays a crucial role in the protonation step of the aromatic substrate. A further proton transfer to olefin with a concomitant C−C bond formation and a final deprotonation step lead to product releasing.
3‐Oxidopyridinium Ions Are Versatile Bioorthogonal Dipoles for Use in Cycloadditions with Cyclooctynes
Authors: Serhan Mariam , Josephson Jason D. , Masoud Shadi Sedghi , Nakajima Masaya , Pezacki John Paul 
Published: February 2024

Abstract3‐oxidopyridinium ions are water stable and soluble heteroaromatic betaines that behave as latent dipoles and undergo a wide variety of cycloadditions. Research into the cycloaddition reactions of 3‐oxidopyridiniums was spearheaded by Alan R. Katritzky and collaborators from the early 1970s until the late 1980s, but they have yet to be used for bioorthogonal applications. Herein we report that 3‐oxidopyridiniums can readily react with 4‐dibenzocyclooctynol (DIBO), a common bioorthogonal handle, in a [3+2] cycloaddition. The mechanism was investigated by altering the electronics of the reaction by changing the substituent on the 5 position of the pyridinium. Electron‐donating 5‐substituents have been shown to significantly increase the rate of the reaction, with bimolecular rate constants ranging from 3.3×10−4 s−1 with 5‐trifluoromethyl‐N‐methyl‐3‐oxidopyridinium to 1.07 M−1 s−1 with 5‐amino‐N‐methyl‐3‐oxidopyridinium. 3‐oxidopyridiniums’ appreciable cycloaddition rates and compatibility with bioorthogonally relevant environments give them the potential to be used in a variety of bioconjugation applications.
Stabilization of Lantern‐Type Metal‐Organic Cages (MOCs) by Protective Control of Ligand Exchange Rates
Authors: Walker Samuel E. , Chant William , Thoonen Shannon , Tuck Kellie L. , Turner David R. 
Published: February 2024

AbstractSelf‐assembling systems in nature display remarkable complexity with assemblies of different sub‐units to generate functional species. Synthetic analogues of such systems are a challenge, often requiring the ability to bias distributions that are under thermodynamic assembly control. Using lantern‐type MOCs (metal‐organic cages) as a prototypical self‐assembling system, herein we explore the role that steric bulk plays in controlling the exchange rate of ligands in paddlewheel‐based assemblies, and thus the stability of cages, in competitive self‐assembling scenarios. The effective lifetime of the lantern‐type MOCs varies over an order of magnitude depending on the steric bulk proximal to the metal nodes with lifetimes of the cages ranging from tens of minutes to several hours. The bulk of the coordinating solvents likewise reduces the rate of ligand exchange, and thus yields longer‐lived species. Understanding this subtle effect has implications for controlling the stability of complex assemblies in competitive environments with implications for guest release and application.
Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging
Authors: Dey Subhayan , Szathmári Balázs , Franz Roman , Bruhn Clemens , Kelemen Zsolt , Pietschnig Rudolf 
Published: February 2024

AbstractA direct route to a doubly ferrocene bridged tetracyclic tetraphosphane 1 was developed via reductive coupling of Fe(CpPCl2)2 (2 a), where a chlorine terminated linear P4‐compound 3 could be identified as an intermediate. Selective P−P bond activation was further achieved by reacting 1 with elemental selenium or [Cp*Al]4, where regioselective insertion of Se or Al atoms resulted in ferrocenylene bridged [P4Se] (4) or [P4Al] (7) moieties. Compound 7 can be transformed to a hydrogen terminated linear P4 species, 8, with protic solvents. Methylation of compound 1 with MeOTf, proceeds via intermediate formation of monomethylated species 5, which gradually produced Me2‐terminated dicationic 6, again containing a linear P4‐unit. Besides spectroscopic characterization, the structural details of compounds 1, 4, 6, and 8 could be determined by SC‐XRD. Moreover, DFT calculations were used to rationalize the reactivity of 1, derived compounds and intermediates. As a key feature, 1 undergoes ring opening polymerization to a linear polyphosphane 9.
N‐Aryl‐DABCO Salts as an Unprecedented Sensing Platform for the Detection of Thiols and Selenols
Authors: Ranishenka Bahdan , Lamekina Yuliya , Seviarynchyk Tatsiana , Bugaenko Dmitry , Shmanai Vadim , Karchava Alexander 
Published: February 2024

AbstractQuaternary N‐aryl‐DABCO salts were introduced for the first time as a highly selective sensing platform for thiols and selenols. By employing this platform, a highly sensitive coumarin based “off‐on” fluorescent probe was designed and synthesized. The probe possesses a good solubility in water, low background fluorescence, and, most importantly, demonstrates high selectivity to aryl thiols and selenols over their aliphatic counterparts and other common nucleophiles. A dramatic increase in fluorescence intensity is achieved through the selective cleavage of the quaternized DABCO‐ring, yielding a piperazine derivatives with a high fluorescence quantum yield (~72 %). Moreover, stability of the probe to the most used reducing agents DTT and TCEP was demonstrated. The limits of detection for p‐thiocresol and phenyl selenide were evaluated to be 22 nM and 6 nM, respectively.
Total Synthesis of Laurane and Guaiane Sesquiterpenoids via Oxidative Nazarov Reaction
Authors: Chen Yuye , Chen Wenqing , Zhang Zhiting , Xu Jing 
Published: February 2024

Comprehensive SummaryAs one of the most common structural motifs in natural products, cyclopentenones usually can be fabricated by Nazarov cyclization using divinyl ketones or functionalized tertiary divinyl carbinols (TDCs) as substrates. However, straightforward method for transforming unfunctionalized TDCs to their corresponding cyclopentenones is currently lacking. Herein, we wish to report the total syntheses of four structurally distinct terpenoids, namely laurane‐type marine sesquiterpenoids isolaurene, debromoaplysin and aplysin, and guaiane sesquiterpenoid guaiadienone A, all using a novel synthetic method, named oxidative Nazarov cyclization, as the key step. This work demonstrated our robust method is suitable for synthesizing various highly substituted cyclopentenones.
Retrospective analysis of cytology and high‐risk HPV testing in 1067 endocervical adenocarcinomas and precursor lesions
Authors: Ye Lei , Gan Meifu , Yao Yeli , Lu Bingjian 
Published: February 2024

AbstractBackgroundCytology and high‐risk human papilloma virus (hrHPV) cotesting is the mainstay in the detection of cervical carcinoma.MethodsEndocervical adenocarcinoma (EAC) is divided into HPV‐associated adenocarcinoma (HPVA) and HPV‐independent adenocarcinoma (HPVI) by the World Health Organization classification (2020). The detection effect of cotesting is suggested to be different among EAC subtypes and precursors, but has not well‐documented yet. In this study, the authors retrospectively analyzed cotesting among adenocarcinoma in situ (AIS), HPVA, and HPVI. The cohort included 569 AIS and 498 EAC consisting of 371 (74.5%) HPVA, 111 (22.3%) HPVI, and 16 (3.2%) adenocarcinoma, not otherwise specified.ResultsThe authors found that AIS patients were significantly younger than HPVA and HPVI (mean ± SD, years: 40.7 ± 8.6; HPVA, 44.8 ± 9.3; HPVI, 50.0 ± 11.3; p < .001) and had a higher prevalence of concurrent squamous intraepithelial lesions (75.5%, HPVA, 37.2%; HPVI, 12.6%; p < .001). The detection rate of hrHPV test or cytology was substantially higher in AIS and HPVA than in HPVI (97.7% and 90.2% vs. 16.5%, p < .001, or 71.1% and 71.9% vs. 60.7%, p = .042, respectively). Cytology and hrHPV cotesting was superior to a single test in the detection of EAC and AIS. The detection rate of cotesting amounted to 100% in AIS and 94.3% in HPVA but was substantially lower in HPVI (72.2%) (p < .001).ConclusionsThe authors conclude that cytology and hrHPV cotesting can maximize the detection effect for HPVA and AIS but is not optimal for HPVI.
Detection of effusion tumor cells under different storage and processing conditions
Authors: Libert Diane M. , Zhu Yili , Wang Aihui , Allard Grace M. , Cheng‐Yi Lowe Alarice 
Published: February 2024

AbstractBackgroundCirculating tumor cells (CTCs) shed into blood provide prognostic and/or predictive information. Previously, the authors established an assay to detect carcinoma cells from pleural fluid, termed effusion tumor cells (ETCs), by employing an immunofluorescence‐based CTC‐identification platform (RareCyte) on air‐dried unstained ThinPrep (TP) slides. To facilitate clinical integration, they evaluated different slide processing and storage conditions, hypothesizing that alternative comparable conditions for ETC detection exist.MethodsThe authors enumerated ETCs on RareCyte, using morphology and mean fluorescence intensity (MFI) cutoffs of >100 arbitrary units (a.u.) for epithelial cellular adhesion molecule (EpCAM) and <100 a.u. for CD45. They analyzed malignant pleural fluid from three patients under seven processing and/or staining conditions, three patients after short‐term storage under three conditions, and seven samples following long‐term storage at –80°C. MFI values of 4′,6‐diamidino‐2‐phenylindol, cytokeratin, CD45, and EpCAM were compared.ResultsETCs were detected in all conditions. Among the different processing conditions tested, the ethanol‐fixed, unstained TP was most similar to the previously established air‐dried, unstained TP protocol. All smears and Pap‐stained TPs had significantly different marker MFIs from the established condition. After short‐term storage, the established condition showed comparable results, but ethanol‐fixed and Pap‐stained slides showed significant differences. ETCs were detectable after long‐term storage at –80°C in comparable numbers to freshly prepared slides, but most marker MFIs were significantly different.ConclusionsIt is possible to detect ETCs under different processing and storage conditions, lending promise to the application of this method in broader settings. Because of decreased immunofluorescence‐signature distinctions between cells, morphology may need to play a larger role.
Hexylation Stabilises Twisted Backbone Configurations in the Prototypical Low‐Bandgap Copolymer PCDTBT
Authors: Stäter Sebastian , Woering Erik F. , Lombeck Florian , Sommer Michael , Hildner Richard 
Published: February 2024

AbstractConjugated donor‐acceptor copolymers hold great potential as materials for high‐performance organic photovoltaics, organic transistors and organic thermoelectric devices. Their low optical bandgap is achieved by alternation of donor and acceptor moieties along the polymer chain, leading to a pronounced charge‐transfer character of electronic excitations. However, the influence of appended side chains and of chemical defects of the backbone on their photophysical and conformational properties remains largely unexplored on the level of individual chains. Here, we employ room temperature single‐molecule photoluminescence spectroscopy on four compounds based on the prototypical copolymer PCDTBT with systematically changed chemical structure. Our results show that an increasing density of statistically added hexyl chains to the TBT comonomer distorts the molecular conformation, likely through the increase of average dihedral angles along the backbone. We find that, although the conformation becomes more twisted with high hexyl density, the side chains appear to stabilize the backbone in this twisted conformation. In addition, we demonstrate that homocoupling defects along the backbone barely influence the PL spectra of single chains, and thus intra‐chain electronic properties.
Inherent D‐A Architecture in Indoloquinoxalines with an Array of Substituents for Non‐Volatile Memory Device Applications
Authors: Swetha Senthilkumar V. , Gayathri Ramesh , Ardra Murali , Imran Predhanekar Mohamed , Nagarajan Samuthira 
Published: February 2024

AbstractDonor–acceptor (D‐A)‐based architecture has been the key to increase storage capability efficiency through the enhanced charge transportation in the fabricated device. We have designed and synthesized a series of functionalized indoloquinoxalines (IQ) for non‐volatile organic memory devices. The investigation on UV‐visible spectra reveals the absorption maxima of the compounds around 420 nm, attributed to the intramolecular charge transfer between indole and quinoxaline moiety. The irreversible anodic peak in the 1.0 to 1.5 V range indicates the indole moiety‘s oxidation ability. Besides, the cathodic peak in the range of −0.5 to −1.0 V, contributed to the stability of the reduced quinoxaline unit. All the compounds exhibited uniformly covered thin film in SEM analysis, potentially facilitating the seamless charge carrier migration between adjacent molecules. The methoxyphenyl substituted compound exhibited the binary write‐once read‐many (WORM) memory behavior with the lowest threshold voltage of −0.81 V. The molecular simulations displayed the efficient intramolecular charge transfer, providing the fabricated device‘s distinctive conductive states. Except for the tert‐butylphenyl compound, which showed volatile dynamic random‐access memory (DRAM) behavior, all the other compounds exhibited non‐volatile WORM memory behavior, suggesting IQs potential as an intrinsic D–A molecule in organic memory devices on further structural refinement.