bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ultrashort Phase‐Matching Wavelength and Strong Second‐Harmonic Generation in Deep‐UV‐Transparent Oxyfluorides by Covalency Reduction
Authors: Hu Yilei , Wu Chao , Jiang Xingxing , Duanmu Kaining , Huang Zhipeng , Lin Zheshuai , Humphrey Mark G. , Zhang Chi 
Published: November 2023

AbstractThe development of urgently‐needed ultraviolet (UV)/deep‐UV nonlinear optical (NLO) materials has been hindered by contradictory requirements of the microstructure, in particular the need for a strong second‐harmonic generation (SHG) response as well as a short phase‐matching (PM) wavelength. We herein employ a “de‐covalency” band gap engineering strategy to adjust the optical linearity and nonlinearity. This has been achieved by assembling two types of transition‐metal (TM) polyhedra ([TaO2F4] and [TaF7]), affording the first tantalum‐based deep‐UV‐transparent NLO materials, A5Ta3OF18 (A = K (KTOF), Rb (RTOF)). Experimental and theoretical studies reveal that the highly ionic bonds and strong electropositivity of tantalum in the two oxyfluorides induce record short PM wavelengths (238 (KTOF) and 240 (RTOF) nm) for d0‐TM‐centered oxides, in addition to strong SHG responses (2.8 × KH2PO4 (KTOF) and 2.6 × KH2PO4 (RTOF)), and sufficient birefringences (0.092 (KTOF) and 0.085 (RTOF) at 546 nm). These results not only broaden the available strategies for achieving deep‐UV NLO materials by exploiting the currently neglected d0‐TMs, but also push the shortest PM wavelength into the short‐wavelength UV region.
Dual Catalysis of Gold Nanoclusters: Photocatalytic Cross‐Dehydrogenative Coupling by Cooperation of Superatomic Core and Molecularly Modified Staples**
Authors: Isozaki Katsuhiro , Iseri Kenta , Saito Ryohei , Ueda Kyosuke , Nakamura Masaharu 
Published: November 2023

AbstractThiolate‐protected gold nanoclusters (AuNCs) have attracted significant attention as nano‐catalysts, revealing a superatomic core and gold‐thiolate staples as distinct structural units. Here, we demonstrate the unprecedented dual catalytic activity of thiolate‐protected [Au25(SR)18]− nanoclusters, involving both photosensitized 1O2 generation by the Au13 superatomic core and catalytic carbon‐carbon bond formation facilitated by Au2(SR)3 staples. This synergistic combination of two different catalytic units enables efficient cross‐dehydrogenative coupling of terminal alkynes and tertiary aliphatic amines to afford propargylamines in high yields of up to 93 %. Mixed‐ligand AuNCs bearing both thiolate and alkynyl ligands revealed the intermediacy of the alkynyl‐exchanged AuNCs toward both photosensitization and C−C bond‐forming catalytic cycles. Density functional theory calculations also supported the intermediacy of the alkynyl‐exchanged AuNCs. Thus, the use of ligand‐protected metal nanoclusters has enabled the development of an exceptional multifunctional catalyst, wherein distinct nanocluster components facilitate cooperative photo‐ and chemo‐catalysis.
Increasing Reduction Potentials of Type 1 Copper Center and Catalytic Efficiency of Small Laccase from Streptomyces coelicolor through Secondary Coordination Sphere Mutations
Authors: Wang Jing‐Xiang , Vilbert Avery C. , Cui Chang , Mirts Evan N. , Williams Lucas H. , Kim Wantae , Jessie Zhang Y. , Lu Yi 
Published: November 2023

AbstractThe key to type 1 copper (T1Cu) function lies in the fine tuning of the CuII/I reduction potential (E°′T1Cu) to match those of its redox partners, enabling efficient electron transfer in a wide range of biological systems. While the secondary coordination sphere (SCS) effects have been used to tune E°′T1Cu in azurin over a wide range, these principles are yet to be generalized to other T1Cu‐containing proteins to tune catalytic properties. To this end, we have examined the effects of Y229F, V290N and S292F mutations around the T1Cu of small laccase (SLAC) from Streptomyces coelicolor to match the high E°′T1Cu of fungal laccases. Using ultraviolet‐visible absorption and electron paramagnetic resonance spectroscopies, together with X‐ray crystallography and redox titrations, we have probed the influence of SCS mutations on the T1Cu and corresponding E°′T1Cu. While minimal and small E°′T1Cu increases are observed in Y229F‐ and S292F‐SLAC, the V290N mutant exhibits a major E°′T1Cu increase. Moreover, the influence of these mutations on E°′T1Cu is additive, culminating in a triple mutant Y229F/V290N/S292F‐SLAC with the highest E°′T1Cu of 556 mV vs. SHE reported to date. Further activity assays indicate that all mutants retain oxygen reduction reaction activity, and display improved catalytic efficiencies (kcat/KM) relative to WT‐SLAC.
In Situ Photoisomerization of an Azobenzene‐Based Triple Helicate with a Prolonged Thermal Relaxation Time
Authors: Zhu Jiajia , Sun Xiao‐Wen , Yang Xintong , Yu Shu‐Na , Liang Lin , Chen Ya‐Zhi , Zheng Xiaoyan , Yu Meng , Yan Li , Tang Juan , Zhao Wei , Yang Xiao‐Juan , Wu Biao 
Published: November 2023

AbstractThe phosphate‐coordination triple helicates A2L3 (A=anion) with azobenzene‐spaced bis‐bis(urea) ligands (L) have proven to undergo a rare in situ photoisomerization (without disassembly of the structure) rather than the typically known, stepwise “disassembly‐isomerization‐reassembly” process. This is enabled by the structural self‐adaptability of the “aniono” assembly arising from multiple relatively weak and flexible hydrogen bonds between the phosphate anion and bis(urea) units. Notably, the Z→E thermal relaxation rate of the isomerized azobenzene unit is significantly decreased (up to 20‐fold) for the triple helicates compared to the free ligands. Moreover, the binding of chiral guest cations inside the cavity of the Z‐isomerized triple helicate can induce optically pure diastereomers, thus demonstrating a new strategy for making light‐activated chiroptical materials.
Fabrication of nano calcium fluoride impregnated organic polyester alkyd coating for anticorrosive and antibacterial applications
Authors: Benitha V. S. , Jeyasubramanian K. , Vijayakumari B. , Prabhin V. S. 
Published: November 2023

AbstractThe advent of organic polyester alkyd resin has revolutionized the coating industry due to its good adherence to any substrate, high gloss, and greater drying speed. This work deals with the characterization of nano calcium fluoride (CaF2 Nps) incorporated polyester alkyd coating for efficient multifunctional coating applications. The CaF2 Nps are prepared by employing a facile co‐precipitation process. The prepared particles are characterized using X‐ray diffraction analysis (XRD) and scanning electron microscopy (SEM) to analyze their size and morphology. By employing the ball milling technique, the CaF2 Nps along with other additives are mixed with alkyd resin to form a coating. The spreading ability, volatile and non‐volatile content, surface roughness, and coating thickness are evaluated. The minimal inhibitory concentration (MIC) is estimated by the turbidimetric assay method against gram‐negative and gram‐positive bacteria strains. Since these pigments hold very good antibacterial properties, the CaF2 are impregnated in alkyd resin coating, in which CaF2 nanoparticles are used as pigments. To reduce the nosocomial infection spreading in the hospital environment the formulated paint is analyzed for its antibacterial and anticorrosive studies. The current study confirmed CaF2 impregnated organic alkyd resin coating possesses promising comparable properties which would be a good choice for coatings, addressing multifunctional properties.
Under whose wings? A conceptual model for incorporating historical sovereignty information in biodiversity data
Authors: Cheng Yi‐Yun 
Published: November 2023

AbstractLinking historical and contemporary geographic information in biodiversity data is a useful approach to approximate species population. However, one of the prominent factors that causes ambiguity in geographic information, and hinders the linking process, is the way sovereignty information is used. While historical biodiversity records often use sovereignties as proxies for geographic information about a species, contemporary records do not. This study proposes a conceptual model that incorporates sovereignty information in biodiversity data to foster the linkage between historical and contemporary geographical information. The model comprises two phases: the first phase relates tangible data sources and core components needed to construct historical sovereignty taxonomies; and the second phase is a process model to align historical sovereignty taxonomies with contemporary taxonomies in four phases. The output of the model presents all possible sovereignties that a geographic entity belongs to based on the degree of congruence between the historical and contemporary taxonomies. The contributions of this work are threefold: (1) making all possible ambiguities in historical geographic information explicit in biodiversity data; (2) bringing attention to the modeling choices that domain experts have to make when deciding which sovereignty a place name belongs to; and (3) extending and improving current geo‐referencing practices.
Converting coconut meal into biothermoplastics for industrial applications
Authors: Reddy Narendra , Guna Vijaykumar , GS Nagananda , Muppuri Supritha , Aramwit Pornanong 
Published: November 2023

AbstractWe present a simple approach to convert coconut (copra) oil cake into biothermoplastics with properties that are suitable for replacing synthetic polymer‐based plastics in current use. About 1.9 million tons of copra meal are generated ever year as coproducts and are available at $0.50–$0.60 per kilogram, making it a renewable, sustainable and low‐cost raw material. Despite containing proteins, carbohydrates and oil, there are limited non‐food applications of oil meals since most oil meals are typically non‐thermoplastic and hence difficult to be processed into bioproducts. In this study, we report the processing of copra meal into biothermoplastics in the presence of various plasticizers, heat and pressure. Compression molded films and bioproducts were developed from copra meal by heating at 130°C in the presence of glycerol, coconut oil or cashew shell oil as plasticizer. The films obtained had tensile strength of up to 4.4 MPa and were inherently stable in water. A one‐step crosslinking with citric acid was done to further improve the strength and stability of the films. With large availability at low cost, copra meal provides an opportunity to develop low‐cost, biodegradable, edible and innovative bioproducts that have the potential to replace the synthetic polymer‐based plastics in current use, particularly single‐use plastics.
Implementing skill‐based treatment within a classroom setting for an adolescent with autism
Authors: Cervi Rebecca , Gruber Deborah J. , Napolitano Deborah A. 
Published: November 2023

AbstractResearch exists to support the efficacy of the Interview‐Informed Synthesized Contingency Analysis (IISCA) and skill‐based treatment (SBT) to address problem behavior within a clinical setting. However, limited research is available to support their use in a classroom setting and especially as a tool to avoid the display of problem behavior altogether. In the current study, the IISCA, informed by an open‐ended interview, was conducted with a single participant in the classroom after a prolonged absence from school due to COVID‐19. Results of the IISCA were used to determine the multiple contingencies that were likely to evoke problem behavior upon re‐introduction of academic task demands. A skill‐based treatment was then developed based on these contingencies, which involved teaching the participant functional communication, delay tolerance, and following academic instruction in relevant contexts. After 25 treatment sessions, the participant had acquired and maintained all of these skills, including the ability to functionally communicate, tolerate removal of preferred items, and follow educational instructions within the typical classroom routine. This study shows the applicability of the IISCA and SBT when implemented within the classroom setting and when used to reintroduce educational instruction to an individual with autism after a prolonged break from school.
Synthesis and application of hypochlorite mediated acylhydrazone fluorescence probes
Authors: Zhang Chenglu , Li Xiangling , Wang Yiming , Nie Shiru , Liu Chang 
Published: November 2023

AbstractHypochlorous acid (HClO/ClO−) is one of the important reactive oxygen species (ROS). It acts as a second signaling molecule within and between cells and is an indispensable active molecule in living organisms to regulate physiological and pathological processes. In this article, two fluorescent probes (PTF and PTA) for highly selective fluorescent recognition of ClO− were successfully synthesized based on the ICT mechanism by condensing phenothiazines with two hydrazides via the hydrazide structure (). PTF can identify different concentrations of ClO− in two steps. Due to its ClO− two site recognition, the probe exhibited good selectivity (specific recognition of ClO− over a wide concentration range), a fast time response (rapid recognition in seconds), a sufficiently low detection limit (3.6 and 11.0 nM), and large Stokes shifts (180 and 145 nm). Furthermore, the recognition of ClO− by contrasting probes with different substituents exhibited different fluorescence changes of ratiometric type and turn‐off. PTF successfully achieves the detection of exogenous and endogenous ClO− in aqueous solution and living cells.
Validation of the online version of the sharenting evaluation scale (SES) in Iranian parents: Psychometric properties and concurrent validity
Authors: Peimanpak Faezeh , Abdollahi Abbas , Allen Kelly A. , Rakhmatova Feruza Abulkosimovna , Aladini Alaa , Alshahrani Shadia Hamoud , Brewer Jocelyn 
Published: November 2023

AbstractIntroductionThis study examines the psychometric properties of the online version of the sharenting evaluation scale (SES) with a sample of Iranian parents.MethodsA sample population of 240 parents (25% fathers and 75% mothers) with an average age of 39.63 (standard deviation = 10.41) were selected by convenience sampling method and completed the Persian version of the SES online.ResultsFindings showed that concurrent validity of the SES with social comparison and social well being was within the acceptable range. The Cronbach's alpha coefficient for the SES was 0.92, and for the subscales of self‐control, social behavior, and implications were, respectively, 0.84, 0.71, and 0.70, which indicated good internal consistency between the items. Confirmatory factor analysis supported the Persian version of this scale same as the English version. The Persian version of the SES demonstrated psychometric properties of validity and reliability within the acceptable range (α = .70 and .84). In the present study, the results of convergent validity showed that there is a positive and significant relationship between sharing and constructs, such as social comparison, self‐control, implications, and social behaviors, but no significant relationship was found between social well being and sharing.ConclusionsPersian version of the SES is a suitable scale to measure the degree to which parents share their children's sensitive content on the Internet and social media.
The mitotic cell cycle‐associated nomogram predicts overall survival in lung adenocarcinoma
Authors: He Xu , Zhou Huafu , Huang Qianyu , Li Yue 
Published: November 2023

AbstractBackgroundThis study aimed to develop a prognostic model for lung adenocarcinoma (LUAD) associated with mitotic cell cycle. The model will predict the probability of survival at different time points and serve as a reference tool to evaluate the effectiveness of LUAD treatment.MethodsA cohort of 442 patients with LUAD from the gene expression omnibus (GEO) database was randomly divided into a training group (n = 299) and a validation group (n = 99). The least absolute shrinkage and selection operator (LASSO)‐COX algorithm was used to reduce the number of predictors based on the clinicopathological and RNA sequencing data to establish mutant characteristics that could predict patient survival. Additionally, gene ontology (GO), Kyoto Encyclopedia of Genes and Genomes (KEGG), gene set variation analysis (GSVA), and gene set enrichment analysis (GSEA) analyses were conducted on the mutant characteristics. The performance of the developed nomogram was evaluated using calibration curves and the C‐index.ResultsThe mutant characteristics had prognostic value for LUAD and acted as an independent prognostic factor. The mutant characteristics profile derived from the LASSO‐COX algorithm demonstrated a significant association with overall survival in patients with LUAD. Functional annotation based on the mutant score, its involvement in the phase transition of the mitotic cell cycle, and its regulatory processes. The nomogram, which combined the mutant score with clinical factors associated with prognosis, showed robust accuracy in both the training and validation groups.ConclusionThis study presents the first individualized model that establishes a mutant score for predicting survival in LUAD. This model can be used as a predictive tool for determining 1‐, 2‐, 3‐, and 5‐year survival probabilities in patients with LUAD.
The impact of intensity‐modulated radiotherapy in conjunction with chemotherapy on proximal pT3N0 rectal cancer patients after total mesorectum excision
Authors: Fang Chuan‐Yin , Chen Hsuan‐Yu , Yang Hsin‐Yi , Tsang Yuk‐Wah , Lee Cheng‐Yen , Chang Chih‐Chia , Lin I‐Chen , Huang Yun‐Jhong , Chu Chun‐Ting , Wang Yu‐Wen 
Published: November 2023

AbstractBackgroundThis study aimed to ascertain if the incorporation of intensity‐modulated radiotherapy (IMRT) with chemotherapy (CTx) offered any advantages for patients diagnosed with stage pT3N0 rectal cancer located in the proximal (upper) region following a complete total mesorectum excision (TME).MethodsWe retrospectively examined medical records of stage II/III rectal cancer patients who had undergone CTx or concurrent chemoradiation (CCRT) with IMRT after a successful TME. We juxtaposed a variety of survival outcomes across two patient cohorts. Each outcome was further classified according to Gunderson's risk stratification between proximal and distal (middle and low) rectal cancer patients, and we evaluated the factors associated with each outcome.ResultsThe median follow‐up duration was 4.9 years. Our research comprised 236 rectal adenocarcinoma patients treated at our institution between 2007 and 2019. They received either the CTx (n = 135) or the CCRT (n = 101) with 10‐year locoregional recurrence‐free survival (LRRFS) of 90.1% and 96.1%, respectively (p = 0.163). However, after performing multivariate adjustments, a pattern emerged hinting at a better LRRFS for the CCRT group (p = 0.052). Perforation had a strong correlation with locoregional recurrence. No significant differences were observed in other survival between the two treatment arms and their respective subgroups. The CCRT group witnessed significantly higher immediate and chronic complications with p = 0.007 and 0.009, respectively. The CCRT group had two secondary cancer‐related fatalities (2%, one attributed to IMRT), and another reported by the CTx group (1%). The sole classified locoregional recurrence within the cohort of 37 individuals treated with CTx for proximal pT3N0 rectal cancer was, in fact, the development of sigmoid colon cancer.ConclusionThe results suggest that for patients with proximal pT3N0 rectal cancer post‐TME, IMRT is better when not combined with CTx, except in highly perilous scenarios or those involving perforation.
A realist evaluation of an enhanced court‐based liaison and diversion service for defendants with neurodevelopmental disorders
Authors: Chaplin Eddie , McCarthy Jane , Marshall‐Tate Karina , Ali Salma , Harvey Denise , Childs Jessica , Xenitidis Kiriakos , Srivastava Samir , McKinnon Iain , Robinson Louise , Allely Clare S. , Hardy Sally , Forrester Andrew 
Published: November 2023

AbstractBackgroundIn England, court‐based mental health liaison and diversion (L&D) services work across courts and police stations to support those with severe mental illness and other vulnerabilities. However, the evidence around how such services support those with neurodevelopmental disorders (NDs) is limited.AimsThis study aimed to evaluate, through the lens of court and clinical staff, the introduction of a L&D service for defendants with NDs, designed to complement the existing L&D service.MethodsA realist evaluation was undertaken involving multiple agencies based within an inner‐city Magistrates' Court in London, England. We developed a logic model based on the initial programme theory focusing on component parts of the new enhanced service, specifically training, screening, signposting and interventions. We conducted semi‐structured interviews with the court staff, judiciary and clinicians from the L&D service.ResultsThe L&D service for defendants with NDs was successful in identifying and supporting the needs of those defendants. Benefits of this service included knowledge sharing, awareness raising and promoting good practice such as making reasonable adjustments. However, there were challenges for the court practitioners and clinicians in finding and accessing local specialist community services.ConclusionA L&D service developed for defendants with NDs is feasible and beneficial to staff and clinicians who worked in the court setting leading to good practice being in place for the defendants. Going forward, a local care pathway would need to be agreed between commissioners and stakeholders including the judiciary to ensure timely and equitable access to local services by both defendants and practitioners working across diversion services for individuals with NDs.
Reductive Release from a Hybrid PKS‐NRPS during the Biosynthesis of Pyrichalasin H
Authors: Heinemann Henrike , Zhang Haili , Cox Russell J. 
Published: November 2023

AbstractThree central steps during the biosynthesis of cytochalasan precursors, including reductive release, Knoevenagel cyclisation and Diels Alder cyclisation are not yet understood at a detailed molecular level. In this work we investigated the reductive release step catalysed by a hybrid polyketide synthase non‐ribosomal peptide synthetase (PKS‐NRPS) from the pyrichalasin H pathway. Synthetic thiolesters were used as substrate mimics for in vitro studies with the isolated reduction (R) and holo‐thiolation (T) domains of the PKS‐NRPS hybrid PyiS. These assays demonstrate that the PyiS R‐domain mainly catalyses an NADPH‐dependent reductive release of an aldehyde intermediate that quickly undergoes spontaneous Knoevenagel cyclisation. The R‐domain can only process substrates that are covalently bound to the phosphopantetheine thiol of the upstream T‐domain, but it shows little selectivity for the polyketide.
Organophotocatalyzed Alkyl/Arylsulfonylation of Vinylcyclopropanes
Authors: Chandu Palasetty , Mallick Manasi , Srinivasu Vinjamuri , Sureshkumar Devarajulu 
Published: November 2023

AbstractAllyl sulfones are an essential pharmacophore in many bioactive compounds. To combat their synthetic barrier, we report a practical, straightforward organophotocatalyzed methodology for accessing miscellaneously functionalized allyl sulfone derivatives using inexpensive and bench‐stable sodium sulfinate salts under mild conditions. This photo‐catalyzed radical sulfonylation provides access to a variety of allyl sulfones in good to excellent yields with high E : Z selectivity. A wide range of vinyl cyclopropanes, as well as aryl/hetero and alkyl sodium sulfinates, were tolerated and reliable in gram‐scale synthesis. Later on, further functionalization of allyl sulfones was demonstrated. A plausible mechanism for radical sulfonylation is proposed from the control experiments.