bluuebunny/crossref_metadata_2025_split huggingface dataset:
Heterocyclic and Alkyne Terpenoids by Terpene Synthase‐Mediated Biotransformation of Non‐Natural Prenyl Diphosphates: Access to New Fragrances and Probes
Authors: Weigel Benjamin , Ludwig Jeanette , Weber Roman A. , Ludwig Steve , Lennicke Claudia , Schrank Paul , Davari Mehdi D. , Nagia Mohamed , Wessjohann Ludger A. 
Published: September 2022

AbstractTwo terpene cyclases were used as biocatalytic tool, namely, limonene synthase from Cannabis sativa (CLS) and 5‐epi‐aristolochene synthase (TEAS) from Nicotiana tabacum. They showed significant substrate flexibility towards non‐natural prenyl diphosphates to form novel terpenoids, including core oxa‐ and thia‐heterocycles and alkyne‐modified terpenoids. We elucidated the structures of five novel monoterpene‐analogues and a known sesquiterpene‐analogue. These results reflected the terpene synthases′ ability and promiscuity to broaden the pool of terpenoids with structurally complex analogues. Docking studies highlight an on‐off conversion of the unnatural substrates.
Chemically Enhanced Immunogenicity of Bacteria by Supramolecular Functionalization with an Adjuvant
Authors: Duszenko Nikolas , van Willigen Danny M. , Bunschoten Anton , Velders Aldrik H. , Roestenberg Meta , van Leeuwen Fijs W. B. 
Published: September 2022

AbstractMany pathogens blunt immune responses because they lack immunogenic structural features, which typically results in disease. Here, we show evidence suggesting that pathogen immunogenicity can be chemically enhanced. Using supramolecular host‐guest chemistry, we complexed onto the surface of a poorly immunogenic bacterium (Staphylococcus aureus) a TLR7 agonist‐based adjuvant. “Adjuvanted” bacteria were readily recognized by macrophages and induced a more pro‐inflammatory immunophenotype. Future applications of this concept could yield treatment modalities that bolster the immune system's response to pathogenic microbes.
An Integrated Cathode Engineered by Hierarchical Honeycomb‐Like Copper‐Molybdenum Sulfide Nanosheets for Hybrid Supercapacitor with Improved Energy Storage Capability
Authors: Li Chao , Li Longbo , Liu Qiong , Liu Lu , Zha Ruhua , Zhang Yu , Li Qing , Fang Linxia 
Published: September 2022

AbstractThe construction of integrated electrodes has been considered as a sensible strategy to boost the electrochemical properties of supercapacitors, which feature improved electron and ion transfer kinetics. In this work, a facile and easy‐controlled synthetic methodology has been established to assemble hierarchical honeycomb‐like copper‐molybdenum sulfide nanosheets (Cu−Mo−S NSs) on a three‐dimensional (3D) porous nickel foam substrate as integrated cathodes for hybrid supercapacitors (HSCs). As expected, the Cu−Mo−S NSs deliver exceptional electrochemical properties including an areal capacity of 1.39 mAh cm−2 at 2 mA cm−2, a superb rate capability (0.86 mAh cm−2 at 20 mA cm−2), and especially, a prominent cycling lifespan with 95.3 % capacity retention after 10000 cycles. Moreover, the as‐obtained Cu−Mo−S NSs are used as integrated cathodes to pair with iron oxide particles encapsulated in reduced graphene oxide (Fe2O3@rGO) as anodes for assembling Cu−Mo−S NSs//Fe2O3@rGO HSCs, which can deliver superior energy density of 79.04 Wh kg−1 and exceptional cyclic stability with 94.9 % capacity retention after 10000 cycles.
Robust Spirobifluorene Core Based Hole Transporters with High Mobility for Long‐Life Green Phosphorescent Organic Light‐Emitting Devices
Authors: Nagamura Natsuo , Sasabe Hisahiro , Sato Hiroki , Ito Nozomi , Abe Shoki , Sukegawa Yoshihito , Yokoyama Daisuke , Kaji Hironori , Kido Junji 
Published: September 2022

AbstractUsing a tailored high triplet energy hole transport layer (HTL) is a suitable way to improve the efficiency and extend the lifetime of organic light‐emitting devices (OLEDs), which can use all molecular excitons of singlets and triplets. In this study, dibenzofuran (DBF)‐end‐capped and spirobifluorene (SBF) core‐based HTLs referred as TDBFSBF1 and TDBFSBF2 were effectively developed. TDBFSBF1 exhibited a high glass transition temperature of 178 °C and triplet energy of 2.5 eV. Moreover, a high external quantum efficiency of 22.0 %, long operational lifetime at 50 % of the initial luminance of 89,000 h, and low driving voltage at 1000 cd m−2 of 2.95 V were achieved in green phosphorescent OLEDs using TDBFSBF1. Further, a high‐hole mobility μh value of 1.9×10−3 cm2 V−1 s−1 was recorded in TDBFSBF2. A multiscale simulation successfully reproduced the experimental μh values and indicated that the reorganization energy was the primary factor in determining the mobility differences among these SBF core based HTLs.
Agar Plate‐Based Screening Approach for the Identification of Enzyme‐Catalyzed Oxidations
Authors: Kinner Alina , Lütz Stephan , Rosenthal Katrin 
Published: September 2022

AbstractBiocatalytic oxidation reactions are in high demand. Among the applied enzymes, the heme‐thiolate enzyme subfamily of unspecific peroxygenases (UPOs), which relies on hydrogen peroxide as cosubstrate and oxidant, has generated great interest. Almost two decades after their first description, databases provide thousands of putative UPO sequences, but only a few enzymes have been characterized. To address this gap, efficient screening methods for the identification of novel UPOs are necessary. Here, a new screening strategy is presented based on solid cultivation of wild‐type fungi. The identification of a promising candidate strain highlights the applicability of this approach.
Reducing smearing effect in contribution plots and improving fault detection via polynomial approximated isomap embeddings
Authors: Alakent Burak 
Published: September 2022

AbstractDimension reduction is an essential method used in multivariate statistical process monitoring for fault detection and diagnosis. Principal component analysis (PCA) and independent component analysis (ICA) are the most frequently used linear dimensional reduction tools, and the contribution plot is the most popular fault isolation method in the absence of any prior information on the faults. These methods, however, come with their shortcomings. The fault detection capability of linear methods may not be sufficient for non‐linear processes, and smearing effect is known to deteriorate the diagnostics obtained from contribution plots. While the fault detection rate may be increased by kernelized methods or deep artificial neural network models, tuning data‐dependent hyperparameter(s) and network structure with limited historical data is not an easy task. Furthermore, the resulting non‐linear models often do not directly possess fault isolation capability. In the current study, we aim to devise a novel method named ICApIso‐PCA, which offers non‐linear fault detection and isolation in a rather straightforward manner. The rationale of ICApIso‐PCA mainly involves building a non‐linear scores matrix, composed of principal component scores and high‐order polynomial approximated isomap embeddings, followed by implementation of the ICA‐PCA algorithm on this matrix. Applications on a toy dataset and the Tennessee Eastman plant show that theI2index from ICApIso‐PCA yields a high fault detection rate and offers accurate contribution plots with diminished smearing effects compared to those from traditional monitoring methods. Easy implementation and the potential for future research are further advantages of the proposed method.
Practical Synthesis of NFSI Derivatives through ArSO2NHF without F2
Authors: Zhang Yu‐Yang , Xu Xiu‐Hua , Qing Feng‐Ling 
Published: September 2022

Comprehensive SummaryN‐Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine‐containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed and synthesized to modify the reactivity and/or selectivity of the parent reagent. However, the hazardous F2 was inevitably required for the synthesis of NFSI derivatives. Herein, we disclosed a practical synthesis of various NFSI derivatives without F2 in common organic chemistry laboratories. This synthetic protocol started from NFSI through pyridine‐promoted desulfonylation for formation of N‐fluoroarenesulfonamide (ArSO2NHF) and followed by condensation with arenesulfonyl chlorides. The reduction potentials and fluorinating reactivities of these NFSI derivatives demonstrated that NFSI derivatives bearing the electron‐withdrawing groups on benzene ring had the higher oxidizing and fluorinating abilities than NFSI.
DFT Insights into the Variety in the Coordination Modes of the Equatorial Halides in [Au13Ag12(PR3)10X8]+ (X=Cl/Br) Clusters
Authors: Wu Xiaohang , Weng Shiyin , Lv Ying , He Shuping , Yu Haizhu 
Published: September 2022

AbstractThe bonding character within metal nanoclusters represents an intriguing topic, shedding light on the inherent driving force for the packing preference in nanomaterials. Herein, density functional theory (DFT) calculations were conducted to investigate the correlation of the series of isomeric [Au13Ag12(PR3)10X8]+ (X=Cl/Br) clusters, which are mainly differentiated by the coordination mode of the equatorial halides (μ2‐, μ3‐ and μ4‐) in the rod‐like, bi‐icosahedral framework. The theoretical simulation corroborates the variety in the configuration of the Au13Ag12 clusters and elucidates the fast isomerization kinetics among the different configurations. The easy tautomerization and the variety in chloride binding modes correspond to a fluxionality character of the equatorial halides and are verified by the potential energy curve analysis. The structural flexibility of the central Au3Ag10 block is the main driving force, while the relatively stronger Ag−X bonding interaction (compared to that of Au−X), and a sufficient number of halides are also requisite for the associating Ag−X tautomerizations.
English as an additional language (EAL): Decolonising provision and practice
Authors: Welply Oakleigh 
Published: September 2022

AbstractThis paper examines ways in which approaches to English as Additional Language (EAL) can be decolonised in schools. In an attempt to break traditional divides between academic research and pedagogical practice in this area, this article adopts a collaborative perspective, between an EAL advisory and support teacher and an academic member of staff working in university. Drawing on dialogues and co‐analysis with EAL practitioners, this article reflects on limitations of current provision and practice and suggests alternative, decolonial and anti‐racist approaches to the education of EAL students. At both school and university level, ‘one size fits all approaches’ tend to negate the deep historical, social and political roots and contexts which underpin the experiences of ‘EAL students’ at different levels of education. Issues related to equitable assessment, inclusion, linguistic support and anti‐racism tend to be side lined in favour of a focus on language proficiency and attainment, which most often overshadows the complex experiences and needs of students labelled ‘EAL’. In this respect, the questions of relevant, decentred and decolonised curricula and forms of assessment that can promote inclusion for students who have experienced migration and are placed in monolingual educational environments in the UK are crucial. Through a decolonial perspective on the curriculum, language and pedagogical practice, inspired by postcolonial studies and Critical Race Theory, this paper discusses three main areas that emerged as crucial to a deeper and critical engagement with English as an Additional Language and the experience of students: (1) the need for a critical reflection on ideas of inclusion and mainstreaming; (2) active anti‐racist work in schools and initial teacher training; and (3) decolonising assessment.
A novel relay‐aided centralized cooperative spectrum sensing scheme using radio frequency energy harvesting
Authors: Majumdar Suvaditya , Thakur Chandrima , Chattopadhyay Sudipta 
Published: September 2022

SummaryIn a cooperative spectrum sensing (CSS) network, the primary signal can be used as a radio frequency (RF) source in order to power the energy‐constrained sensor nodes of the secondary network. This work presents a novel hybrid model combining an optimal relay selection scheme to incorporate RF energy harvesting in a centralized CSS network. The secondary users, which are equipped with RF energy harvesting capabilities, act as relays in order to forward the sensing information to a fusion center. Here, we have derived an enhanced multi‐relay selection strategy to maximize the end‐to‐end signal‐to‐noise ratio of the links. Furthermore, a new voting rule is proposed based on the generalized K‐out‐of‐M rule, such that it minimizes our objective error function. The performance analysis of our proposed model is presented with respect to the flexible relay positions. We have used complementary receiver operating characteristic curves for analyzing the detection performance of the CSS model with our derived voting rule. Simulation results using MATLAB show that the proposed model gives a better detection probability and a smaller error rate than some related existing works.
Interpretable deep learning‐based hippocampal sclerosis classification
Authors: Kim Dohyun , Lee Jungtae , Moon Jangsup , Moon Taesup 
Published: September 2022

AbstractObjectiveTo evaluate the performance of a deep learning model for hippocampal sclerosis classification on the clinical dataset and suggest plausible visual interpretation for the model prediction.MethodsT2‐weighted oblique coronal images of the brain MRI epilepsy protocol performed on patients were used. The training set included 320 participants with 160 no, 100 left and 60 right hippocampal sclerosis, and cross‐validation was implemented. The test set consisted of 302 participants with 252 no, 25 left and 25 right hippocampal sclerosis. As the test set was imbalanced, we took an average of the accuracy achieved within each group to measure a balanced accuracy for multiclass and binary classifications. The dataset was composed to include not only healthy participants but also participants with abnormalities besides hippocampal sclerosis in the control group. We visualized the reasons for the model prediction using the layer‐wise relevance propagation method.ResultsWhen evaluated on the validation of the training set, we achieved multiclass and binary classification accuracy of 87.5% and 88.8% from the voting ensemble of six models. Evaluated on the test sets, we achieved multiclass and binary classification accuracy of 91.5% and 89.76%. The distinctly sparse visual interpretations were provided for each individual participant and group to suggest the contribution of each input voxel to the prediction on the MRI.SignificanceThe current interpretable deep learning‐based model is promising for adapting effectively to clinical settings by utilizing commonly used data, such as MRI, with realistic abnormalities faced by neurologists to support the diagnosis of hippocampal sclerosis with plausible visual interpretation.
OSL‐14C‐10Be: A novel composite geochronometer for simultaneous quantification of timing and magnitude of change in bedrock outcrop erosion rate
Authors: Sohbati Reza , Hippe Kristina 
Published: September 2022

AbstractQuantifying past changes in erosion rate is essential for deciphering earth surface processes and their driving mechanisms. Coupledin situcosmogenic14C‐10Be has been shown to be a useful chronometer in detecting changes in erosion rate, but its detection ability is limited to rapidly eroding fluvial landscapes and changes greater than a factor of two; and in any case, it cannot uniquely quantify both the magnitude and the timing of change in erosion rate. Here, we establish a theoretical framework to show that this limitation can be overcome by combining the recently developed optically stimulated luminescence (OSL) rock surface exposure dating with the14C‐10Be chronometer. We demonstrate that the resulting OSL‐14C‐10Be composite geochronometer can determine both the magnitude and the timing of an abrupt change in bedrock erosion rate by a factor of < 0.8 or > 1.2 over 100–104a timescales, where erosion rates are < 10−2 cm a−1.
Intermediate‐sulfidation epithermal mineralization at Monterado goldfield in Western Borneo (Indonesia): Geological, mineralogical, and fluid inclusion microthermometric perspectives
Authors: Ilmawan Ilham , Idrus Arifudin , Lai Chun‐Kit , Dana Cendi Diar Permata , Nugroho Andhika Patria Adi 
Published: September 2022

Gold mining in Western Borneo can be traced back over a century in the Dutch era. Many of these gold deposits are hosted in auriferous quartz veins, yet their geology and alteration/mineralization features have never been well documented. In this study, we present the first detailed account on gold mineralization in Western Borneo, using the Monterado goldfield as an example. Our results reveal that the auriferous quartz veining occurred in both intrusions (Mensibau granodiorite and Sintang Suite diorite porphyry) and volcanic‐sedimentary sequences (Raya Volcanics and Hamisan Formation), and wallrock alterations are well developed. Distributions of the veins are controlled largely by N‐S‐trending (tensional veins, e.g., Nek Rimban and Muisan) and NW‐SE (en‐échelon tensional gash veins, e.g., Mertua, Lipan, and Sekar) structures. Vein textures include mainly massive, breccia, comb, drusy, and stockwork. Advanced Mineral Identification and Characterization System mineral mapping on the ore veins and mineralized wallrocks show the presence of electrum, acanthite, pyrite, chalcopyrite, bornite, sphalerite, galena, and supergene products such as malachite, covellite, cuprite, chalcocite and rosasite. Polymetallic sulfide mineralization is spatially associated with adularia within auriferous quartz veins and silicic alteration. Ore chemistry on 285 vein ore samples yielded on average 1.46 g/t Au and 6.58 g/t Ag. Fluid inclusion microthermometry indicates that the homogenization temperature ranges from 273 to 362°C (avg. 338°C), with salinities of 1.1–8.7 wt% NaCl eq. (avg. 4.4 wt% NaCl eq.). Accordingly, the Monterado Au–Ag quartz vein‐type mineralization is best classified as intermediate‐sulfidation epithermal style.
Strengthening internal accountability by avoiding fantasy documents in responsibility center budgeting
Authors: Harris Nathan F. 
Published: September 2022

AbstractHigher education scholars often investigate the policy mechanisms of external accountability, but rarely explore institutional mechanisms of internal accountability. This chapter, which reports select findings from an in‐depth case study of institutional budgeting at an American public research university, examines an underexplored mechanism of internal accountability – annual budget reviews. The findings illustrate that the university's budget review often constitutes a fantasy practice that affirms the institution's commitment to fiscal prudence as much as scrutinizes budgetary decisions in academic units. The findings reveal opportunities to strengthen budget reviews at institutions that have adopted decentralized budget models such as Responsibility Center Budgeting.
The elderly prognostic index predicts early mortality in older patients with diffuse large B‐cell lymphoma. An ad hoc analysis of the elderly project by the Fondazione Italiana Linfomi
Authors: Cencini Emanuele , Tucci Alessandra , Puccini Benedetta , Cavallo Federica , Luminari Stefano , Usai Sara Veronica , Fabbri Alberto , Pennese Elsa , Marino Dario , Zilioli Vittorio Ruggero , Balzarotti Monica , Petrucci Luigi , Tafuri Agostino , Arcari Annalisa , Botto Barbara , Zanni Manuela , Hohaus Stefan , Sartori Roberto , Merli Michele , Gini Guido , Al Essa Wael , Musurca Gerardo , Tani Monica , Nassi Luca , Daffini Rosa , Mammi Caterina , Marcheselli Luigi , Bocchia Monica , Spina Michele , Merli Francesco 
Published: September 2022

AbstractThe Elderly Prognostic Index (EPI) is based on the integration of a simplified geriatric assessment, hemoglobin levels and International Prognostic Index and has been validated to predict overall survival in older patients with diffuse large B‐cell lymphoma (DLBCL). In this study, we evaluated the ability of EPI to predict the risk of early mortality. This study included all patients registered in the Elderly Project for whom treatment details and a minimum follow‐up of 3 months were available. Three main treatment groups were identified based on the anthracycline amount administered: cases receiving >70% of the theoretical anthracyclines dose (Full Dose [FD] group), ≤70% (Reduced Dose [RD]) and palliative therapy (PT; no anthracyclines). The primary endpoint was early mortality rate, defined as death for any cause occurring within 90 days from diagnosis. We identified 1150 patients with a median age of 76 years (range 65–94). Overall, 69 early deaths were observed, accounting for 19% of all reported deaths. The cumulative rate of early mortality at 90 days was 6.0%. Comparing early with delayed deaths, we observed a lower frequency of deaths due to lymphoma progression (42% vs. 75%; p < 0.001) and a higher frequency due to toxicity and infections (22% vs. 4%, p < 0.001, and 22% vs. 3%, p < 0.001, respectively) for early events. A multivariable logistic analysis on 931 patients (excluding PT) confirmed an independent association of high‐risk EPI (odds ratio [OR] 3.60; 95% confidence interval [CI] 1.15–11.2) and bulky disease (OR 2.08; 95% CI 1.09–3.97) with the risk of early mortality. The cumulative incidence of early mortality for older patients with DLBCL is not negligible and is mainly associated with non‐lymphoma related events. For patients receiving anthracyclines, high‐risk EPI and bulky disease are associated with a higher probability of early mortality.
Re‐intervention with 10‐mm vs 12‐mm covered self‐expandable metallic stent for recurrent unresectable distal biliary obstruction in patients with previous stent implantation
Authors: Chikugo Koki , Hayashi Tsuyoshi , Tanaka Kazunari , Kin Toshifumi , Toyonaga Haruka , Nasuno Osamu , Ishii Tatsuya , Takahashi Kuniyuki , Yamazaki Hajime , Katanuma Akio 
Published: September 2022

AbstractBackgroundTreatment for unresectable distal malignant biliary obstruction (DMBO) involves placing a 10‐mm covered self‐expandable metallic stent (CSEMS). In recurrent biliary obstruction (RBO), replacement of the CSEMS is recommended; however, the appropriate stent type remains unknown. We speculated that large‐bore CSEMSs would provide longer patency. We compared the efficacy of 10‐mm and 12‐mm CSEMS in patients with RBO.MethodsWe retrospectively retrieved data on patients who underwent CSEMS replacement from the endoscopic database. We investigated the time to RBO (TRBO) after CSEMS replacement. The hazard ratio (HR) for the the second TRBO was estimated using the Cox proportional hazard model. The estimated median second TRBO was determined using the Kaplan‐Meier method.ResultsAmong the 493 patients with DMBOs treated with 10‐mm CSEMS, 48 and 29 patients underwent re‐intervention with 10‐mm and 12‐mm CSEMS, respectively. The use of 12‐mm CSEMS was inversely associated with second TRBO (multivariable‐adjusted HR, 0.62; 95% CI, 0.39‐0.98; P = .042). The estimated median second TRBO was greater with the 12 mm CSEMS than with the 10 mm variety (562 days vs 207 days; P = .019).ConclusionThe second intervention with 12‐mm CSEMS was associated with a longer TRBO.