bluuebunny/crossref_metadata_2025_split huggingface dataset:
Catalytic Hydrogenation of N‐protected α‐Amino Acids Using Ruthenium Complexes with Monodentate Phosphine Ligands
Authors: Saito Akari , Yoshioka Shota , Naruto Masayuki , Saito Susumu 
Published: November 2019

AbstractA ruthenium complex with a monodentate phosphine ligand was used to catalytically hydrogenate N‐protected α‐amino acids under essential retention of the configuration of their α‐chiral centers. Among the ligands tested for this hydrogenation, which proceeds at a relatively low temperature, tris(para‐fluorophenyl)phosphine exhibited the best performance. In comparison, electron‐rich monodentate, bidentate, and tridentate phosphines were far less effective. The precatalyst Ru(OAc)2[(p‐FC6H4)3P]2 was synthesized and isolated, and its structure was determined by a single‐crystal X‐ray diffraction analysis. N‐protected α‐amino acids with neutral alkyl side chains, including polar functional groups such as sulfides, indoles, ethers, phenols, pyrroles, and arenes, are compatible with the applied hydrogenation conditions, affording the corresponding optically active 2‐substituted‐2‐(1H‐pyrrol‐1‐yl)ethan‐1‐ol (2‐amino ethanol) derivatives in moderate to high yield.magnified image
Semicarbazide: A Transient Directing Group for C(sp3)−H Arylation of 2‐Methylbenzaldehydes
Authors: Wen Fei , Li Zheng 
Published: November 2019

AbstractSemicarbazide as an effective transient directing group for C(sp3)−H arylation of 2‐methylbenzaldehydes is described. Various substituted 2‐benzylbenzaldehydes are efficiently synthesized by this strategy. The salient features of this protocol are the use of inexpensive transient directing group, wide scope of substrates with good functional group compatibility, up to 98% yield, and applicability to gram scale.magnified image
Anti‐Muslim hate speech and displacement narratives: Case studies from Sri Lanka and Australia
Authors: Stewart James 
Published: November 2019

AbstractMuslim communities have frequently been the victim of vilification and discrimination in Australia and the broader Asian region. This article discusses and compares the narratives around Muslim vilification in Australia and Sri Lanka. Despite the fact that these two nations are vastly different in size, demographics and cultural history, I will argue that there are remarkable similarities in how Muslims are subject to attack in both nations. The hate speech occasioned against Muslims in Sri Lanka and Australia is shaped by almost identical narrative structures and is cultivated in similar online environments. In both cases, anti‐Muslim animus is fuelled by a fear of displacement and perceived contamination of what nativists regard as ethnically sovereign territory. I will argue that the underlying sub‐text in both cases is owed to a repulsion to the physical presence of Muslims which can be understood in terms of Mary Douglas' concept of the moral pollutant.
Sonographers’ communication in obstetrics: Challenges to their professional role and practice in Australia
Authors: Thomas Samantha , O'Loughlin Kate , Clarke Jillian 
Published: November 2019

AbstractIntroduction/PurposeDespite the clinical importance of patient‐centred care in the sonographer/patient interaction in obstetric ultrasound, there has been very little current research in Australia on sonographer and sonologist communication practices in the event of an adverse finding. This study sought the views, experiences and practices of Australian sonographers, particularly in relation to adverse findings, with consideration of the implications for their professional role and practice.MethodsQualified and trainee sonographers who perform obstetric ultrasound were invited to complete a survey through the Australasian Sonographers Association. Using qualitative methodology, the authors developed themes on a range of issues related to sonographer and sonologist communication practices and roles from responses to three open‐ended questions within the survey.ResultAnalysis of 249 responses revealed three distinct ‘Communicator types’. ‘Open Communicators’ confidently practice open and direct communication; ‘Limited Communicators’ perceived barriers preventing them from openly communicating; ‘Variable Communicators’ indicated various challenging ‘grey areas’ which created inconsistent communication practices. Variables, such as the complexity of an adverse finding and a reporting sonologist's role, attitude and level of control they exercised over sonographer communication, all influenced respondents’ communication practices. Respondents believed professional bodies should agree on a standardised policy regarding sonographers’ roles.DiscussionThis paper highlights the complexity of the sonographer/patient interaction and outlines the difficulty in providing true patient‐centred care in obstetric ultrasound.ConclusionThe need for a collaborative, patient‐focussed policy, which defines and recognises the role of the sonographer in the event of obstetric adverse findings, will improve the current model of care.
Total Synthesis of Talatisamine
Authors: Kamakura Daiki , Todoroki Hidenori , Urabe Daisuke , Hagiwara Koichi , Inoue Masayuki 
Published: November 2019

AbstractTalatisamine (1) is a member of the C19‐diterpenoid alkaloid family, and exhibits K+ channel inhibitory and antiarrhythmic activities. The formidable synthetic challenge that 1 presents is due to its highly oxidized and intricately fused hexacyclic 6/7/5/6/6/5‐membered‐ring structure (ABCDEF‐ring) with 12 contiguous stereocenters. Here we report an efficient synthetic route to 1 by the assembly of two structurally simple fragments, chiral 6/6‐membered AE‐ring 7 and aromatic 6‐membered D‐ring 6. AE‐ring 7 was constructed from 2‐cyclohexenone (8) through fusing an N‐ethylpiperidine ring by a double Mannich reaction. After coupling 6 with 7, an oxidative dearomatization/Diels–Alder reaction sequence generated fused pentacycle 4 b. The newly formed 6/6‐membered ring system was then stereospecifically reorganized into the 7/5‐membered BC‐ring of 3 via a Wagner–Meerwein rearrangement. Finally, Hg(OAc)2 induced an oxidative aza‐Prins cyclization of 2, thereby forging the remaining 5‐membered F‐ring. The total synthesis of 1 was thus accomplished by optimizing and orchestrating 33 transformations from 8.
Polyfunctional, Proinflammatory, Tissue‐Resident Memory Phenotype and Function of Synovial Interleukin‐17A+CD8+ T Cells in Psoriatic Arthritis
Authors: Steel Kathryn J. A. , Srenathan Ushani , Ridley Michael , Durham Lucy E. , Wu Shih‐Ying , Ryan Sarah E. , Hughes Catherine D. , Chan Estee , Kirkham Bruce W. , Taams Leonie S. 
Published: November 2019

ObjectiveGenetic associations imply a role for CD8+ T cells and the interleukin‐23 (IL‐23)/IL‐17 axis in psoriatic arthritis (PsA) and other spondyloarthritides (SpA). IL‐17A+CD8+ (Tc17) T cells are enriched in the synovial fluid (SF) of patients with PsA, and IL‐17A blockade is clinically efficacious in PsA/SpA. This study was undertaken to determine the immunophenotype, molecular profile, and function of synovial Tc17 cells in order to elucidate their role in PsA/SpA pathogenesis.MethodsPeripheral blood (PB) and SF mononuclear cells were isolated from patients with PsA or other types of SpA. Cells were phenotypically, transcriptionally, and functionally analyzed by flow cytometry (n = 6–18), T cell receptor β (TCRβ) sequencing (n = 3), RNA‐Seq (n = 3), quantitative reverse transcriptase–polymerase chain reaction (n = 4), and Luminex or enzyme‐linked immunosorbent assay (n = 4–16).ResultsIL‐17A+CD8+ T cells were predominantly TCRαβ+ and their frequencies were increased in the SF versus the PB of patients with established PsA (P < 0.0001) or other SpA (P = 0.0009). TCRβ sequencing showed that these cells were polyclonal in PsA (median clonality 0.08), while RNA‐Seq and deep immunophenotyping revealed that PsA synovial Tc17 cells had hallmarks of Th17 cells (RORC/IL23R/CCR6/CD161) and Tc1 cells (granzyme A/B). Synovial Tc17 cells showed a strong tissue‐resident memory T (Trm) cell signature and secreted a range of proinflammatory cytokines. We identified CXCR6 as a marker for synovial Tc17 cells, and increased levels of CXCR6 ligand CXCL16 in PsA SF (P = 0.0005), which may contribute to their retention in the joint.ConclusionOur results identify synovial Tc17 cells as a polyclonal subset of Trm cells characterized by polyfunctional, proinflammatory mediator production and CXCR6 expression. The molecular signature and functional profiling of these cells may help explain how Tc17 cells can contribute to synovial inflammation and disease persistence in PsA and possibly other types of SpA.
Alginate Hydrogels as Scaffolds and Delivery Systems to Repair the Damaged Spinal Cord
Authors: Grijalvo Santiago , Nieto‐Díaz Manuel , Maza Rodrigo M. , Eritja Ramón , Díaz David Díaz 
Published: November 2019

AbstractAlginate (ALG) is a lineal hydrophilic polysaccharide present in brown algae cell walls, which turns into a gel state when hydrated. Gelation readily produces a series of three dimensional (3D) architectures like fibers, capillaries, and microspheres, used as biosensors and bio‐actuators in a plethora of biomedical applications like drug delivery and wound healing. Hydrogels have made a great impact on regenerative medicine and tissue engineering because they are able to mimic the mechanical properties of natural tissues due to their high water content. Recent advances in neurosciences have led to promising strategies for repairing and/or regenerating the damaged nervous system. Spinal cord injury (SCI) is particularly challenging, owing to its devastating medical, human, and social consequences. Although effective therapies to repair the damaged spinal cord (SC) are still lacking, multiple pharmacological, genetic, and cell‐based therapies are currently under study. In this framework, ALG hydrogels constitute a source of potential tools for the development of implants capable of promoting axonal growth and/or delivering cells or drugs at specific damaged sites, which may result in therapeutic strategies for SCI. In this mini‐review, the current state of the art of ALG applications in neural tissues for repairing the damaged spinal cord is discussed.
Three‐Enzyme Phosphorylase Cascade for Integrated Production of Short‐Chain Cellodextrins
Authors: Zhong Chao , Nidetzky Bernd 
Published: November 2019

AbstractCellodextrins are linear β‐1,4‐gluco‐oligosaccharides that are soluble in water up to a degree of polymerization (DP) of ≈6. Soluble cellodextrins have promising applications as nutritional ingredients. A DP‐controlled, bottom‐up synthesis from expedient substrates is desired for their bulk production. Here, a three‐enzyme glycoside phosphorylase cascade is developed for the conversion of sucrose and glucose into short‐chain (soluble) cellodextrins (DP range 3–6). The cascade reaction involves iterative β‐1,4‐glucosylation of glucose from α‐glucose 1‐phosphate (αGlc1‐P) donor that is formed in situ from sucrose and phosphate. With final concentration and yield of the soluble cellodextrins set as targets for biocatalytic synthesis, three major factors of reaction efficiency are identified and partly optimized: the ratio of enzyme activity, the ratio of sucrose and glucose, and the phosphate concentration used. The efficient use of the phosphate/αGlc1‐P shuttle for cellodextrin production is demonstrated and the soluble product at 40 g L−1 is obtained under near‐complete utilization of the donor substrate offered (88 mol% from 200 mm sucrose). The productivity is 16 g (L h)−1. Through a simple two‐step route, the soluble cellodextrins are recovered from the reaction mixture in ≥95% purity and ≈92% yield. Overall, this study provides the basis for their integrated production.
Serum metabolite profiling of ST‐segment elevation myocardial infarction using liquid chromatography quadrupole time‐of‐flight mass spectrometry
Authors: Gundogdu Gulsah , Senol Onur , Demirkaya Miloglu Fatma , Koza Yavuzer , Gundogdu Fuat , Hacımüftüoğlu Ahmet , Abd El‐Aty A.M. 
Published: November 2019

AbstractST segment elevation myocardial infarction (STEMI) is one of the most common global causes of cardiovascular disease‐related death. Several metabolites may change during STEMI. Hence, analysis of metabolites in body fluid may be considered as a rapid and accurate test for initial diagnosis. This study has therefore attempted to determine the variation in metabolites identified in the serum of STEMI patients (n = 20) and 15 controls. Samples collected from the Cardiology Department, Medical Faculty, Ataturk University, were extracted by liquid–liquid extraction and analysed using liquid chromatography quadrupole time‐of‐flight mass spectrometry. The METLIN database was used for the identification and characterization of metabolites. According to Q‐TOF/MS measurements, 231 m/z values, which were significantly different between groups (P < 0.01 and fold analysis >1.5) were detected. Metabolite identification was achieved via the Human Metabolome database. According to the multivariate data analysis, leucine, isoleucine, l‐proline, l‐alanine, glycine, fumaric acid, citrate, succinate and carnitine levels were decreased, whereas levels of propionic acid, maleic acid, butyric acid, urea, oleic acid, palmitic acid, lysoPC [18:2(9Z)], glycerol, phoshpatidylethanolamine, caffeine and l‐lactic acid were increased in STEMI patients compared with controls. In conclusion, malonic acid, maleic acid, fumaric acid and palmitic acid can be used as biomarkers for early risk stratification of patients with STEMI.
Immune checkpoint inhibitor‐associated pituitary‐adrenal dysfunction: A systematic review and meta‐analysis
Authors: Lu Jingli , Li Lulu , Lan Yan , Liang Yan , Meng Haiyang 
Published: November 2019

AbstractWith the growing use of immune checkpoint inhibitors (ICIs), case reports of rare yet life‐threatening pituitary‐adrenal dysfunctions, particularly for hypopituitarism, are increasingly being published. In this analysis, we focus on these events by including the most recent publications and reports from early phase I/II and phase III clinical trials and comparing the incidence and risks across different ICI regimens. PubMed, Embase, and the Cochrane Library were systematically searched from inception to April 2019 for clinical trials that reported on pituitary‐adrenal dysfunction. The rates of events, odds ratios (ORs), and 95% confidence intervals (CIs) were obtained using random effects meta‐analysis. The analyses included data from 160 trials involving 40 432 participants. The rate was 2.43% (95% CI, 1.73%‐3.22%) for all‐grade adrenal insufficiency and 3.25% (95% CI, 2.15%‐4.51%) for hypophysitis. Compared with the placebo or other therapeutic regimens, ICI agents were associated with a higher incidence of serious‐grade adrenal insufficiency (OR 3.19, 95% CI, 1.84 to 5.54) and hypophysitis (OR 4.77, 95% CI, 2.60 to 8.78). Among 71 serious‐grade hypopituitarism instances in 12 336 patients, there was a significant association between ICIs and hypopituitarism (OR 3.62, 95% CI, 1.86 to 7.03). Substantial heterogeneity was noted across the studies for the rates of these events, which in part was attributable to the different types of ICIs and varied phases of the clinical trials. Although the rates of these events were low, the risk was increased following ICI‐based treatment, particularly for CTLA‐4 inhibitors, which were associated with a higher incidence of pituitary‐adrenal dysfunction than PD‐1/PD‐L1 inhibitors.
The Activity of Small Urea‐γ‐AApeptides Toward Gram‐Positive Bacteria
Authors: Su Ma , Shi Yan , Wang Minghui , Gao Ruixuan , Wu Jianfeng , Xu Hai , Xi Chuanwu , Cai Jianfeng 
Published: November 2019

AbstractHost Defense Peptides (HDPs) have gained considerable interest due to the omnipresent threat of bacterial infection as a serious public health concern. However, development of HDPs is impeded by several drawbacks, such as poor selectivity, susceptibility to proteolytic degradation, low‐to‐moderate activity and requiring complex syntheses. Herein we report a class of lipo‐linear α/urea‐γ‐AApeptides with a hybrid backbone and low molecular weight. The heterogeneous backbone not only enhances chemodiversity, but also shows effective antimicrobial activity against Gram‐positive bacteria and is capable of disrupting bacterial membranes and killing bacteria rapidly. Given their low molecular weight and ease of access via facile synthesis, they could be practical antibiotic agents.
USB powered microfluidic paper‐based analytical devices
Authors: Schaumburg Federico , Kler Pablo A. , Carrell Cody S. , Berli Claudio L. A. , Henry Charles S. 
Published: November 2019

AbstractMicrofluidic paper‐based analytical devices (μPADs) allow user‐friendly and portable chemical determinations, although they provide limited applicability due to insufficient sensitivity. Several approaches have been proposed to address poor sensitivity in μPADs, but they frequently require bulky equipment for power and/or read‐outs. Universal serial buses (USB) are an attractive alternative to less portable power sources and are currently available in many common electronic devices. Here, USB‐powered μPADs (USB μPADs) are proposed as a fusion of both technologies to improve performance without adding instrumental complexity. Two ITP USB μPADs were developed, both powered by a 5 V potential provided through standard USB ports. The first device was fabricated using the origami approach. Its operation was analyzed experimentally and numerically, yielding a two‐order‐of‐magnitude sample focusing in 15 min. The second ITP USB μPAD is a novel design, which was numerically prototyped with the aim of handling larger sample volumes. The reservoirs were moved away from the ITP channel and capillary action was used to drive the sample and electrolytes to the separation zone, predicting 25‐fold sample focusing in 10 min. USB μPADs are expected to be adopted by minimally‐trained personnel in sensitive areas like resource‐limited settings, the point‐of‐care and in emergencies.
Power coefficient measurements of a novel vertical axis wind turbine
Authors: Hilewit Doma , Matida Edgar A. , Fereidooni Amin , Abo el Ella Hamza , Nitzsche Fred 
Published: November 2019

AbstractWind tunnel experiments were performed to evaluate the power coefficients of three vertical axis wind turbines (VAWTs), namely, (a) conventional VAWT (two‐bladed troposkien shape), (b) novel 50% shifted troposkien shape‐vertical axis wind turbine (50% STS‐VAWT), and (c) novel 100% STS‐VAWT. All turbines had the same height, swept area, and NACA0015 airfoil with the same chord length. During the power coefficient measurements for each one of the turbines, the wind tunnel velocity was varied while the turbine rotation was kept constant through rheostatic load adjustment. Two different turbine rotations were used (600 rpm and 700 rpm). The resulting tip speed ratios (TSRs) ranged from approximately 2 to 6 in the current investigation. Both the power coefficients and the tip speed ratios were corrected against wind tunnel blockage effects. The 50% STS‐VAWT model showed an overall better aerodynamic performance (both corrected and uncorrected power coefficients) when compared against the other two configurations, likely due to a combination of (a) power generation increased due to blade‐wake interaction (BWI) reductions and (b) power generation capacity related to the blade length of each turbine.
Short‐term forecasting of the US unemployment rate
Authors: Maas Benedikt 
Published: November 2019

AbstractThis paper aims to assess whether Google search data are useful when predicting the US unemployment rate among other more traditional predictor variables. A weekly Google index is derived from the keyword “unemployment” and is used in diffusion index variants along with the weekly number of initial claims and monthly estimated latent factors. The unemployment rate forecasts are generated using MIDAS regression models that take into account the actual frequencies of the predictor variables. The forecasts are made in real time, and the forecasts of the best forecasting models exceed, for the most part, the root mean squared forecast error of two benchmarks. However, as the forecasting horizon increases, the forecasting performance of the best diffusion index variants decreases over time, which suggests that the forecasting methods proposed in this paper are most useful in the short term.
Reconstruction of rearranged T‐cell receptor loci by whole genome and transcriptome sequencing gives insights into the initial steps of T‐cell prolymphocytic leukemia
Authors: Patil Paurnima , Cieslak Agata , Bernhart Stephan H. , Toprak Umut H. , Wagener Rabea , López Cristina , Wiehle Laura , Bens Susanne , Altmüller Janine , Franitza Marek , Scholz Ingrid , Jayne Sandrine , Ahearne Matthew J. , Scheffold Annika , Jebaraj Billy M. C. , Schneider Christof , Costa Dolors , Braun Till , Schrader Alexandra , Campo Elias , Dyer Martin J. S. , Nürnberg Peter , Dürig Jan , Johansson Patricia , Böttcher Sebastian , Schlesner Matthias , Herling Marco , Stilgenbauer Stephan , Macintyre Elizabeth , Siebert Reiner 
Published: November 2019

AbstractT‐cell prolymphocytic leukemia (T‐PLL) is an aggressive tumor with leukemic presentation of mature T‐lymphocytes. Here, we aimed at characterizing the initial events in the molecular pathogenesis of T‐PLL and particularly, at determining the point in T‐cell differentiation when the hallmark oncogenic events, that is, inv(14)(q11q32)/t(14;14)(q11;q32) and t(X;14)(q28;q11) occur. To this end, we mined whole genome and transcriptome sequencing data of 17 and 11 T‐PLL cases, respectively. Mapping of the 14q32.1 locus breakpoints identified only TCL1A, which was moreover significantly overexpressed in T‐PLL as compared to benign CD4+ and CD8+ T‐cells, as the only common oncogenic target of aberrations. In cases with t(14;14), the breakpoints mapped telomeric and in cases with inv(14) centromeric or in the 3′‐untranslated region of TCL1A. Regarding the T‐cell receptor alpha (TRA) locus‐TCL1A breakpoint junctions, all 17 breakpoints involved recombination signal sequences and 15 junctions contained nontemplated (N‐) nucleotides. All T‐PLL cases studied carried in‐frame TRA rearrangements on the intact allele, which skewed significantly toward usage of distal/central TRAV/TRAJ gene segments as compared to the illegitimate TRA rearrangements. Our findings suggest that the oncogenic TRA‐TCL1A/MTCP1 rearrangements in T‐PLL occur during opening of the TRA locus, that is, during the progression from CD4+ immature single positive to early double positive thymocyte stage, just before physiologic TCL1A expression is silenced. The cell carrying such an oncogenic event continues maturation and rearranges the second TRA allele to achieve a functional T‐cell receptor. Thereafter, it switches off RAG and DNTT expression in line with the mature T‐cell phenotype at presentation of T‐PLL.