bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stereoselective Synthesis of α‐Linked 2‐Deoxy Glycosides Enabled by Visible‐Light‐Mediated Reductive Deiodination
Authors: Wang Hao , Tao Jinyi , Cai Xinpei , Chen Wei , Zhao Yueqi , Xu Yang , Yao Wang , Zeng Jing , Wan Qian 
Published: November 2014

Abstract2‐Deoxy sugars and their derivatives occur abundantly in many pharmaceutically important natural products. However, the construction of specific 2‐deoxy‐glycosidic bonds remains as a challenge. Herein, we report an efficient way to prepare 2‐deoxy‐α‐glycosides by glycosylation of 2‐iodo‐glycosyl acetate and subsequent visible‐light‐mediated tin‐free reductive deiodination. We have successfully applied the postglycosylational‐deiodination strategy in the synthesis of more than 30 mono‐, di‐, tri‐, tetra‐ and pentadeoxysaccharides with excellent stereoselectivity and efficiency. This method has also been applied to the synthesis of a 2‐deoxy‐tetrasaccharide containing four α‐linkages.
Neue Trends in der homogenen Übergangsmetallkatalyse
Authors: Behr Arno , Vorholt Andreas J. 
Published: November 2014

AbstractDieser Beitrag gibt eine ausgewählte Übersicht über aktuelle Entwicklungen in der homogenen Übergangsmetallkatalyse. Im Vordergrund stehen hier vor allem technisch relevante Reaktionen, wie z. B. Hydroformylierung, Carbonylierung, Hydrierung, Oxidation, Aminierung, Metathese und resultierende Tandemreaktionen. Neben dem Einsatz klassischer petrochemischer Grundstoffe wird ebenfalls die Umsetzung nachwachsender Rohstoffe diskutiert. An ausgewählten Beispielen werden kontinuierlich durchgeführte Umsetzungen der Reaktionen in Miniplants gezeigt.
Anticancer Profile of a Series of Gold(III) (2‐phenyl)pyridine Complexes
Authors: Rubbiani Riccardo , Zehnder Thomas N. , Mari Cristina , Blacque Olivier , Venkatesan Koushik , Gasser Gilles 
Published: November 2014

AbstractSix phosphorescent (2‐phenyl)pyridine (ppy) gold(III) 2,4,6‐tris(trifluoromethyl)phenyl (FMes) complexes were synthesized and investigated for their anticancer potential. The compounds demonstrated strong antiproliferative activity, with EC50 values in the low micromolar range, along with significant accumulation in HeLa cancer cells after treatment for only 6 h (up to 119 ng gold per milligram of protein as measured by high‐resolution continuum source atomic spectroscopy). Enzyme inhibition studies showed interaction of the gold(III) complexes with thioredoxin reductase (TrxR), a key homeostasis‐regulation flavoprotein. TrxR was inhibited with IC50 values in the micromolar range. Furthermore, five of the complexes displayed selectivity toward TrxR against glutathione reductase (GR, a disulfide reductase structurally related to TrxR) by up to >49‐fold. Because no major differences in bioactivity were observed across the series, [(ppy)Au(FMes)(PPh3)OTf] (complex 4) was chosen for further in‐depth biological characterization. Complex 4 was also found to interact with guanosine monophosphate in 1H NMR studies under long incubation times. Interestingly, 4 induced a significant increase in intracellular levels of reactive oxygen species, which led to late apoptotic events and cytocidal effects.
Combining region‐based and imprecise boundary‐based cues for interactive medical image segmentation
Authors: Jones Jonathan‐Lee , Xie Xianghua , Essa Ehab 
Published: November 2014

SUMMARYIn this paper, we present an approach combining both region selection and user point selection for user‐assisted segmentation as either an enclosed object or an open curve, investigate the method of image segmentation in specific medical applications (user‐assisted segmentation of the media–adventitia border in intravascular ultrasound images, and lumen border in optical coherence tomography images), and then demonstrate the method with generic images to show how it could be utilized in other types of medical image and is not limited to the applications described. The proposed method combines point‐based soft constraint on object boundary and stroke‐based regional constraint. The user points act as attraction points and are treated as soft constraints rather than hard constraints that the segmented boundary has to pass through. The user can also use strokes to specify region of interest. The probabilities of region of interest for each pixel are then calculated, and their discontinuity is used to indicate object boundary. The combinations of different types of user constraints and image features allow flexible and robust segmentation, which is formulated as an energy minimization problem on a multilayered graph and is solved using a shortest path search algorithm. We show that this combinatorial approach allows efficient and effective interactive segmentation, which can be used with both open and closed curves to segment a variety of images in different ways. The proposed method is demonstrated in the two medical applications, that is, intravascular ultrasound and optical coherence tomography images, where image artefacts such as acoustic shadow and calcification are commonplace and thus user guidance is desirable. We carried out both qualitative and quantitative analysis of the results for the medical data; comparing the proposed method against a number of interactive segmentation techniques. Copyright © 2014 John Wiley & Sons, Ltd.
Applicability of the polynomial chaos expansion method for personalization of a cardiovascular pulse wave propagation model
Authors: Huberts W. , Donders W. P. , Delhaas T. , van de Vosse F. N. 
Published: November 2014

SUMMARYPatient‐specific modeling requires model personalization, which can be achieved in an efficient manner by parameter fixing and parameter prioritization. An efficient variance‐based method is using generalized polynomial chaos expansion (gPCE), but it has not been applied in the context of model personalization, nor has it ever been compared with standard variance‐based methods for models with many parameters. In this work, we apply the gPCE method to a previously reported pulse wave propagation model and compare the conclusions for model personalization with that of a reference analysis performed with Saltelli's efficient Monte Carlo method. We furthermore differentiate two approaches for obtaining the expansion coefficients: one based on spectral projection (gPCE‐P) and one based on least squares regression (gPCE‐R). It was found that in general the gPCE yields similar conclusions as the reference analysis but at much lower cost, as long as the polynomial metamodel does not contain unnecessary high order terms. Furthermore, the gPCE‐R approach generally yielded better results than gPCE‐P. The weak performance of the gPCE‐P can be attributed to the assessment of the expansion coefficients using the Smolyak algorithm, which might be hampered by the high number of model parameters and/or by possible non‐smoothness in the output space. Copyright © 2014 John Wiley & Sons, Ltd.
Safety, tolerability, and pharmacokinetics of single oral doses of tofacitinib, a Janus kinase inhibitor, in healthy volunteers
Authors: Krishnaswami Sriram , Boy Mary , Chow Vincent , Chan Gary 
Published: November 2014

AbstractTofacitinib is an oral Janus kinase inhibitor. This randomized, double‐blind, parallel‐group, placebo‐controlled study was the first evaluation of tofacitinib in humans. The objectives were to characterize the safety and tolerability, pharmacokinetics (PK), and pharmacodynamics of escalating single tofacitinib doses in healthy subjects. Tofacitinib (0.1, 0.3, 1, 3, 10, 30, 60, and 100 mg) or placebo was administered as oral powder for constitution. For each dose, 7–9 subjects were randomized to tofacitinib and 3–5 subjects to placebo. Ninety‐five males and females (age range 19–45) completed the study. Forty‐nine treatment‐emergent all‐causality adverse events (AEs) were observed; nausea and headache were the most frequently reported. Tofacitinib PK was characterized by rapid absorption (time to peak serum concentration [Tmax] 0.5–1 hour), rapid elimination (mean terminal half‐lives 2.3–3.1 hours), and dose‐proportional systemic exposures (peak serum concentration [Cmax] and area under the serum concentration‐time curve from time zero to infinity [AUC0–∞]). No appreciable correlation was observed between tofacitinib dose and lymphocyte subset counts. Single‐dose tofacitinib up to 100 mg in healthy subjects had a safety profile of mostly mild AEs, and no deaths, serious AEs, severe AEs or discontinuations due to AEs.
Palatogenesis and cutaneous repair: A two‐headed coin
Authors: Biggs Leah C. , Goudy Steven L. , Dunnwald Martine 
Published: November 2014

ABSTRACTBackground:The reparative mechanism that operates following post‐natal cutaneous injury is a fundamental survival function that requires a well‐orchestrated series of molecular and cellular events. At the end, the body will have closed the hole using processes like cellular proliferation, migration, differentiation and fusion.Results:These processes are similar to those occurring during embryogenesis and tissue morphogenesis. Palatogenesis, the formation of the palate from two independent palatal shelves growing towards each other and fusing, intuitively, shares many similarities with the closure of a cutaneous wound from the two migrating epithelial fronts.Conclusions:In this review, we summarize the current information on cutaneous development, wound healing, palatogenesis and orofacial clefting and propose that orofacial clefting and wound healing are conserved processes that share common pathways and gene regulatory networks.Developmental Dynamics 244:289–310, 2015. © 2014 Wiley Periodicals, Inc.
Worsening heart failure, a critical event during hospital admission for acute heart failure: results from the VERITAS study
Authors: Cotter Gad , Metra Marco , Davison Beth A. , Senger Stefanie , Bourge Robert C. , Cleland John G.F. , Jondeau Guillaume , Krum Henry , O'Connor Christopher M. , Parker John D. , Torre‐Amione Guillermo , van Veldhuisen Dirk J. , Milo Olga , Kobrin Isaac , Rainisio Maurizio , McMurray John J.V. , Teerlink John R. ,   for the VERITAS Investigators
Published: November 2014

AimsWorsening heart failure (WHF) in the first 7 days after an admission for acute HF (AHF) has been proposed as a therapeutic target in several recent AHF studies and was a co‐primary endpoint of the VERITAS studies.Methods and resultsPatients were randomized within 24 h of admission for AHF. WHF was defined as worsening or persistent signs and symptoms of HF requiring additional intravenous or mechanical therapy for HF or death within 7 days of randomization. Multivariable models were developed to predict the time to WHF through day 7. Unadjusted and multivariable‐adjusted associations of WHF with the length of stay (LOS) of the index hospitalization, and 30‐ and 90‐day outcomes were estimated. WHF occurred by day 7 in 27% of the 1347 patients enrolled. Age, co‐morbidities, and markers of HF severity were moderately predictive of WHF; the C‐index for a multivariable model for WHF was 0.66. After multivariable adjustment for baseline characteristics, WHF was associated with an increase in LOS of 4.33 days [95% confidence interval (CI) 3.54–5.13 days], a hazard ratio (HR) for 30‐day HF readmission or death of 2.43 (95% CI 1.75–3.40), and a HR for 90‐day mortality of 2.57 (95% CI 1.81–3.65), all with P < 0.0001.The associations of WHF with these outcomes remained largely unchanged after adjustment for both baseline characteristics and changes in markers of renal and hepatic dysfunction during the first day of admission.ConclusionsIn patients admitted for AHF, WHF is a significant clinical event that is associated with delays in discharge and higher rates for readmission and death.
Monothiolato‐Bridged Dinuclear Arene Ruthenium Complexes: The Missing Link in the Reaction of Arene Ruthenium Dichloride Dimers with Thiols
Authors: Stíbal David , Therrien Bruno , Giannini Federico , Paul Lydia E. H. , Furrer Julien , Süss‐Fink Georg 
Published: November 2014

AbstractThe monothiolato complexes [(η6‐p‐MeC6H4iPr)2Ru2Cl2(μ‐Cl)(μ‐SR)] with R = CH2C6H5 (1), p‐CH2C6H4NO2 (2), C10H15 (3), m‐9‐B10C2H11 (4) were synthesized by treating [(η6‐p‐MeC6H4iPr)2Ru2Cl2(μ‐Cl)2] with the corresponding thiols RSH. The reaction of p‐cymene ruthenium dichloride dimer with thiols is well known to give the cationic trithiolato complexes [(η6‐p‐MeC6H4iPr)2Ru2(μ‐SR)3]+, but recently the intermediary dithiolato complexes [(η6‐p‐MeC6H4iPr)2Ru2Cl2(μ‐SR)2] could also be isolated and characterized in some cases. The monothiolato complexes 1–4 now observed represent the missing link in the stepwise formation of the trithiolato complexes. The single‐crystal X‐ray structure analyses of complexes 1 and 2 show the two ruthenium atoms to be bridged by a chlorido ligand and by the thiolato ligand without a metal–metal bond, which is in accordance with the eighteen‐electron rule.
A Synthetic Route to Sulfobetaine Methacrylates with Varying Charge Distance
Authors: Kratzer Domenic , Barner Leonie , Friedmann Christian , Bräse Stefan , Lahann Joerg 
Published: November 2014

AbstractA general synthetic strategy is described that enables access to a library of new sulfobetaine methacrylates starting from commercially available precursors. The three‐step procedure allows the distance between the quaternary amine and the sulfonate group (inner charge distance) to be varied by selecting the corresponding dibromoalkane in the first step. A key step is the final esterification, in which methacrylic acid acts as solvent as well as reagent for the zwitterionic hydroxy intermediates. Thus, it is possible to synthesize monomeric precursors with up to twelve methylene groups between the positive and the negative charge. A selection of these monomers has been successfully tested for their ability to polymerize using free‐radical polymerization.
Alberta Breakthrough Pain Assessment Tool: A validation multicentre study in cancer patients with breakthrough pain
Authors: Sperlinga R. , Campagna S. , Berruti A. , Laciura P. , Ginosa I. , Paoletti S. , Giuliano P.L. , Tucci M. , Rosato R. , Scagliotti G.V. , Saini A. 
Published: November 2014

AbstractBackgroundCancer‐related breakthrough pain (BTP) is a common and quite challenging pain syndrome, with significant impact on quality of life. To date, no widely recognized and validated tool for the diagnosis and evaluation of BTP exists. The Alberta Breakthrough Pain Assessment Tool (ABPAT) underwent a validation process during its development, but no experience of its implementation in clinical practice has been reported.MethodsABPAT was tested in a cohort of cancer patients suffering from chronic severe cancer‐related pain in order to assess its acceptability and efficacy as a tool for the characterization of BTP.ResultsA total of consecutive 249 patients from seven different centres were included in a 2‐month study period and all completed the questionnaire; 231 out of the 249 (92.8%) stated that questions were easily understandable and 217 out of the 249 (87.1%) stated that the tool allowed to explain extensively the BTP problem. Physician–patient correlation tests about baseline BTP intensity and BTP relief by medication showed statistical significance at the level of p = 0.001 and p = 0.0001, respectively. Evaluation of the efficacy of BPT medication revealed a 78.2% of patients declaring a good relief from BTP, with a significant reduction of mean BTP numeric rating scale score (p = 0.0001), but only 55.9% of patients responded to be satisfied about time for onset of the relief.ConclusionsIn this study, ABPAT resulted to be a well‐accepted tool for BTP assessment and characterization in a relatively large cohort of cancer patients. It is effective in discovering the unmet needs of cancer patients and in exploring the outcomes of BTP treatment.
A Polyionic, Large‐Format Energy Storage Device Using an Aqueous Electrolyte and Thick‐Format Composite NaTi2(PO4)3/Activated Carbon Negative Electrodes
Authors: Whitacre J. F. , Shanbhag S. , Mohamed A. , Polonsky A. , Carlisle K. , Gulakowski J. , Wu W. , Smith C. , Cooney L. , Blackwood D. , Dandrea J. C. , Truchot C. 
Published: November 2014

AbstractA composite anode comprising blended NASICON‐structured NaTi2(PO4)3 and activated carbon has been implemented in an aqueous electrolyte electrochemical energy storage device. A simple solid‐state synthetic route based on low‐cost precursors was used to produce the NaTi2(PO4)3, and thick (>1 mm) freestanding electrodes were fabricated with a range of activated carbon mass fractions. Electrochemical analyses showed the efficacy and stability of this composite anode combination in a functional paradigm where both Na+ and Li+ cations can participate in the charge storage reactions. Use of this composite anode in concert with a λ‐MnO2‐based cathode results in an energy storage device that is low cost, robust, and of sufficient energy density to be implemented in stationary applications. Data from large‐format units that contain many cells in series indicate that string‐level self‐balancing occurs, an effect that can be relied on for making cycle‐stable high‐voltage strings of cells.
Models and experiments for energy consumption and quality of green tea drying
Authors: Langat Nickson , Thoruwa Thomas , Wanyoko John , Kiplagat Jeremiah , Plourde Brian , Abraham John 
Published: November 2014

AbstractAn experimental apparatus has been developed to evaluate the drying process of green tea leaves. Tea drying is an energy‐intensive process which results in the removal of leaf moisture; it is essential to the quality of the final product. In order to more efficiently use process energy, a prototype drying system has been built and tested. The prototype incorporates a rotating perforated drum which helps speed the drying process. Experiments were carried out with multiple temperatures, airflow rates, and drum rotation rates; a subset of those results is shown here. In particular, the impact of airflow rate on the process was studied. It was found that as the airflow increased, the drying rate increased, as expected. However, the efficiency of energy use, which was quantified by the Specific Energy Consumption rate, varied considerably with flow. While higher flows led to faster drying, it resulted in a lower energy efficiency. Also, a two parameter predictive model was developed that was able to accurately match the moisture removal rates for a very wide range of flows. This predictive model, which is based on thermal‐fluid fundamentals, can be used to extrapolate the presented results to cases which were not considered.
Hg-contaminated terrestrial spiders pose a potential risk to songbirds at Caddo Lake (Texas/Louisiana, USA)
Authors: Gann Gretchen L. , Powell Cleveland H. , Chumchal Matthew M. , Drenner Ray W. 
Published: November 2014

Abstract

Methylmercury (MeHg) is an environmental contaminant that can have adverse effects on wildlife. Because MeHg is produced by bacteria in aquatic ecosystems, studies of MeHg contamination of food webs historically have focused on aquatic organisms. However, recent studies have shown that terrestrial organisms such as songbirds can be contaminated with MeHg by feeding on MeHg-contaminated spiders. In the present study, the authors examined the risk that MeHg-contaminated terrestrial long-jawed orb weaver spiders (Tetragnatha sp.) pose to songbirds at Caddo Lake (Texas/Louisiana, USA). Methylmercury concentrations in spiders were significantly different in river, wetland, and open-water habitats. The authors calculated spider-based wildlife values (the minimum spider MeHg concentrations causing physiologically significant doses in consumers) to assess exposure risks for arachnivorous birds. Methylmercury concentrations in spiders exceeded wildlife values for Carolina chickadee (Poecile carolinensis) nestlings, with the highest risk in the river habitat. The present study indicates that MeHg concentrations in terrestrial spiders vary with habitat and can pose a threat to small-bodied nestling birds that consume large amounts of spiders at Caddo Lake. This MeHg threat to songbirds may not be unique to Caddo Lake and may extend throughout the southeastern United States. Environ Toxicol Chem 2014;9999:1–4. © 2014 SETAC
Sources of endocrine-disrupting compounds in North Carolina waterways: A geographic information systems approach
Authors: Sackett Dana K. , Pow Crystal Lee , Rubino Matthew J. , Aday D. Derek , Cope W. Gregory , Kullman Seth , Rice James A. , Kwak Thomas J. , Law Mac 
Published: November 2014

Abstract

The presence of endocrine-disrupting compounds (EDCs), particularly estrogenic compounds, in the environment has drawn public attention across the globe, yet a clear understanding of the extent and distribution of estrogenic EDCs in surface waters and their relationship to potential sources is lacking. The objective of the present study was to identify and examine the potential input of estrogenic EDC sources in North Carolina water bodies using a geographic information system (GIS) mapping and analysis approach. Existing data from state and federal agencies were used to create point and nonpoint source maps depicting the cumulative contribution of potential sources of estrogenic EDCs to North Carolina surface waters. Water was collected from 33 sites (12 associated with potential point sources, 12 associated with potential nonpoint sources, and 9 reference), to validate the predictive results of the GIS analysis. Estrogenicity (measured as 17β-estradiol equivalence) ranged from 0.06 ng/L to 56.9 ng/L. However, the majority of sites (88%) had water 17β-estradiol concentrations below 1 ng/L. Sites associated with point and nonpoint sources had significantly higher 17β-estradiol levels than reference sites. The results suggested that water 17β-estradiol was reflective of GIS predictions, confirming the relevance of landscape-level influences on water quality and validating the GIS approach to characterize such relationships. Environ Toxicol Chem 2014;9999:1–9. © 2014 SETAC
Relationship between tumour necrosis factor‐related apoptosis inducing ligand (TRAIL) and vascular endothelial growth factor in human multiple myeloma patients
Authors: Bolkun Lukasz , Lemancewicz Dorota , Piszcz Jaroslaw , Moniuszko Marcin , Bolkun‐Skornicka Urszula , Szkiladz Malgorzata , Jablonska Ewa , Kloczko Janusz , Dzieciol Janusz 
Published: November 2014

AbstractTumour necrosis factor‐alfa (TNF‐α) is an inflammatory cytokine with a wide spectrum of biological activity, including angiogenesis. Tumour necrosis factor‐related apoptosis inducing ligand (TRAIL), which belongs to the TNF family of proteins, plays a role in the regulation of vascular responses, but its effect on the formation of new blood vessels (angiogenesis) is unclear. We analysed TRAIL concentrations in parallel with pro‐angiogenic cytokines in serum and their expression in trephine biopsy (TB) in 56 patients with newly diagnosed IgG MM and 24 healthy volunteers. The study showed statistically higher concentrations of TRAIL and TNF‐α, as well as of VEGF and its receptor, in MM patients compared to healthy volunteers and patients in advanced stages of the disease. Furthermore, we observed a significant decrease in all studied pro‐angiogenic cytokines and significant increase of TRAIL concentration after anti‐angiogenic therapy, with meaningful differences between responders (at least partial remission) and patients with progression during the induction treatment. It was also established that TRAIL correlated statistically and negatively with pro‐angiogenic cytokines such as VEGF with its receptor and expression of VEGF and syndecan‐1 in TB.In summary, our data indicate that in MM patients, both clinical course and treatment responsiveness are associated with dynamic yet corresponding changes of levels of TRAIL parallel pro‐angiogenic mediators such as VEGF with its receptor and expression of VEGF and syndecan‐1 in TB. Copyright © 2014 John Wiley & Sons, Ltd.