bluuebunny/crossref_metadata_2025_split huggingface dataset:
Pretreatment lesional volume impacts clinical outcome and thrombectomy efficacy
Authors: Xie Yu , Oppenheim Catherine , Guillemin Francis , Gautheron Vincent , Gory Benjamin , Raoult Hélène , Soize Sébastien , Felblinger Jacques , Hossu Gabriela , Bracard Serge ,   on behalf of the THRACE investigators
Published: January 2018

ObjectiveWe aimed to characterize the association between pretreatment lesional volume measured on diffusion‐weighted images and functional outcome, and estimate the impact on thrombectomy efficacy for ischemic stroke with anterior proximal intracranial arterial occlusion.MethodsAnterior circulation ischemic stroke patients who had pretreatment diffusion‐weighted imaging in the THRACE study were included. Lesional volume was semiautomatically segmented. Logistic regression was applied to model clinical outcome as a function of lesional volume. Outcomes included functional independence (modified Rankin Scale [mRS] 0–2), degree of disability (ordinal mRS 0–6), and mortality at 3 months.ResultsOf 298 included patients, with median lesional volume 17.2ml (interquartile range [IQR], 9.2–51.8) and median mRS 2 (IQR, 1–4), 51.0% achieved functional independence. Increased lesional volume was an independent predictor for a lower probability of functional independence (odds ratio [OR], 0.90 [95% confidence interval {CI}, 0.81–0.99] per 10ml; p < 0.001), a less favorable degree of disability (common OR, 0.86 [95% CI, 0.81–0.90] per 10ml; p < 0.001), and a higher mortality rate (OR, 1.21 [95% CI, 1.08–1.37] per 10ml; p < 0.001). For additional thrombectomy, the number of patients needed to treat to achieve functional independence in 1 patient increased with lesional volume (10 for a volume of 80ml; 15 for 135ml). No significant treatment‐by‐dichotomized volume interaction for functional independence and mortality was observed.InterpretationPretreatment lesional volume is an independent predictor for functional outcome in acute ischemic stroke with proximal intracranial occlusion. The clinical benefit of adding mechanical thrombectomy to thrombolysis decreased with the increase of lesional volume. Ann Neurol 2018;83:178–185
Association of prothrombin complex concentrate administration and hematoma enlargement in non–vitamin K antagonist oral anticoagulant–related intracerebral hemorrhage
Authors: Gerner Stefan T. , Kuramatsu Joji B. , Sembill Jochen A. , Sprügel Maximilian I. , Endres Matthias , Haeusler Karl Georg , Vajkoczy Peter , Ringleb Peter A. , Purrucker Jan , Rizos Timolaos , Erbguth Frank , Schellinger Peter D. , Fink Gereon R. , Stetefeld Henning , Schneider Hauke , Neugebauer Hermann , Röther Joachim , Claßen Joseph , Michalski Dominik , Dörfler Arnd , Schwab Stefan , Huttner Hagen B. ,   for the RETRACE II (German‐Wide Multicenter Analysis of Oral Anticoagulation–Associated Intracerebral Hemorrhage II) Investigators
Published: January 2018

ObjectiveTo investigate parameters associated with hematoma enlargement in non–vitamin K antagonist oral anticoagulant (NOAC)‐related intracerebral hemorrhage (ICH).MethodsThis retrospective cohort study includes individual patient data for 190 patients with NOAC‐associated ICH over a 5‐year period (2011–2015) at 19 departments of neurology across Germany. Primary outcome was the association of prothrombin complex concentrate (PCC) administration with hematoma enlargement. Subanalyses were calculated for blood pressure management and its association with the primary outcome. Secondary outcomes include associations with in‐hospital mortality and functional outcome at 3 months assessed using the modified Rankin Scale.ResultsThe study population for analysis of primary and secondary outcomes consisted of 146 NOAC‐ICH patients with available follow‐up imaging. Hematoma enlargement occurred in 49/146 (33.6%) patients with NOAC‐related ICH. Parameters associated with hematoma enlargement were blood pressure ≥ 160mmHg within 4 hours and—in the case of factor Xa inhibitor ICH—anti‐Xa levels on admission. PCC administration prior to follow‐up imaging was not significantly associated with a reduced rate of hematoma enlargement either in overall NOAC‐related ICH or in patients with factor Xa inhibitor intake (NOAC: risk ratio [RR] = 1.150, 95% confidence interval [CI] = 0.632–2.090; factor Xa inhibitor: RR = 1.057, 95% CI = 0.565–1.977), regardless of PCC dosage given or time interval until imaging or treatment. Systolic blood pressure levels < 160mmHg within 4 hours after admission were significantly associated with a reduction in the proportion of patients with hematoma enlargement (RR = 0.598, 95% CI = 0.365–0.978). PCC administration had no effect on mortality and functional outcome either at discharge or at 3 months.InterpretationIn contrast to blood pressure control, PCC administration was not associated with a reduced rate of hematoma enlargement in NOAC‐related ICH. Our findings support the need of further investigations exploring new hemostatic reversal strategies for patients with factor Xa inhibitor–related ICH. Ann Neurol 2018;83:186–196
Insights into the Desaturation of Cyclopeptin and its C3 Epimer Catalyzed by a non‐Heme Iron Enzyme: Structural Characterization and Mechanism Elucidation
Authors: Liao Hsuan‐Jen , Li Jikun , Huang Jhih‐Liang , Davidson Madison , Kurnikov Igor , Lin Te‐Sheng , Lee Justin L. , Kurnikova Maria , Guo Yisong , Chan Nei‐Li , Chang Wei‐chen 
Published: January 2018

AbstractAsqJ, an iron(II)‐ and 2‐oxoglutarate‐dependent enzyme found in viridicatin‐type alkaloid biosynthetic pathways, catalyzes sequential desaturation and epoxidation to produce cyclopenins. Crystal structures of AsqJ bound to cyclopeptin and its C3 epimer are reported. Meanwhile, a detailed mechanistic study was carried out to decipher the desaturation mechanism. These findings suggest that a pathway involving hydrogen atom abstraction at the C10 position of the substrate by a short‐lived FeIV‐oxo species and the subsequent formation of a carbocation or a hydroxylated intermediate is preferred during AsqJ‐catalyzed desaturation.
p–π Conjugated Polymers Based on Stable Triarylborane with n‐Type Behavior in Optoelectronic Devices
Authors: Meng Bin , Ren Yi , Liu Jun , Jäkle Frieder , Wang Lixiang 
Published: January 2018

Abstractp–π conjugation with embedded heteroatoms offers unique opportunities to tune the electronic structure of conjugated polymers. An approach is presented to form highly electron‐deficient p–π conjugated polymers based on triarylboranes, demonstrate their n‐type behavior, and explore device applications. By combining alternating [2,4,6‐tris(trifluoromethyl)phenyl]di(thien‐2‐yl)borane (FBDT) and electron‐deficient isoindigo (IID)/pyridine‐flanked diketopyrrolopyrrole (DPPPy) units, we achieve low‐lying lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels, high electron mobilities, and broad absorptions in the visible region. All‐polymer solar cells with these polymers as electron acceptors exhibit encouraging photovoltaic performance with power conversion efficiencies of up to 2.83 %. These results unambiguously prove the n‐type behavior and demonstrate the photovoltaic applications of p–π conjugated polymers based on triarylborane.
RuBisCO‐inspirierte CO2‐Aktivierung und Umwandlung durch einen Iridium(I)‐Komplex
Authors: Langer Jens , Hamza Andrea , Pápai Imre 
Published: January 2018

AbstractDie Synthese eines neuen Iridium(I)‐Komplexes mit dem Enamidophosphan‐Anion dbuP− und seine einzigartige Reaktivität gegenüber CO2 werden vorgestellt. Der Komplex bindet zwei Äquivalente CO2 und initiiert dabei eine hoch selektive Reaktionskaskade, die reversibel zur Spaltung sowohl von CO2 als auch des Enamido‐Liganden führt. Die computergestützte Analyse des Systems lässt auf die Bildung eines relativ stabilen CO2‐Komplexes als Schlüsselintermediat der CO2‐Spaltung schließen, was experimentell bestätigt werden konnte. Die untersuchte Umwandlung weist einige Parallelen zur enzymatischen CO2‐Fixierung durch RuBisCO auf.
Palladium(II)‐Mediated C−H Tritiation of Complex Pharmaceuticals
Authors: Yang Haifeng , Dormer Peter G. , Rivera Nelo R. , Hoover Andrew J. 
Published: January 2018

AbstractTritium‐labeled molecules are critical tools for elucidating the binding and metabolic properties of bioactive compounds, particularly during pharmaceutical discovery. Direct tritiation of inert C−H bonds with T2 gas is an ideal approach for tritium labeling, but significant gaps remain for direct tritiation of structurally complex molecules with diverse functional groups. Here we report the first application of palladium(II) C−H activation chemistry for tritiation with T2 gas. This practical transformation exhibits novel substrate scope and greater functional group tolerance compared to previous state of the art tritiation methods, and has been applied to directly tritiate 9 complex pharmaceuticals and an unprotected dipeptide. The isolated tritium‐labeled products exhibit >15 Ci mmol−1 specific activity, exceeding the typical requirements for application in studies of molecular interaction and metabolism.
Synthesis of a phosphorus‐ and nitrogen‐containing flame retardant and evaluation of its application in waterborne polyurethane
Authors: Wang Shuang , Du Zongliang , Cheng Xu , Liu Yuansen , Wang Haibo 
Published: January 2018

ABSTRACTA phosphorus‐ and nitrogen‐containing intumescent flame retardant, pentaerythritol di‐N‐hydroxyethyl phosphamide (PDNP), was synthesized with phosphorus oxychloride, pentaerythritol, and ethanolamine as raw materials. Using the prepared PDNP as a chain extender, a series of flame‐retardant waterborne polyurethanes (WPU) were prepared, and their structures were characterized using NMR and Fourier transform infrared spectroscopy (FTIR). Additionally, the thermal properties and flame retardancy of WPU films were investigated by thermogravimetric analysis, limiting oxygen index (LOI) tests, cone calorimeter tests, and thermogravimetry‐FTIR. These results indicated that PDNP materials exhibit good char‐forming ability at high temperature and that PDNP‐modified waterborne polyurethane obtained an LOI value of 26.0% for a PDNP content of 9 wt %. Finally, the morphology and the element distributions of char residues of WPU were analyzed by scanning electron microscopy and energy dispersive spectrometry after combustion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46093.
Garlic oil–loaded PLGA nanoparticles with controllable size and shape and enhanced antibacterial activities
Authors: Fahmy Sherif Ashraf , Mamdouh Wael 
Published: January 2018

ABSTRACTThe present work focuses on producing polymer composite nanoparticles (NPs) composed of garlic oil (GO) and poly(lactic‐co‐glycolic) acid (PLGA) by the single emulsion/solvent evaporation (SE/SE) method and high‐speed homogenizing. Different preparation parameters were found to greatly affect the stability and size uniformity of the prepared PLGA/GO NP formulations, which were carefully controlled. Scanning electron microscopy, Fourier transform infrared spectroscopy, and UV–vis spectroscopy and dynamic light scattering and zeta potential were used to characterize the NPs. Antibacterial assessment of the prepared PLGA/GO NPs against E. coli and S. aureus was carried out. Interestingly, the NP size ranged between 201 and 319 nm, which is 10 times less than the size of the regular GO particles in bulk solution. The antibacterial activities show enhancement by 70–78% of bacterial inhibition compared with a GO bulk solution. This work sheds light on the potential use of GO NP formulations as nanobiotics and the critical NP preparation parameters that need to be considered. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46133.
In situ downstream strategies for cost‐effective bio/surfactant recovery
Authors: Najmi Ziba , Ebrahimipour Gholamhossein , Franzetti Andrea , Banat Ibrahim M. 
Published: January 2018

AbstractSince 60–80% of total costs of production are usually associated with downstream collection, separation, and purification processes, it has become advantageous to investigate how to replace traditional methods with efficient and cost‐effective alternative techniques for recovery and purification of biosurfactants. In the traditional techniques, large volumes of organic solvents are usually used for increasing production cost and the overall environmental burden. In addition, traditional production and separation methods typically carried out in batch cultures reduce biosurfactant yields due to product inhibition and lower biosurfactants activity as a result of interaction with the organic solvents used. However, some in situ recovery methods that allow continuous separation of bioproducts from culture broth leading to an improvement in yield production and fermentation efficiency. For biosurfactants commercialization, enhancement of product capacity of the separation methods and the rate of product removal is critical. Recently, interest in the integration of separation methods with a production step as rapid and efficient techniques has been increasing. This review focuses on the technology gains and potentials for the most common methods used in in situ product removal: foam fractionation and ultrafiltration, especially used to recover and purify two well‐known biosurfactants: glycolipids (rhamnolipids) and lipopeptides (surfactins).
A validated LC‐MS/MS method for the determination of senkyunolide I in dog plasma and its application to a pharmacokinetic and bioavailability studies
Authors: Li Jin‐Qi , Wang Jia‐Feng , Li Jie , Zhang Shu‐han , He Dan , Tong Rong‐Sheng , She Shu‐Ya 
Published: January 2018

AbstractSenkyunolide I is one of the major bioactive components in the herbal medicine Ligusticum chuanxiong. The aim of this study was to develop and validate a fast, simple and sensitive LC‐MS/MS method for the determination of senkyunolide I in dog plasma. The plasma samples were processed with acetonitrile and separated on a Waters Acquity UPLC BEH C18 column (50 × 2.1 mm, 1.7 μm). The mobile phase consisted of 0.1% formic acid aqueous and acetonitrile was delivered at a flow rate of 0.3 mL min−1. The detection was achieved in the positive selected reaction monitoring mode with precursor‐to‐product transitions at m/z 225.1 → 161.1 for senkyunolide I and at m/z 349.1 → 305.1 for an internal standard. The assay was linear over the tested concentration range, from 0.5 ng mL−1 to 1000 ng mL−1, with a correlation coefficient >0.9992. The mean extraction recovery from dog plasma was within the range of 85.78–93.25%, while the matrix effect of the analyte was within the range of 98.23–108.89%. The intra‐ and inter‐day precisions (RSD) were <12.12% and the accuracy (RR) ranged from 98.89% to 104.24%. The validated assay was successfully applied to pharmacokinetic and bioavailability studies of senkyunolide I in dogs. The results demonstrated that (a) senkyunolide I showed short elimination half‐life (<1 h) in dog, (b) its oral bioavailability was >40% and (c) senkyunolide I showed dose‐independent pharmacokinetic profiles in dog plasma over the dose range of 1–50 mg kg−1.
Use of a novel embolic filter in carotid artery stenting: 30‐Day results from the EMBOLDEN Clinical Study
Authors: Gray William A. , Mehta Manish , Alani Firas , Kasirajan Karthikeshwar , Begg Richard J. , Bacharach J. Michael , Soukas Peter A. ,   EMBOLDEN Clinical Study Investigators
Published: January 2018

AbstractObjectivesThe EMBOLDEN study was conducted to test the safety and efficacy of a novel emboli protection filter design for use in carotid artery stenting (CAS) in patients with severe carotid stenosis who were at high risk of operative complications from carotid endarterectomy (CEA).BackgroundGeneral considerations for filter design usually involve trade‐offs between trackability/profile and wall apposition/capture efficiency. The GORE® Embolic Filter (GEF) is intended to address these design goals via a hybrid construction.MethodsPatients at high risk for CEA (N = 250) were treated with CAS using the GEF study device paired with an FDA‐approved carotid stent. The primary outcome was death, stroke, and myocardial infarction (MI) at 30 days, compared to a pre‐determined performance goal. Neurologic outcomes were judged by an independent assessor and angiographic results evaluated by an independent central core lab.ResultsThe GEF study device was successfully deployed in 96.4% of procedures. The primary endpoint of 30‐day death, stroke, and MI occurred in 4.0% of subjects and was significantly lower than the pre‐defined performance goal (P < 0.001). The 30‐day rate for death and major stroke was 1.2% and for death and any stroke was 3.6%. The rate of major adverse events was 5.4% among octogenarians and 3.2% among non‐octogenarians.ConclusionIn patients at high risk for CEA undergoing CAS, the GEF not only showed high rates of successful deployment but also met the primary endpoint of low death, stroke, and MI rates, thus demonstrating safety and effectiveness.
A Seed‐Mediated Approach for the Preparation of Modified Heterogeneous Catalysts
Authors: Harmel Justine , Berliet Adrien , Dembélé Kassiogé , Marcelot Cécile , Gay Anne‐Sophie , Ersen Ovidiu , Maury Sylvie , Fécant Antoine , Chaudret Bruno , Serp Philippe , Soulantica Katerina 
Published: January 2018

AbstractColloidal chemistry is very efficient in providing nanocrystals of well‐controlled structural characteristics. Although nanoparticles are essential components of heterogeneous catalysts, colloidal methods are rarely employed for their preparation. We have employed a seed‐mediated growth approach for modifying the structural characteristics of a conventional cobalt‐based Fischer–Tropsch catalyst. The Co particles of this catalyst can play the role of seeds for the overgrowth of shape‐ and structure‐controlled cobalt nanostructures by using a simple wet chemical method involving a molecular cobalt precursor and stabilizing agents. Thus, cobalt nanorods exhibiting the hexagonal compact structure were selectively grown on the immobilized Co particles of a reference Co/Al2O3–SiO2 catalyst. The as‐obtained catalyst shows a better stability than a reference catalyst for the Fischer–Tropsch reaction. The removal of most of the ligands from the nanorod catalyst allows the catalyst activity to be improved while maintaining its stability. This is a proof of concept concerning the implementation of wet chemistry nanoparticle synthesis for the modification of heterogeneous catalysts.
Commercial Gold(I) and Gold(III) Compounds Supported on Carbon Materials as Greener Catalysts for the Oxidation of Alkanes and Alcohols
Authors: Carabineiro Sónia A. C. , Martins Luísa M. D. R. S. , Pombeiro Armando J. L. , Figueiredo José L. 
Published: January 2018

AbstractStrategies are presented for single‐pot efficient oxidative functionalization of cyclohexane and alcohols, under mild conditions, catalysed by Au(I) or Au(III) compounds supported on different carbon materials with three different surface treatments. The obtained materials were tested for the oxidation of cyclohexane under mild conditions (room temperature and atmospheric pressure), using an environmentally friendly oxidant (tert‐butyl hydroperoxide, TBHP, 70 % aqueous solution). All materials were very selective to the production of cyclohexanol and cyclohexanone with no trace of by‐products detected. The catalysts were also tested in the selective oxidation of methyl benzyl alcohol, cyclohexanol, and 2‐octanol with TBHP, under microwave irradiation, to the corresponding aldehydes or ketones. In general, better results are obtained for the heterogenised complexes and that the most efficient support is CNT‐ox‐Na. This is the first report on the oxidation of C−H bonds using the mononuclear gold complexes used; only the oxidation of unsaturated units had been reported previously. The sp3‐C−H activation is much more difficult than the oxidation of unsaturated molecules with molecular oxidants.
Detection of Indistinct Fe−N Stretching Bands in Iron(V) Nitrides by Photodissociation Spectroscopy
Authors: Andris Erik , Navrátil Rafael , Jašík Juraj , Sabenya Gerard , Costas Miquel , Srnec Martin , Roithová Jana 
Published: January 2018

AbstractWe report for the first time infrared spectra of three non‐heme pseudo‐octahedral iron(V) nitride complexes with assigned Fe−N stretching vibrations. The intensities of the Fe−N bands in two of the complexes are extremely weak. Their detection was enabled by the high resolution and sensitivity of the experiments performed at 3 K for isolated complexes in the gas phase. Multireference CASPT2 calculations revealed that the Fe−N bond in the ground doublet state is influenced by two low‐lying excited doublet states. In particular, configuration interaction between the ground and the second excited state leads to avoided crossing of their potential energy surfaces along the Fe−N coordinate, which thus affects the ground‐state Fe−N stretching frequency and intensity. Therefore, DFT calculated Fe−N stretching frequency strongly depends on the amount of Hartree–Fock exchange potential. As a result, by tuning the amount of Hartree–Fock exchange potential in the B3LYP functional, it was possible to obtain theoretical spectra perfectly consistent with the experimental data. The theory shows that the intensity of the Fe−N stretching vibration can almost vanish due to strong coupling with other stretching modes of the ligands.
Synthesis of Galactosylated Glycosylphosphatidylinositol Derivatives from Trypanosoma brucei
Authors: Grube Maurice , Lee Bo‐Young , Garg Monika , Michel Dana , Vilotijević Ivan , Malik Ankita , Seeberger Peter H. , Varón Silva Daniel 
Published: January 2018

AbstractTrypanosoma brucei uses variant surface glycoproteins (VSGs) to evade the host immune system and ensure parasitic longevity in animals and humans. VSGs are attached to the cell membrane by complex glycosylphosphatidylinositol anchors (GPI). Distinguishing structural feature of VSG GPIs are multiple α‐ and β‐galactosides attached to the conserved GPI core structure. T. brucei GPIs have been associated with macrophage activation and alleviation of parasitemia during infection, acting as disease onset delaying antigens. Literature reports that link structural modifications in the GPIs to changes in biological activity are contradictory. We have established a synthetic route to prepare structurally overlapping GPI derivatives bearing different T. brucei characteristic structural modifications. The GPI collection will be used to assess the effect of galactosylation and phosphorylation on T. brucei GPI immunomodulatory activity, and to perform an epitope mapping of this complex glycolipid as potential diagnostic marker for Trypanosomiasis. A strategy for the synthesis of a complete α‐tetragalactoside using the 2‐naphthylmethyl protecting group and for subsequent attachment of GPI fragments to peptides is presented.