bluuebunny/crossref_metadata_2025_split huggingface dataset:
Conventional vascular access site approach versus fully trans‐wrist approach for chronic total occlusion percutaneous coronary intervention: a multicenter registry
Authors: Poletti Enrico , Azzalini Lorenzo , Ayoub Mohamed , Ojeda Soledad , Zivelonghi Carlo , La Manna Alessio , Bellini Barbara , Lostalo Adrián , Luque Aurora , Venuti Giuseppe , Montorfano Matteo , Agostoni Pierfrancesco , Pan Manuel , Carlino Mauro , Mashayekhi Kambis 
Published: October 2019

AbstractObjectivesTo evaluate the incidence of vascular complication and major bleeding in patients undergoing chronic total occlusion (CTO) percutaneous coronary intervention (PCI) with a fully trans‐wrist access (TWA) approach versus a conventional approach based on trans‐femoral access (TFA).BackgroundTFA is the preferred vascular access in CTO PCI, but it has been associated with a non‐negligible risk of complications.MethodsThis retrospective registry included all patients undergoing CTO PCI at five institutions between July 2011 and October 2018. Patients were divided into two groups: Conventional (patients treated with at least one TFA) and Fully TWA (subjects exclusively treated with one or two TWA). The primary safety endpoint was a composite of vascular complications and major bleeding. The primary efficacy endpoint was procedural success.ResultsWe included 1,900 patients (Conventional n = 1,496 and Fully TWA n = 404). Conventional patients showed higher occlusion complexity (J‐CTO score 2.1 ± 1.2 vs. 1.5 ± 1.1, p < .001). Procedural success showed no significant difference between both groups (85.7 vs. 83.0%, p = .17). The primary safety endpoint occurred more frequently in the Conventional group (10.3 vs. 4.5%, p < .001), driven by vascular complications (9.4 vs. 3.7%, p < .001). On multivariate analysis, not using a Fully TWA approach was an independent predictor of the study endpoint, after adjusting for age, sex, diabetes, body mass index, chronic kidney disease, prior coronary artery bypass graft, and J‐CTO score.ConclusionsEmbracing a Fully TWA approach for CTO PCI might be associated with lower incidence of a composite endpoint of vascular complications and major bleeding, compared with a Conventional approach.
Targeted Fe‐Doping of Ni−Al Catalysts via the Surface Redox Reaction Technique for Unravelling its Promoter Effect in the CO2 Methanation Reaction
Authors: Burger Thomas , Augenstein Hannah M. S. , Hnyk Franziska , Döblinger Markus , Köhler Klaus , Hinrichsen Olaf 
Published: October 2019

AbstractIn promoted catalyst systems, the location of dopants is of very high interest to investigate promoter effects. A Ni/Al2O3 catalyst (wNi=11 wt. %) prepared by deposition‐precipitation and a co‐precipitated NiAlOx (nNi/nAl=1) catalyst are modified with Fe by means of the surface redox reaction technique and tested for activity under differential and integral conditions and for thermal stability (aging at 500 °C, 8 bar, 32 h) in the methanation reaction of CO2. By applying detailed material characterization studies comprising H2 and CO2 chemisorption, ICP‐OES, XRD, STEM‐EDX, FMR and BET, it is shown that the surface deposition techniques can be used to selectively deposit Fe in the vicinity of Ni nanoparticles. Doping with Fe leads to an increase of the catalytic activity, attributed to electronic effects through the formation of surface Ni−Fe alloys, and, for the co‐precipitated Ni−Al catalyst, to an enhancement of the apparent thermal stability at higher Fe loadings, which is assumed to be caused by a dynamic variation of Ni, Fe, and Al interactions depending on the reaction conditions.
Sky‐Blue Triplet Emitters with Cyclometalated Imidazopyrazine‐Based NHC‐Ligands and Aromatic Bulky Acetylacetonates
Authors: Pinter Piermaria , Soellner Johannes , Strassner Thomas 
Published: October 2019

AbstractPlatinum(II) complexes with an N‐heterocyclic carbene and a cyclometalating phenyl ligand (C^C*) are excellent candidates as efficient blue triplet emitters for OLED applications. The electronic and photophysical properties of these complexes can be fine‐tuned with the objective to increase the quantum yields and lower the phosphorescence decay times. We found that platinum complexes with an imidazopyrazine C^C* ligand and bulky acetylacetonates are sky‐blue triplet emitters, characterised by an almost unitary quantum yield and short phosphorescence decay times.
Covalent Organic Frameworks: A Sustainable Photocatalyst toward Visible‐Light‐Accelerated C3 Arylation and Alkylation of Quinoxalin‐2(1H)‐ones
Authors: Tian Miao , Liu Shuyang , Bu Xiubin , Yu Jipan , Yang Xiaobo 
Published: October 2019

AbstractA practical and scalable protocol for visible‐light‐accelerated arylation and alkylation of quinoxalin‐2(1H)‐ones with hydrazines is reported. In this protocol, a hydrazone‐based two‐dimensional covalent organic frameworks (2D‐COF‐1) was employed as the heterogeneous photocatalyst (PC). Due to its excellent photocatalytic properties, good chemical stability and heterogeneous nature, the present method exhibits high efficiency, good functional group tolerance, easy scalability and remarkable catalyst reusability. More importantly, it provides an alternative way that allows rapid access to various C3 arylated or alkylated quinoxalin‐2(1H)‐ones in a greener and sustainable manner.
Histidinium‐Driven Chirality Control of Self‐Assembled Hybrid Molybdenum Oxyfluorides
Authors: Jo Hongil , Ok Kang Min 
Published: October 2019

AbstractExploring macroscopic chiral materials with extended structures has become an important and fundamental topic in chemistry. To systematically control the chirality of novel organic–inorganic frameworks, histidinium‐based cationic structure‐directing agents containing specific chiral information are introduced. In this way, two chiral compounds, [(l‐hisH2)MoO2F4]3⋅H2O (L) and [(d‐hisH2)MoO2F4]3⋅H2O (D), and an achiral oxyfluoride, (l/d‐hisH2)MoO2F4 (LD) (his=histidine, C6H9N3O2) have been successfully self‐assembled by a slow evaporation method. The structures of these compounds are composed of histidinium cations and distorted [MoO2F4]2− octahedra. Surprisingly, the histidinium cations not only control macroscopic chirality, but also induce O/F ordering in MoO2F4 octahedra through hydrogen‐bonding interactions. Compounds L and D crystallize in the extremely rare polar space group P1, and exhibit positive second harmonic generation (SHG) signals attributable to a net moment originating from the MoO2F4 groups. Solid‐state circular dichroism (CD) spectra indicate that the MoO2F4 units templated by histidinium cations are chirally aligned through ionic interactions. Crystallization processes influenced by the chirality of the reported materials are also discussed herein.
α‐Unsaturated 3‐Amino‐1‐carboxymethyl‐β‐lactams as Bacterial PBP Inhibitors: Synthesis and Biochemical Assessment
Authors: Decuyper Lena , Magdalenić Katarina , Verstraete Marie , Jukič Marko , Sosič Izidor , Sauvage Eric , Amoroso Ana Maria , Verlaine Olivier , Joris Bernard , Gobec Stanislav , D'hooghe Matthias 
Published: October 2019

AbstractInnovative monocyclic β‐lactam entities create opportunities in the battle against resistant bacteria because of their PBP acylation potential, intrinsically high β‐lactamase stability and compact scaffold. α‐Benzylidene‐substituted 3‐amino‐1‐carboxymethyl‐β‐lactams were recently shown to be potent PBP inhibitors and constitute eligible anchor points for synthetic elaboration of the chemical space around the central β‐lactam ring. The present study discloses a 12‐step synthesis of ten α‐arylmethylidenecarboxylates using a microwave‐assisted Wittig olefination as the crucial reaction step. The library was designed aiming at enhanced β‐lactam electrophilicity and extended electron flow after enzymatic attack. Additionally, increased β‐lactamase stability and intermolecular target interaction were envisioned by tackling both the substitution pattern of the aromatic ring and the β‐lactam C4‐position. The significance of α‐unsaturation was validated and the R39/PBP3 inhibitory potency shown to be augmented the most through decoration of the aromatic ring with electron‐withdrawing groups. Furthermore, ring cleavage by representative β‐lactamases was ruled out, providing new insights in the SAR landscape of monocyclic β‐lactams as eligible PBP or β‐lactamase inhibitors.
Visible‐Light‐Mediated Dearomatisation of Indoles and Pyrroles to Pharmaceuticals and Pesticides
Authors: Schilling Waldemar , Zhang Yu , Riemer Daniel , Das Shoubhik 
Published: October 2019

AbstractDearomatisation of indole derivatives to the corresponding isatin derivatives has been achieved with the aid of visible light and oxygen. It should be noted that isatin derivatives are highly important for the synthesis of pharmaceuticals and bioactive compounds. Notably, this chemistry works excellently with N‐protected and protection‐free indoles. Additionally, this methodology can also be applied to dearomatise pyrrole derivatives to generate cyclic imides in a single step. Later this methodology was applied for the synthesis of four pharmaceuticals and a pesticide called dianthalexin B. Detailed mechanistic studies revealed the actual role of oxygen and photocatalyst.
Alkaline Earth Metal Template (Cross‐)Coupling Reactions with Hybrid Disila‐Crown Ether Analogues
Authors: Dankert Fabian , Donsbach Carsten , Rienmüller Julia , Richter Roman M. , von Hänisch Carsten 
Published: October 2019

AbstractAlkaline earth metal iodides were used as templates for the synthesis of novel silicon‐based ligands. Siloxane moieties were (cross‐)coupled and ion‐specific, silicon‐rich crown ether analogues were obtained. The reaction of 1,2,7,8‐tetrasila[12]crown‐4 (I) and 1,2‐disila[9]crown‐3 (II) with MgI2 yielded exclusively [Mg(1,2,7,8‐tetrasila[12]crown‐4)I2] (1). The larger Ca2+ ion was then employed for cross‐coupling of I and II and yielded the complex [Ca(1,2,7,8‐tetrasila[15]crown‐5)I2] (2). Cross‐coupling of I and 1,2,4,5‐tetrasila[9]crown‐3 (III) with SrI2 enables the synthesis of the silicon‐dominant 1,2,4,5,10,11‐hexasila[15]crown‐5 ether complex of SrI2 (3). Further, the compounds [Sr(1,2,10,11‐tetrasila[18]crown‐6)I2] (4), [Sr(1,2,13,14‐tetrasila[24]crown‐8)I2] (5), and [Sr(1,2,13,14‐tetrasila‐dibenzo[24]crown‐8)I2] (6) were obtained by coupling I, 1,2‐disila[12]crown‐4 (IV) or 1,2‐disila‐benzo[12]crown‐4 (V), respectively. Using various anions, the (cross‐)coupled ligands were also observed in an X‐ray structure within the mentioned complexes. These template‐assisted (cross‐)couplings of various ligands are the first of their kind and a novel method to obtain macrocycles and/or their metal complexes to be established. Further, the Si−O bond activations presented herein might be of importance for silane or even organic functionalization.
Ultrafine PtRu Dilute Alloy Nanodendrites for Enhanced Electrocatalytic Methanol Oxidation
Authors: Zhang Shuping , Rong Hongpan , Yang Tianyi , Bai Bing , Zhang Jiatao 
Published: October 2019

AbstractDilute alloy nanostructures have been demonstrated to possess distinct catalytic properties. Noble‐metal‐induced reduction is one effective synthesis strategy to construct dilute alloys and modify the catalytic performance of the host metal. Herein, we report the synthesis of ultrafine PtRu dilute alloy nanodendrites (PtRu NDs, molar ratio Ru/Pt is 1:199) by the reduction of RuIII ions induced by Pt metal. For the methanol oxidation reaction, PtRu NDs showed the highest forward peak current density (2.66 mA cm−2, 1.14 A/mgPt) and the best stability compared to those of pure‐Pt nanodendrites (pure‐Pt NDs), commercial PtRu/C and commercial Pt/C catalysts.
Time Evolution of Local pH Around a Photo‐Acid in Water and a Polymer Hydrogel: Time Resolved Fluorescence Spectroscopy of Pyranine
Authors: Chakraborty Subhajit , Nandi Somen , Bhattacharyya Kankan , Mukherjee Saptarshi 
Published: October 2019

AbstractIn this work, we propose a new analysis of the time resolved emission spectra of a photo‐acid, HA, pyranine (8‐hydroxypyrene‐1,3,6‐trisulphonic acid, HPTS) based on time resolved area normalized emission spectra (TRANES). Presence of an isoemissive point in TRANES confirms the presence of two emissive species (HA and A−) inside the system in bulk water and inside a co‐polymer hydrogel [F127, (PEO)100–(PPO)70–(PEO)100]. We show that following electronic excitation, the local pH around HPTS, is much lower than the bulk pH presumably because of ejection of proton from the photo‐acid in the excited state. With increase in time, the local pH increases and reaches the bulk value. We further, demonstrate that the excited state pKa of HPTS may be estimated from the emission intensities of HA and A− at long time. The time constant for time evolution of pH is ∼630 ps in water, ∼1300 ps in F127 gel and ∼4700 ps in CTAB micelle. The location and local viscosity sensed by the probe is ascertained using fluorescence correlation spectroscopy (FCS) and fluorescence anisotropy decay. The different values of the local viscosity reported by these two methods are reconciled.
Performance of Density Functional Theory for Transition Metal Oxygen Bonds
Authors: Moltved Klaus A. , Kepp Kasper P. 
Published: October 2019

AbstractThe accuracy of density functional theory (DFT) limits predictions in theoretical catalysis, and strong chemical bonds between transition metals and oxygen pose a particular challenge. We benchmarked 30 diverse density functionals against the bond dissociation enthalpies (BDE) of the 30 MO and 30 MO+ diatomic systems of all the 3d, 4d, and 5d metals, to test universality across the d‐block as required in comparative studies. Seven functionals, B98, B97‐1, B3P86, B2PLYP, TPSSh, B3LYP, and B97‐2, display mean absolute errors (MAE) <30 kJ/mol. In contrast, many commonly used functionals such as PBE and RPBE overestimate M−O bonding by +30 kJ/mol and display MAEs from 48–76 kJ/mol. RPBE and OPBE reduce the over‐binding of PBE but remain very inaccurate. We identify a linear relationship (p‐value 7.6 ⋅ 10−5) between the precision and accuracy of DFT, i. e. inaccurate functionals tend to produce larger, unpredictable random errors. Some functionals commonly deviate from this relationship: Thus, M06‐2X is very precise but not very accurate, whereas B3LYP* and MN15‐L are more accurate but less precise than M06‐2X. The best‐performing hybrids have 10–30 % HF exchange, but this can be relieved by double hybrids (B2PLYP). Most functionals describe trends well, but errors comparing 5d to 4d/3d are ∼10 kJ/mol larger than group‐wise errors, due to uncertainties in the spin‐orbit coupling corrections for effective core potentials, affecting e. g. Pt/Pd or Au/Ag comparisons.
Erweiterung des Anwendungsbereichs von DIN EN 1996‐3/NA für hohe Wände
Authors: Förster Valentin , Graubner Carl‐Alexander 
Published: October 2019

AbstractAccording to Eurocode 6, unreinforced masonry walls can be designed using different verification methods, whereby the simplified calculation methods are contained in Part 3 of DIN EN 1996 [1]. If the associated application limits and boundary conditions are fulfilled, a large part of the usual problems occurring in masonry construction can be dealt with without great effort. A limiting condition for the application of the simplified calculation methods is a maximum clear wall height of h = 2.75 m or h = 12 • t. Changes in user requirements for modern buildings with masonry walls nowadays often require greater wall heights, wherefore a verification according to the general rules from DIN EN 1996‐1‐1/NA [2] is necessary. This means a considerably higher effort for the structural engineer.A considerable amount of calculations was done to verify whether the results of the simplified calculation methods are also valid for greater wall heights. The results were transferred into a consistent standardization proposal with regard to extended application limits of DIN EN 1996‐3/NA, which is contained in a new draft Amendment A3 for the National Application Document for Germany.
Comparison of fish detections, community diversity, and relative abundance using environmental DNA metabarcoding and traditional gears
Authors: Sard Nicholas M. , Herbst Seth J. , Nathan Lucas , Uhrig Genelle , Kanefsky Jeannette , Robinson John D. , Scribner Kim T. 
Published: October 2019

AbstractBackgroundDetecting species at low abundance, including aquatic invasive species (AIS), is critical for making informed management decisions. Environmental DNA (eDNA) methods have become a powerful tool for rare or cryptic species detection; however, many eDNA assays offer limited utility for community‐level analyses due to their use of species‐specific (presence/absence) ‘barcodes’. Metabarcoding methods provide information on entire communities based on sequencing of all taxon‐specific barcodes within an eDNA sample.AimsEvaluate measures of fish species detections, community diversity, and estimates of relative abundance based on eDNA metabarcoding and traditional fisheries sampling approaches in the context of fish community characterization and AIS survellience.Materials and MethodsIn 2016, eight limnologically diverse lakes (surface area range: 13 – 1,728 ha) in Michigan, USA were sampled using a variety of traditional fisheries gears to characterize fish community composition. Environmental DNAs from surface (33 ± 6, mean ± 1 SD) and benthic (14 ± 2) water samples from each lake were isolated and amplified for two metabarcoding markers (mitochondrial 12S and 16S rDNA loci) using fish‐specific primers. Fish species detected within each lake were determined by comparing the sequencing data to a database of sequences from native Michigan fish species and 19 AIS on the Michigan's Watch List.ResultsAnalysis of species accumulation curves indicated multi‐locus eDNA metabarcoding assays can enhance species detection capacities and characterize 95% of a fish community in fewer sampling efforts than traditional gear (range: 2 – 62, median: 14). In addition, all AIS detected in traditional gear samples were also detected by eDNA, while some AIS detected by eDNA assays were absent from traditional gear samples.DiscussionResults reported here are, in part, driven by the lack of species‐selectivity during eDNA sampling events. Given the efficacy of eDNA assays, we suggest multi‐locus eDNA metabarcoding assays be implemented in early detection efforts.
Aroma‐Relevant Volatile Compounds as Markers for the Sensory Quality of Argan Oil
Authors: Matthäus Bertrand , Bonte Anja , Sinning Bernadette , Charrouf Zoubida 
Published: October 2019

AbstractThe aim of the present work is to identify and characterize the most important aroma active compounds of argan oil from unroasted and roasted argan almonds as well as roasted almonds obtained from goat‐digested fruits by dynamic headspace GC and GC‐olfactometry with aroma dilution analysis to classify samples from the market according to their processing. While fresh ground argan almonds are characterized by only seven aroma active compounds, in argan oil from unroasted and roasted almonds, 22 and 35 aroma active compounds are found, respectively. As a result of the roasting process, 14 aroma active compounds with dilution factors >64 are detected in the oil by GC‐olfactometry. 17 aroma active compounds show significant differences between the three different argan oil qualities. These compounds are used to differentiate the quality of argan oil from the market.Practical Application: Argan oil belongs to the high‐price oils on the market but sometimes the sensory quality of the oil contradicts the positive image that has been built up for oil by unpleasant cheese‐like and fusty sensory attributes. Although some information about the composition of the volatile compounds of cold‐pressed argan oil from unroasted and roasted kernels is available, the knowledge about compounds that are typical for the aroma of argan oil is important in order to develop analytical methods for the classification of different argan oil qualities. This reduces the work for a panel group that is often time and labor consuming and sometimes the results are not reliable. The present paper demonstrates which volatile compounds show significant differences between argan oil from unroasted and roasted argan almonds as well as roasted almonds obtained from goat‐digested fruits allowing a differentiation of these oils.
Trading risk control model of electricity retailers in multi‐level power market of China
Authors: Yu Xiaobao , Sun Yixin 
Published: October 2019

AbstractThe decision‐making and risk assessment of electricity purchase and sales is the key to adapt to the electricity market for independent electricity retailers in China. This research carried out the purchase and sales risks of electricity for electricity retailers and constructed the multi‐level market purchase and sales combination optimization model. Based on the portfolio optimization theory, the conditional value at risk theory (CVaR) was proposed. Based on the evaluation index about the conditional risk profit and CVaR, electricity retailers purchase and sales combined optimization model has been constructed to explore the impact of purchase and sales risks by different factors in multi‐level electricity market. The example analysis was carried out by the fixed spread mode and the linkage spread mode. The results showed that the mathematical mean and variance of market spread had great influence on the electricity purchase and sales combination. Especially in the mature electricity market, the mathematical mean of spread and risk in medium‐ and long‐term market was smaller than that in spot market, and the best point of the electricity purchase and sales combination was shown on the smallest value of CVaR, while the electricity purchase and sales combination was optimal under limited conditions.
A National-Scale Framework for Visualizing Riverine Concentrations of Microplastics Released from Municipal Wastewater Treatment Incorporating Generalized Instream Losses
Authors: Holmes Christopher M. , Dyer Scott D. , Vamshi Raghu , Maples-Reynolds Nikki , Davies Iain A. 
Published: October 2019

Abstract
Down-the-drain exposure models provide a valuable tool for estimating environmental exposure to substances which are treated and discharged by municipal wastewater-treatment plants (WWTPs). Microplastics may enter WWTPs from consumer activities and disposal. An exposure framework was developed using the iSTREEM® model, which estimates spatially explicit concentrations of substances in riverine systems across the United States and portions of Ontario, Canada. One hundred simulations covering a range of WWTP removal and instream loss rates (proxy for net sedimentation) were incorporated into a Web-based visualization tool for user exploration of relative concentrations across simulations. Surface water concentrations specific to user-supplied tonnage were examined via interactive heat maps and cumulative distributions. Exploring the spatial aspect of iSTREEM results showed that modeling 90% WWTP removal and no instream loss resulted in 8.5% of the mass entering WWTPs discharged to marine estuaries (7.4%) or Great Lakes (1.1%) environments, with the remainder of the mass discharged (1.5%) in inland sinks or exiting the United States via rivers. Modeling an example instream loss of k = 0.1 d–1 (i.e., half-life = 7 d), terminal river segments contained 3.3% of influent mass (2.3% marine estuaries, 1.0% Great Lakes). Varying instream loss rates had substantial impacts on the total mass exported. The Web-based tool provided a user-based mechanism to visualize relative freshwater concentrations of microplastics across a large geographic area by varying simplified particle fate assumptions. Environ Toxicol Chem 2019;39:210–219. © 2019 SETAC
Abstract
Hypothetical microplastic particles emitted from municipal wastewater treatment were modeled to estimate relative environmental concentrations in rivers when wastewater and in-stream removal rates were varied. Comparisons of marine and Great Lakes discharge reaches were made with the overall set of more than 28 000 river segments in the conterminous United States and portions of Ontario, Canada. WWTP = wastewater-treatment plant.