bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Metallaphotoredox Strategy for the Cross‐Electrophile Coupling of α‐Chloro Carbonyls with Aryl Halides
Authors: Chen Tiffany Q. , MacMillan David W. C. 
Published: August 2019

AbstractHere, we demonstrate that a metallaphotoredox‐catalyzed cross‐electrophile coupling mechanism provides a unified method for the α‐arylation of diverse activated alkyl chlorides, including α‐chloroketones, α‐chloroesters, α‐chloroamides, α‐chlorocarboxylic acids, and benzylic chlorides. This strategy, which is effective for a wide variety of aryl bromide coupling partners, is predicated upon a halogen atom abstraction/nickel radical‐capture mechanism that is generically successful across an extensive range of carbonyl substrates. The construction and use of arylacetic acid products have further enabled two‐step protocols for the delivery of valuable building blocks for medicinal chemistry, such as aryldifluoromethyl and diarylmethane motifs.
Building a Bridge from Papermaking to Solar Fuels
Authors: Jiang Zaiyong , Zhang Xinhan , Sun Wei , Yang Deren , Duchesne Paul N. , Gao Yugang , Wang Zeyan , Yan Tingjiang , Yuan Zhimin , Yang Guihua , Ji Xingxiang , Chen Jiachuan , Huang Baibiao , Ozin Geoffrey A. 
Published: August 2019

AbstractBlack liquor, an industrial waste product of papermaking, is primarily used as a low‐grade combustible energy source. Despite its high lignin content, the potential utility of black liquor as a feedstock in products manufacturing, remains to be exploited. Demonstrated here in is the use of black liquor as a primary feed‐stock for synthesizing graphene quantum dots that exhibit both up‐conversion and photoluminescence when excited using visible/near‐infrared radiation, thereby enabling the photosensitization of ultraviolet‐absorbing TiO2 nanosheets. In addition, these graphene quantum dots can trap photo‐generated electrons to realize the effective separation of electron‐hole pairs. Together, these two processes facilitate the solar‐powered generation of H2 from H2O, and CO from H2O–CO2, using broadband solar radiation.
Network latency and long‐distance robotic telestenting: Exploring the potential impact of network delays on telestenting performance
Authors: Madder Ryan D. , VanOosterhout Stacie , Mulder Abbey , Bush Jared , Martin Samuel , Rash Adam J. , Tan Jose Mariano , Parker Jessica L. , Kalafut Andrew , Li Yao , Kottenstette Nicholas , Bergman Per , Nowak Brent 
Published: August 2019

AbstractObjectiveThis study evaluated the impact of network latency on telestenting performance.BackgroundThe feasibility of long‐distance robotic telestenting was recently demonstrated, yet the impact of network performance on telestenting remains unknown.MethodsEx vivo and in vivo telestenting models were constructed by connecting a robotic drive over a wired network to a robotic control system up to 103 miles away. During consecutive attempts to robotically wire a coronary artery, investigators randomly added signal latencies from 0 to 1,000 ms. Outcomes included wiring success, wiring time (time to advance wire to preselected target landmark), and perceived latency score (5 = imperceptible; 4 = noticeable but minor; 3 = noticeable; 2 = noticeable and major; 1 = unacceptable).ResultsWiring success was achieved in 95 of 95 attempts in the ex vivo model and in 57 of 57 attempts in vivo. No significant difference in wiring time was observed across added latencies from 0 to 1,000 ms in the ex vivo (p = .64) or in vivo (p = .40) models. Compared to an added latency of 0 ms, perceived latency scores were not significantly different for added latencies of 150 and 250 ms (p = NS for both), but were significantly lower for latencies ≥400 ms (p < .001).ConclusionsAdded latencies up to 250 ms were not associated with perceived latency, but latencies ≥400 ms were perceptible. Based on these findings, future telestenting studies should utilize networks with latencies ≤250 ms if perceived latency is to be avoided.
Carotid artery stenting is safe and effective for symptomatic patients with acute coronary syndrome
Authors: Casana Renato , Tolva Valerio Stefano , Odero Andrea , Malloggi Chiara , Silani Vincenzo , Parati Gianfranco 
Published: August 2019

AbstractBackgroundPatients with symptomatic carotid stenosis recently treated with percutaneous transluminal coronary angioplasty (PTCA) for acute coronary syndrome (ACS) are always classified as at high risk for surgery, given that they are required uninterrupted dual antiplatelet therapy. In this regard, carotid artery stenting (CAS) may represent a valid alternative.ObjectiveThe purpose of this study is to overview CAS outcomes in symptomatic patients with and without ACS.MethodsOne hundred fifty‐one consecutive symptomatic patients who underwent CAS between 2010 and 2017 in a single institution were included in this study, of which 66 (43.7%) were identified as having ACS. All patients were followed‐up with carotid duplex ultrasound scan and a neurological assessment of symptoms status at 30‐day postprocedure and at 3, 6, and 12 months, with annual follow‐up after that for 3 years.ResultsAmong symptomatic ACS patients, common risks factors were active smoking, metabolic syndrome, diabetes, and hypertension. In the short‐term follow‐up, no significant differences were observed among rates of death, stroke, myocardial infarction (MI), and restenosis, between patients with and without ACS. Mean clinical follow‐up was 28.2 (12.3) months. In the long‐term follow‐up, higher rates of death and MI were recorded in patients with ACS (death: 11.4% vs. 5.4%, p = .04; MI: 11.4% vs. 3.6%, p = .02), owing to the complexity of these patients.ConclusionsThis single‐center study suggested that CAS is a safe and effective treatment for patients with symptomatic carotid artery stenosis, who recently underwent PTCA for ACS, requiring uninterrupted dual antiplatelet therapy.
Catalysts Supported by Homochiral Molecular Helices: A New Concept to Implement Asymmetric Amplification in Catalytic Science
Authors: Li Yan , Bouteiller Laurent , Raynal Matthieu 
Published: August 2019

AbstractConnecting intrinsically achiral catalytic centers to helical polymers provides a new class of asymmetric catalysts whose selectivity exclusively stems from the chiral environment provided by the helical polymer. Chirality amplification phenomena allow to control the handedness and the helical sense excess of these polymers which in turn dictate the stereochemical direction and the extent of enantioinduction, respectively, obtained in the course of the asymmetric reaction. This minireview is focused on such helical catalysts built either on a covalent or a non‐covalent scaffold and for which the handedness is controlled by an asymmetric polymerization reaction, by enantiopure monomers or by chiral additives. The selectivity of catalysts based on a dynamic helical backbone can be tuned by changing the solvent or with additives. The fact that the enantiomeric state of such asymmetric catalysts can be switched in a predictable way is particularly emphasized.
Electrons and Holes as Catalysts in Organic Electrosynthesis
Authors: Francke Robert , Little R. Daniel 
Published: August 2019

AbstractInvited for this month's cover picture is Robert Francke from the University of Rostock (Germany) and R. Daniel Little from the University of California Santa Barbara (USA). The cover picture highlights the catalytic effect of heterogeneous electron transfers on chemical reactions of organic molecules (“electrochemical catalysis”). A comparison is shown between the typical energy profile of a thermally induced reaction and the corresponding electrochemically catalyzed transformation using the example of the Newman‐Kwart rearrangement. Read the full text of the Minireview at 10.1002/celc.201900432.
Bis‐4,4′‐biphenyl Ring Embedded Octaphyrin with Three Distinct Conformational Structures
Authors: Chitranshi Sangya , Adinarayana B. , Das Mainak , Cha Won‐Young , Kim Dongho , Srinivasan A. 
Published: August 2019

AbstractThree distinct conformational structures of carbaoctaphyrins were prepared by incorporating bis‐4,4'‐biphenyl units in the macrocyclic core. The free‐base form adopts a figure‐eight conformation, whereas the protonation triggers a conformational change with a pyrrole ring inversion and acquires an open‐framework structure. The insertion of bis‐RhI metal ion in the macrocyclic core affords a singly twisted conformational structure. Furthermore, the local aromaticity in the bis‐4,4'‐biphenyl ring dominates the overall macrocyclic aromaticity in all three forms, and thus adopts nonaromatic characteristics. These results are supported by spectral as well as theoretical studies, and they are unambiguously confirmed by X‐ray crystal analyses.
Barium Siloxides and Catalysed Formation of Si−O−Si' Motifs
Authors: Le Coz Erwann , Kahlal Samia , Saillard Jean‐Yves , Roisnel Thierry , Dorcet Vincent , Carpentier Jean‐François , Sarazin Yann 
Published: August 2019

AbstractThe first unsupported barium siloxide, the homoleptic dimer [Ba2{μ2‐OSi(SiMe3)3}3{OSi(SiMe3)3}], is presented, and its structural features are discussed in the light of DFT computations. This complex, together with the related [Ba{μ2‐OSi(SiMe3)3}{N(SiMe3)2}]2 and their parent [Ba{N(SiMe3)2}2]2, mediates the formation of asymmetric siloxanes R3Si−O−SiR′3 through the first case of main group metal‐mediated dehydrocoupling of silanols and hydrosilanes. Early kinetic analysis highlights an unusual catalytic manifold.
The multi‐stage vertical bioreactor in water engineering
Authors: Alvarez Cuenca Manuel , Reza Maryam 
Published: August 2019

AbstractThe excess of nutrients like nitrogen and phosphorous compounds in surface water (ie, coastal areas, lakes, and rivers) is responsible for major economic, public health, and environmental crises. Their impact is measured in multi‐billion‐dollar losses, in greenhouse gas emissions and severe algal blooms whose toxicity and geographical dimensions are being monitored and recorded. The present paper focuses on four areas, namely: (a) the economic impact of nutrient pollution, (b) a brief glance at the evolution of the technologies associated with nutrient removal from water/wastewater, (c) a review of the existing conventional planar reactors used in nutrient removal plants, and (d) a description of a novel multi‐stage vertical bioreactor and its removal performance, microbial ecology, comparative costs, and construction flexibility. This bioreactor with acronym STAR (simultaneous treatment for ammonia/phosphate removal) is the first multistage bioreactor with vertical configuration used for the simultaneous nitrification, denitrification, and biological phosphorus removal from wastewater. The bioreactor shows high nutrient removal efficiencies of over 95% for both phosphorous and nitrogen compounds. Due to its vertical configuration, this bioreactor requires a smaller footprint and its modularity makes it exceedingly flexible to accommodate to the restricted construction spaces in urban areas.
Removal of aluminum from alkaline aqueous solution by adsorption on Degussa P25 TiO2 and vermiculite concrete‐supported ferric oxyhydroxide
Authors: Popugaeva Daria , Kreyman Konstantin , Ray Ajay K. 
Published: August 2019

AbstractThe current investigation on aluminum adsorption from an aqueous solution originated from the need to implement a water treatment technology that would decrease the prohibitive aluminum concentrations in the groundwater of the Khibiny Alkaline Massif (Kola Peninsula), which is limiting the use of this water source as a source for the household water supply in the area. TiO2 and vermiculite concrete‐supported ferric oxyhydroxide (VC) were used as adsorbents to remove aluminum from the alkaline aqueous solution, considering the water‐specific natural conditions of the Khibiny aquifer. The effects of pH, initial aluminum concentration, contact time, adsorbent dose, and ions present in Khibiny groundwater were investigated. The results showed that the adsorption kinetics followed the pseudo‐second order model, and the equilibrium data were described well by Langmuir and Freundlich isotherm models. The aluminum adsorption on TiO2 exhibited a dramatically higher adsorption rate compared to VC; the adsorption equilibrium was reached in 30 and 240 minutes, respectively, while the maximum TiO2 and VC adsorption capacities were similar and had values of 6.85 and 6.75 mg g−1 as the results of laboratory tests revealed. It was shown that when these two adsorbents worked jointly the capacity reached 8.28 mg g−1 within 60 minutes at pH 9.0. No apparent significant effects on aluminum removal by adsorbents tested in the presence of SO42−, NO3−, and Cl− were observed. The obtained outcomes identify a possible approach and reliable foundation for water treatment technology to solve the problem of elevated aluminum concentrations in the household water of the Khibiny Alkaline Massif area as well as within other locations where the solution of this problem can improve living conditions or industrial technologies.
Assessment of Bezlotoxumab Immunogenicity
Authors: Montgomery Diana L. , Matthews Randolph P. , Yee Ka Lai , Tobias Lori M. , Dorr Mary Beth , Wrishko Rebecca E. 
Published: August 2019

AbstractBezlotoxumab is a fully human monoclonal antibody that binds and neutralizes Clostridium difficile toxin B. This analysis investigated the potential of bezlotoxumab to induce immunogenicity in healthy phase 1 trial participants and in phase 2/3 trial participants receiving oral antibacterial therapy for primary or recurrent C difficile infection. Immunogenicity to bezlotoxumab was evaluated following a single intravenous dose (≤20 mg/kg) or 2 consecutive doses (10 mg/kg) given 84 days apart in healthy participants across 3 phase 1 trials (Protocol MK‐3415A‐004, N = 30; Protocol CA‐GCDX‐05‐01, N = 54; Protocol MK‐3415A‐006, N = 12) and following a single 10 mg/kg dose in 1 phase 2 trial (Protocol CA‐GCDX‐06‐02, ClinicalTrials.gov identifier: NCT00350298; N = 97) and 2 phase 3 trials (Protocols MK‐3415A‐001 and MK‐3415A‐002, ClinicalTrials.gov identifiers: NCT01241552 and NCT01513239; N = 1414). No treatment‐emergent antidrug antibodies were observed following single or repeated dosing of bezlotoxumab. No phase 1 participants and only 1 phase 2 participant tested positive before bezlotoxumab exposure (non–treatment‐emergent positive). Nine participants tested non–treatment‐emergent positive in phase 3 trials, 1 of whom was neutralizing antibody–positive. Overall, the immunogenicity potential of bezlotoxumab is considered to be low.
Structure and Density Comparison of Noble Gas Hydrates Encapsulating Xenon, Krypton and Argon
Authors: Takeya Satoshi , Hachikubo Akihiro 
Published: August 2019

AbstractUnderstanding the effect of guest species on the host framework is important for the development of structure‐based properties of inclusion compounds. Herein, the crystal structures of the noble gas hydrates encapsulating Xe, Kr, and Ar were studied by powder X‐ray diffraction measurements. The crystal structures and hydration numbers of these noble gas hydrates were solved by Rietveld refinements using optimized models with the direct‐space technique. It was revealed that host cage size of these hydrates changed depending on the type of guest species even though their unit‐cell parameters were the same. Based on the structure models obtained, the densities of Xe, Kr, and Ar gas hydrates were also determined to be 1.837, 1.445 and 1.097 g/cm3 at 93 K, respectively. Our findings, from a crystallographic point of view, may give insight into further understanding the thermodynamic stability and physical properties of gas hydrates encapsulating small guests.
Hydrogenation of Carbon Dioxide to C2–C4 Hydrocarbons Catalyzed by Pd(PtBu3)2–FeCl2 with Ionic Liquid as Cocatalyst
Authors: Wang Huan , Zhao Yanfei , Wu Yunyan , Li Ruipeng , Zhang Hongye , Yu Bo , Zhang Fengtao , Xiang Junfeng , Wang Zhenpeng , Liu Zhimin 
Published: August 2019

AbstractDirect hydrogenation of CO2 to C2+ hydrocarbons is very interesting, but achieving this transformation below 200 °C is challenging and seldom reported. Herein, a homogeneous catalytic system was developed composed of the ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIm][PF6]), Pd(PtBu3)2, FeCl2, and the ligand 4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene (Xantphos) for hydrogenation of CO2 under mild conditions, which resulted in C2–C4 hydrocarbons in selectivities up to 98.3 C‐mol % at 180 °C. The combination of [BMIm][PF6]) with Xantphos endowed the Pd–Fe catalysts with the ability of activating CO2 and H2 simultaneously via [HPd(PtBu3)(BMIm‐COO)(BMIm)(PF6)Fe]+ species, thus catalyzing the formation of C2–C4 hydrocarbons through CO2 hydrogenation. In addition, this catalytic system is stable and recyclable, which may have promising applications.
Solid‐phase extraction–liquid chromatography–tandem mass spectrometry method for the qualitative analysis of 61 synthetic cannabinoid metabolites in urine
Authors: Gaunitz Franziska , Kieliba Tobias , Thevis Mario , Mercer‐Chalmers‐Bender Katja 
Published: August 2019

AbstractThis article comprises the development and validation of a protocol for the qualitative analysis of 61 phase I synthetic cannabinoid metabolites in urine originating from 29 synthetic cannabinoids, combining solid‐phase extraction (SPE) utilizing a reversed phase silica‐based sorbent (phenyl) with liquid chromatography–tandem mass spectrometry (LC−MS/MS). Validation was performed according to the guidelines of the German Society of Toxicological and Forensic Chemistry. Sufficient chromatographic separation was achieved within a total runtime of 12.3 minutes. Validation included specificity and selectivity, limit of detection (LOD), recovery and matrix effects, as well as auto‐sampler stability of processed urine samples. LOD ranged between 0.025 ng/mL and 0.5 ng/mL in urine. Recovery ranged between 43% and 97%, with only two analytes exhibiting recoveries below 50%. However, for those two analytes, the LODs were 0.05 ng/mL in urine. In addition, matrix effects between 81% and 185% were determined, whereby matrix effects over 125% were observed for 10 non‐first‐generation synthetic cannabinoid metabolites. The developed method enables the rapid and sensitive detection of synthetic cannabinoid metabolites in urine, complementing the spectrum of existing analytical tools in forensic case work. Finally, application to 61 urine samples from both routine and autopsy case work yielded one urine sample that tested positive for ADB‐PINACA N‐pentanoic acid.
Evolution and diversity of two cisco forms in an outlet of glacial Lake Algonquin
Authors: Piette‐Lauzière Gabriel , Bell Allan H. , Ridgway Mark S. , Turgeon Julie 
Published: August 2019

AbstractThe diversity of Laurentian Great Lakes ciscoes (Coregonus artedi, sensu lato) arose via repeated local adaptive divergence including deepwater ciscoes that are now extirpated or threatened. Thenigripinnisform, or Blackfin Cisco, is extirpated from the Great Lakes and remains only in Lake Nipigon. Putativenigripinnispopulations were recently discovered in sympatry withartediin a historical drainage system of glacial Lake Algonquin, the precursor of lakes Michigan and Huron. Given the apparent convergence on Great Lakes form, we labeled this form blackfin. Here, we test the hypothesis thatnigripinnismay have colonized this area from the Great Lakes as a distinct lineage. It would then represent a relict occurrence of the historical diversity of Great Lakes ciscoes. Alternatively, blackfin could have evolved in situ in several lakes. We captured more than 600 individuals in the benthic or pelagic habitat in 14 lakes in or near Algonquin Provincial Park (Ontario, Canada). Fish were compared based on habitat, morphology, and genetic variation at 6,676 SNPs. Contrary to our expectations, both cisco and blackfin belonged to an Atlantic lineage that colonized the area from the east, not from the Great Lakes. Sympatric cisco and blackfin were closely related while fish from different lakes were genetically differentiated, strongly suggesting the repeated in situ origin of each form. Across lakes, there was a continuum of ecological, morphological, and genetic differentiation that could be associated with alternative resources and lake characteristics. This study uncovers a new component of cisco diversity in inland lakes of Canada that evolved independently from ciscoes of the Laurentian Great lakes. The diversity of cisco revealed in this study and across their Canadian range presents a challenge for designating conservation units at the intraspecific level within the framework of the Committee on the Status of Endangered Wildlife in Canada (COSEWIC).
In Situ Investigation of the Thermal Decomposition of Cl4(CH3CN)W(NiPr) During Simulated Chemical Vapor Deposition
Authors: Nolan Michelle M. , Kim Seo Young , Koley Arijit , Anderson Tim , McElwee‐White Lisa 
Published: August 2019

AbstractInvited for the cover of this issue is Lisa McElwee‐White from the University of Florida, USA. The cover image shows a look inside CVD to elucidate the decomposition mechanism for tungsten imido complex Cl4(CH3CN)WNiPr.
Electrochemical Reduction and Oxidation of Six Natural 2′‐Deoxynucleosides at a Pyrolytic Graphite Electrode in the Presence or Absence of Ambient Oxygen
Authors: Špaček Jan , Fojta Miroslav , Wang Joseph 
Published: August 2019

AbstractRecently we have demonstrated that pyrolytic graphite electrodes (PGE) offer a broad analytically useful potential window, ranging from about −2.0 V to +1.6 V vs. Ag|AgCl|3 M KCl, which enables to use the PGE not only for anodic measurements, but also for direct reduction of nucleobases in DNA oligonucleotides. In this follow‐up study, we have focused on the electrochemical behavior of four 2′‐deoxynucleosides derived from adenine, guanine, cytosine, thymine, uracil, and 5‐methyl cytosine on the PGE. On one hand we have obtained analogous primary redox responses as previously with the oligonucleotides. On the other hand, significant differences were observed, particularly when considering secondary responses involving products of the primary conversions, suggesting involvement of different mechanisms. Further we have found that presence of the ambient oxygen in the electrolyte does not dramatically affect the redox signals of the nucleosides. This finding is in contrast with DNA responses measured at the mercury‐based electrodes, where deaeration prior to the measurements was necessary. We demonstrate that all studied nucleosides can be analyzed using a simple ex situ (medium exchange) procedure.
How is collapse risk of RC buildings affected by the angle of seismic incidence?
Authors: Skoulidou Despoina , Romão Xavier , Franchin Paolo 
Published: August 2019

SummaryDespite the undeniable influence of the angle of seismic incidence on seismic demand, limited research has been performed to determine its effect when assessing the probabilistic seismic performance of a structure. Since the ground motion group size has a well‐known significant effect on the variability of collapse risk, the joint effect of both the ground motion group size and the angle of seismic incidence on the estimation of collapse risk is investigated. Results show that the two variables have a different effect on the collapse risk estimates, with one affecting the bias in the expected value of the estimates and the other their variability. In order to ensure acceptable levels of variability and bias, practical proposals are made regarding the minimum number of records and angles of seismic incidence that should be considered.