bluuebunny/crossref_metadata_2025_split huggingface dataset:
Evolution of Ate‐Organoiron(II) Species towards Lower Oxidation States: Role of the Steric and Electronic Factors
Authors: Rousseau Lidie , Herrero Christian , Clémancey Martin , Imberdis Arnaud , Blondin Geneviève , Lefèvre Guillaume 
Published: November 2019

AbstractAte‐iron(II) species such as [Ar3FeII]− (Ar=aryl) are key intermediates in Fe‐catalyzed couplings between aryl nucleophiles and organic electrophiles. They can be active species in the catalytic cycle, or lead to Fe0 and FeI oxidation states, which can themselves be catalytically active or lead to unwished organic byproducts. Analysis of the reactivity of the intermediates obtained by step‐by‐step displacement of the mesityl groups in high‐spin [Mes3FeII]− by less hindered phenyl ligands was performed, and uncovered the crucial role of both steric and electronic parameters in the formation of the Fe0 and FeI oxidation states. The formation of quaternized [Ar4FeIIMgBr(THF)]− intermediates allows the bielectronic reductive elimination energy required for the formation of Fe0 to be reduced. Similarly, the small steric pressure of the aryl groups in [Ar3FeII]− enables the formation of aryl‐bridged [{FeII(Ar)2}2(μ‐Ar)2]2− species, which afford the FeI oxidation state by bimetallic reductive elimination. These results are supported by 1H NMR, EPR, and 57Fe Mössbauer spectroscopies, as well as by DFT calculations.
Fe‐Doped CoP Flower‐Like Microstructure on Carbon Membrane as Integrated Electrode with Enhanced Sodium Ion Storage
Authors: Xu Yalin , Li Xueying , Wang Jiangang , Yu Qing , Qian Xiu , Chen Lizhuang , Dan Yuanyuan 
Published: November 2019

AbstractPoor cyclability and rate performance always impede the development of transition metal phosphide‐based anode materials. Many strategies have been used to address the above problems, such as the designing of hierarchical structures, combination with carbon materials, and doping with other metal elements. Considering those strategies, a flower‐like Fe‐doped CoP material is designed. The synthesis consists of microsheets grown on a carbon membrane (CM, leaves as precursor) through a hydrothermal method and in situ phosphorization. The Fe doping and carbon membrane synergistically induce the formation of a flower‐like hierarchical microstructure during the crystal‐growing process. The unique hierarchical microstructure increases the contact area between electrode and electrolyte, and accommodates the volume expansion during cycling. The hierarchical Fe‐doped CoP grown directly on the carbon membrane increases the active sites for intercalation of sodium species and further promotes the internal electron conduction in the Fe‐doped CoP/CM electrode. Thereby, the Fe‐doped CoP/CM as the anode electrode for sodium ion batteries exhibits a high specific capacity of 515 mA h g−1 at 100 mA g−1 after 100 cycles. Even if the current density rises to 500 mA g−1, the specific capacity is still maintained at 324 mA h g−1 after 500 cycles, showing superior rate performances and cyclability.
Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of AuIII Dicarboranyl Chemistry
Authors: Chambrier Isabelle , Hughes David L. , Jeans Rebekah J. , Welch Alan J. , Budzelaar Peter H. M. , Bochmann Manfred 
Published: November 2019

AbstractThe reaction of 1,1′‐Li2[(2,2′‐C2B10H10)2] with the cyclometallated gold(III) complex (C^N)AuCl2 afforded the first examples of gold(III) dicarboranyl complexes. The reactivity of these complexes is subject to the trans‐influence exerted by the dicarboranyl ligand, which is substantially weaker than that of non‐carboranyl anionic C‐ligands. In line with this, displacement of coordinated pyridine by chloride is only possible under forcing conditions. While treatment of (C^N)Au{(2,2′‐C2B10H10)2} (2) with triflic acid leads to Au−C rather than Au−N bond protonolysis, aqueous HBr cleaves the Au−N bond to give the pyridinium bromo complex 7. The trans‐influence of a series of ligands including dicarboranyl and bis(dicarboranyl) was assessed by means of DFT calculations. The analysis demonstrated that it was not sufficient to rely exclusively on geometric descriptors (calculated or experimental) when attempting to rank ligands for their trans influence. Complex (C^N)Au(C2B10H11)2 containing two non‐chelating dicarboranyl ligands was prepared similar to 2. Its reaction with trifluoroacetic acid also leads to Au−N cleavage to give trans‐(Hpy^C)Au(OAcF)(C2B10H11)2 (8). In crystals of 8 the pyridinium N−H bond points towards the metal centre, while in 7 it is bent away. The possible contribution of gold(III)⋅⋅⋅H−N hydrogen bonding in these complexes was investigated by DFT calculations. The results show that, unlike the situation for platinum(II), there is no evidence for an energetically significant contribution by hydrogen bonding in the case of gold(III).
Evidence for Non‐Innocence of a β‐Diketonate Ligand
Authors: Vinum Morten Gotthold , Voigt Laura , Bell Colby , Mihrin Dmytro , Larsen René Wugt , Clark Kensha Marie , Pedersen Kasper S. 
Published: November 2019

Abstractβ‐Diketonates, such as acetylacetonate, are amongst the most common bidentate ligands towards elements across the entire periodic table and are considered wholly redox‐inactive in their complexes. Herein we show that complexation of 1,1,1,5,5,5‐hexafluoroacetylacetonate (hfac−) to CrII spontaneously affords CrIII and a reduced β‐diketonate radical ligand scaffold, as evidenced by crystallographic analysis, magnetic measurements, optical spectroscopy, reactivity studies, and DFT calculations. The possibility of harnessing β‐diketonates as electron reservoirs opens up possibilities for new metal–ligand concerted reactivity in the ubiquitous β‐diketonate coordination chemistry.
Stereospecific Synthesis and Photophysical Properties of Propeller‐Shaped C90H48PAH
Authors: Zhang Fangyuan , Michail Evripidis , Saal Fridolin , Krause Ana‐Maria , Ravat Prince 
Published: November 2019

AbstractHerein, we have synthesized an enantiomerically pure propeller‐shaped PAH, C90H48, possessing three [7]helicene and three [5]helicene subunits. This compound can be obtained in gram quantities in a straightforward manner. The photophysical and chiroptical properties were investigated using UV/Vis absorption and emission, optical rotation and circular dichroism spectroscopy, supported by DFT calculations. The nonlinear optical properties were investigated by two‐photon absorption measurements using linearly and circularly polarized light. The extremely twisted structure and packing of the homochiral compound were investigated by single‐crystal X‐ray diffraction analysis.
Determination of kinetic parameters of homogenous continuous flow esterification of monobutyl chlorophosphate in a microreactor
Authors: Zhang Yuqiang , Li Jun , Jin Yang , Chen Ming , Wang Yubin 
Published: November 2019

AbstractSynthesized by phosphorus oxychloride and n‐butanol, tri‐n‐butyl phosphate from a three‐step esterification reaction has an extensive range of applications in industrial processes. Similarly, monobutyl chlorophosphate can be obtained rapidly by mixing n‐butanol and phosphorus oxychloride. In view of this, we investigated the kinetics of esterification of monobutyl chlorophosphate with a microchannel system composed of micromixer and coiled capillaries. The reaction started from mixing the phosphorus oxychloride solution and n‐butanol solution in a micromixer, with temperature and residence time in a delayed loop controlled, and then quenching the solution in a container with magnetic agitation. The rate constants for the esterification reaction of monobutyl chlorophosphate were determined to be within a temperature range of 298‐318 K. It was found that the reaction kinetics is second order with respect to monobutyl chlorophosphate concentration and first order to n‐butanol concentration. In our research, a kinetic model was established, the values of the pre‐exponential factor and the activation energy of the reaction were obtained. The reaction kinetic model can interpret the synthesis mechanism of phosphate esters well, thus playing a guiding role in process intensification of phosphate esters synthesis in the future. Additionally, our model is also valuable because it contributes to the establishment of a reaction kinetics network model for the cascade reaction to synthesize phosphate esters.
Update on risk stratification in the Papanicolaou Society of Cytopathology System for Reporting Pancreaticobiliary Cytology categories: 3‐Year, prospective, single‐institution experience
Authors: Sung Simon , Del Portillo Armando , Gonda Tamas A. , Kluger Michael D. , Tiscornia‐Wasserman Patricia G. 
Published: November 2019

BackgroundRisk stratification is a critical element for the successful implementation of cytopathology reporting systems. To the authors' knowledge, there are limited prior studies regarding risk stratification for The Papanicolaou Society of Cytopathology System for Reporting Pancreaticobiliary Cytology (PSCPC). In the current study, the authors reported on a single‐institution experience on 3‐year prospective PSCPC regarding risk of malignancy (ROM) and the overall risk of malignancy (OROM).MethodsA computerized search was performed from August 2014 to December 2017 for all pancreatic fine‐needle aspiration (FNA) samples. Pathology from surgical resections and biopsies and relevant radiologic and clinical follow‐up data were collected. The ROM and the OROM were calculated. The OROM was based on the total number of FNA samples in each category.ResultsA total of 1017 pancreatic FNA cases were identified, with surgical and/or clinical follow‐up data available for 548 cases. The cytopathologic diagnoses included 242 nondiagnostic (category I), 162 benign (category II), 142 atypical (category III), 20 neoplastic‐benign (category IV: benign), 133 neoplastic‐other (category IV: other), 28 suspicious (category V), and 290 malignant (category VI) cases. A total of 364 malignancies were documented in 11 cases, 4 cases, 36 cases, 0 cases, 36 cases, 21 cases, and 255 cases, respectively, from categories I, II, III, IV: benign, IV:other, V, and VI. The ROM was 25%, 17.4%, 41.8%, 0%, 34.3% (95.2%), 95.5%, and 99.6%, respectively, and the OROM was 4.5%, 2.5%, 25.3%, 0%, 27.1% (83.3%), 75%, and 87.9%, respectively, for categories I, II, III, IV: benign, IV: other (with high‐grade dysplasia), V, and VI.ConclusionsThe true ROM for PSCPC is likely between the ROM and OROM for the benign and indeterminate categories. In the neoplastic‐other category (category IV: other), identifying high‐grade dysplasia is important for its association with malignancy and a higher ROM.
Deletion of the cannabinoid CB1 receptor impacts on the ultrastructure of the cerebellar parallel fiber‐Purkinje cell synapses
Authors: Buceta Ianire , Elezgarai Izaskun , Rico‐Barrio Irantzu , Gerrikagoitia Inmaculada , Puente Nagore , Grandes Pedro 
Published: November 2019

AbstractThe cannabinoid CB1 receptor localizes to the glutamatergic parallel fiber (PF) terminals of the cerebellar granule cells and participates in synaptic plasticity, motor control and learning that are impaired in CB1 receptor knockout (CB
1‐KO) mice. However, whether ultrastructural changes at the PF‐Purkinje cell (PC) synapses occur in CB
1‐KO remains unknown. We studied this in the vermis of the spinocerebellar lobule V and the vestibulocerebellar lobule X of CB
1‐KO and wild‐type (CB
1‐WT) mice by electron microscopy. Lobule V, but not lobule X, of CB
1‐KO had significantly less and longer synapses than in CB
1‐WT. PF terminals were significantly larger in both lobules of CB
1‐KO with no changes in PC dendritic spines. The PF terminals in lobule V of CB
1‐KO contained less synaptic vesicles and lower vesicle density; by contrast, vesicle density in lobule X of CB
1‐KO remained unchangeable relative to CB
1‐WT. There were as many vesicles in lobule V of CB
1‐KO as in CB
1‐WT, but their distribution decreased drastically at 300 nm of the active zone. In lobule X of CB
1‐KO, less vesicles were found within 150 nm from the presynaptic membrane; however, no vesicles were at 450–600 nm of the active zone. A significant higher amount of synaptic vesicles close to the active zone in lobule V and X of CB
1‐KO was observed. In conclusion, the absence of CB1 receptors strikingly and distinctively impacts on the ultrastructural architecture of the PF‐PC synapses located in cerebellar lobules that differ in vulnerability to damage and motor functions.
Characterization of striatal phenotypes in heterozygous Disc1 mutant mice, a model of haploinsufficiency
Authors: Baskaran Rathinasamy , Lai Chuan‐Ching , Li Wai‐Yu , Tuan Li‐Heng , Wang Chia‐Chuan , Lee Lukas J.‐H. , Liu Chih‐Min , Hwu Hai‐Gwo , Lee Li‐Jen 
Published: November 2019

AbstractDisrupted‐in‐Schizophrenia 1 (DISC1) is a susceptibility gene for several psychiatric illnesses. To study the pathogenesis of these disorders, we generated Disc1 mutant mice by introducing the 129S6/SvEv 25‐bp deletion Disc1 variants into the C57BL/6J strain. In this study, we used heterozygous Disc1 mutant (Het) mice to evaluate the DISC1 haploinsufficiency model of schizophrenia. No changes in locomotor behaviors were observed in Het mice; however, after amphetamine injection, greater locomotor activity was observed in Het mice compared with wild‐type (WT) mice. Moreover, amphetamine‐induced elevations of c‐Fos expression and dopamine level in the striatum were greater in Het mice than in WT controls, suggesting an altered dopaminergic regulation in the striatum of Het mice. Compared with those in WTs, the striatal protein levels of dopamine transporter and D2 dopamine receptor were increased in Het mice, while D1 dopamine receptor level was decreased. DISC1 interacting proteins, GSK3α and GSK3β, were downregulated in Het mice, whereas the levels of PDE4B and CREB were not altered. Morphologically, the complexities of striatal median spiny neurons (MSNs), parvalbumin‐positive interneurons and Iba1‐positive microglia were all decreased in Het mice. The density and head diameter of dendritic spines in the MSNs of Het mice were also reduced. Our results indicate that mice lacking one WT Disc1 allele are more sensitive to psychostimulant amphetamine challenge, which might be attributed to the altered structure and function of the striatal dopaminergic system. Here, we demonstrated striatal phenotypes in heterozygous Disc1 mutant mice, which could be a promising model of DISC1 haploinsufficiency.
In Silico Evidence That Protein Unfolding is a Precursor of Protein Aggregation
Authors: Bianco Valentino , Franzese Giancarlo , Coluzza Ivan 
Published: November 2019

AbstractWe present a computational study on the folding and aggregation of proteins in an aqueous environment, as a function of its concentration. We show how the increase of the concentration of individual protein species can induce a partial unfolding of the native conformation without the occurrence of aggregates. A further increment of the protein concentration results in the complete loss of the folded structures and induces the formation of protein aggregates. We discuss the effect of the protein interface on the water fluctuations in the protein hydration shell and their relevance in the protein‐protein interaction.
Physiologically‐Based Pharmacokinetic Modeling for Optimal Dosage Prediction of Quinine Coadministered With Ritonavir‐Boosted Lopinavir
Authors: Saeheng Teerachat , Na‐Bangchang Kesara , Siccardi Marco , Rajoli Rajith K.R. , Karbwang Juntra 
Published: November 2019

The coformulated lopinavir/ritonavir significantly reduces quinine concentration in healthy volunteers due to potential drug–drug interactions (DDIs). However, DDI information in malaria and HIV coinfected patients are lacking. The objective of the study was to apply physiologically‐based pharmacokinetic (PBPK) modeling to predict optimal dosage regimens of quinine when coadministered with lopinavir/ritonavir in malaria and HIV coinfected patients with different conditions. The developed model was validated against literature. Model verification was evaluated using the accepted method. The verified PBPK models successfully predicted unbound quinine disposition when coadministered with lopinavir/ritonavir in coinfected patients with different conditions. Suitable dose adjustments to counteract with the DDIs have identified in patients with various situations (i.e., a 7‐day course at 1,800 mg t.i.d. in patients with malaria with HIV infection, 648 mg b.i.d. in chronic renal failure, 648 mg t.i.d. in hepatic insufficiency except for severe hepatic insufficiency (324 mg b.i.d.), and 648 mg t.i.d. in CYP3A4 polymorphism).
Room‐Temperature Synthesis of High‐Entropy Perovskite Oxide Nanoparticle Catalysts through Ultrasonication‐Based Method
Authors: Okejiri Francis , Zhang Zihao , Liu Jixing , Liu Miaomiao , Yang Shize , Dai Sheng 
Published: November 2019

AbstractIn the present study, a sonochemical‐based method for one‐pot synthesis of entropy‐stabilized perovskite oxide nanoparticle catalysts with high surface area was developed. The high‐entropy perovskite oxides were synthesized as monodispersed, spherical nanoparticles with an average crystallite size of approximately 5.9 nm. Taking advantage of the acoustic cavitation phenomenon in the ultrasonication process, BaSr(ZrHfTi)O3, BaSrBi(ZrHfTiFe)O3 and Ru/BaSrBi(ZrHfTiFe)O3 nanoparticles were crystallized as single‐phase perovskite structures through ultrasonication exposure without calcination. Notably, the entropically‐driven stability of Ru/BaSrBi(ZrHfTiFe)O3 with excellent dispersion of Ru in the perovskite phase bestowed the nanoparticles of Ru/BaSrBi(ZrHfTiFe)O3 with good catalytic activity for CO oxidation.
Synthesis of Metal Phosphide Nanoparticles Supported on Porous N‐Doped Carbon Derived from Spirulina for Universal‐pH Hydrogen Evolution
Authors: Yang Ming , Feng Fan , Wang Kaizhi , Li Shuwen , Huang Xiaokang , Gong Li , Ma Lei , Li Rong 
Published: November 2019

AbstractTransition metal phosphides (TMPs) are regarded as highly active electrocatalysts for the hydrogen evolution reaction (HER). However, traditional synthetic routes usually use expensive and dangerous precursors as P donors. The development of a low‐cost and ecofriendly method for the synthesis of TMPs is significant for sustainable energy development. Herein, cobalt phosphides anchored on or embedded in a spirulina‐derived porous N‐doped carbon matrix (Co2P/NC) was fabricated by two‐step hydrothermal treatment and carbonization method, which utilized the intrinsic C, N, and P of biomass cleverly as the sources of C, N, and P, respectively. As a result of the high surface area and porosity that enhance the mass‐transfer dynamics, Co2P/NC shows good electrocatalytic activity at all pH values in the HER. This work not only provides a facile and effective method for the fabrication of TMP nanoparticles loaded onto carbon materials but also opens a new strategy for the utilization of the intrinsic ingredients of biomass for the preparation of other functional electrocatalysts.
Appropriateness of action prompts for hypoglycaemia and hyperglycaemia in type 2 diabetes self‐management apps
Authors: Lum Elaine , Jimenez Geronimo , Huang Zhilian , Thai Linh , Car Josip 
Published: November 2019

AbstractBackgroundControl of blood glucose levels is needed not only to alleviate symptoms of hypoglycaemia and hyperglycaemia, but also to prevent or delay diabetes‐related complications. Advice for glucose control is usually provided to patients by members of the health care team. However, many diabetes apps claim to enhance self‐management of blood glucose by providing decision support to patients when an out‐of‐range blood glucose level is recorded. In this study, we investigated the appropriateness of action prompts provided by diabetes apps for hypoglycaemia and hyperglycaemia against evidence‐based guidelines.MethodsWe used methods previously reported to identify and select diabetes apps, which were downloaded and assessed against the American Diabetes Association (ADA) guidelines. Screenshots of action prompts corresponding to low or high out‐of‐range blood glucose values were subjected to content analysis.ResultsOf 371 diabetes self‐management apps evaluated, only 217 and 216 apps alerted patients about hypoglycaemia and hyperglycaemia, respectively. Of these, 20.7% (45/217) and 15.3% (33/216) also provided action prompts. We found 5.1% of apps (hypoglycaemia: 11/217; hyperglycaemia: 11/216) provided prompts that were either too general to be helpful or not aligned with ADA guidelines. Overall, only 17.9% (39/217) and 14.8% (32/216) provided appropriate action prompts for hypoglycaemia and hyperglycaemia, respectively.ConclusionLess than one fifth of apps provided evidence‐based steps to guide patients through hypoglycaemia and hyperglycaemia. The majority of apps failed to provide just‐in‐time diabetes self‐management education to prevent frequent or severe episodes of hypoglycaemia and hyperglycaemia. Our findings emphasize the need for better design and quality assurance of diabetes apps.
A high‐order nodal discontinuous Galerkin method to solve preconditioned multiphase Euler/Navier‐Stokes equations for inviscid/viscous cavitating flows
Authors: Hajihassanpour Mahya , Hejranfar Kazem 
Published: November 2019

SummaryIn this study, a high‐order accurate numerical method is applied and examined for the simulation of the inviscid/viscous cavitating flows by solving the preconditioned multiphase Euler/Navier‐Stokes equations on triangle elements. The formulation used here is based on the homogeneous equilibrium model considering the continuity and momentum equations together with the transport equation for the vapor phase with applying appropriate mass transfer terms for calculating the evaporation/condensation of the liquid/vapor phase. The spatial derivative terms in the resulting system of equations are discretized by the nodal discontinuous Galerkin method (NDGM) and an implicit dual‐time stepping method is used for the time integration. An artificial viscosity approach is implemented and assessed for capturing the steep discontinuities in the interface between the two phases. The accuracy and robustness of the proposed method in solving the preconditioned multiphase Euler/Navier‐Stokes equations are examined by the simulation of different two‐dimensional and axisymmetric cavitating flows. A sensitivity study is also performed to examine the effects of different numerical parameters on the accuracy and performance of the solution of the NDGM. Indications are that the solution methodology proposed and applied here is based on the NDGM with the implicit dual‐time stepping method and the artificial viscosity approach is accurate and robust for the simulation of the inviscid and viscous cavitating flows.
On the directional predictability of equity premium using machine learning techniques
Authors: Iworiso Jonathan , Vrontos Spyridon 
Published: November 2019

AbstractThis paper applies a plethora of machine learning techniques to forecast the direction of the US equity premium. Our techniques include benchmark binary probit models, classification and regression trees, along with penalized binary probit models. Our empirical analysis reveals that the sophisticated machine learning techniques significantly outperformed the benchmark binary probit forecasting models, both statistically and economically. Overall, the discriminant analysis classifiers are ranked first among all the models tested. Specifically, the high‐dimensional discriminant analysis classifier ranks first in terms of statistical performance, while the quadratic discriminant analysis classifier ranks first in economic performance. The penalized likelihood binary probit models (least absolute shrinkage and selection operator, ridge, elastic net) also outperformed the benchmark binary probit models, providing significant alternatives to portfolio managers.