bluuebunny/crossref_metadata_2025 huggingface dataset:
Bayesian knowledge integration for an in vitro–in vivo correlation model
Authors: Erhardt Elvira M. , Ursino Moreno , Biewenga Jeike , Jacobs Tom , Gasparini Mauro
Published: September 2018

The primary goal of “in vitro–in vivo correlation” (IVIVC) is the reliable prediction of the in vivo serum concentration‐time course, based on the in vitro drug dissolution or release profiles. IVIVC methods are particularly appropriate for formulations that are released over an extended period of time or with a lag in absorption and may support approving a change in formulation of a drug without additional bioequivalence trials in human subjects. Most of the current IVIVC models are assessed using frequentist methods, such as linear regression, based on averaged data and entail complex and potentially unstable mathematical deconvolution. The proposed IVIVC approach includes (a) a nonlinear‐mixed effects model for the in vitro release data; (b) a population pharmacokinetic (PK) compartment model for the in vivo immediate release (IR) data; and (c) a system of ordinal differential equations (ODEs), containing the submodels (a) and (b), which approximates and predicts the in vivo controlled release (CR) data. The innovation in this paper consists of splitting the parameter space between submodels (a) and (b) versus (c). Subsequently, the uncertainty on these parameters is accounted for using a Bayesian framework, that is estimates from the first two submodels serve as priors for the Bayesian hierarchical third submodel. As such, the Bayesian method explained ensures a natural integration and transfer of knowledge between various sources of information, balancing possible differences in sample size and parameter uncertainty of in vitro and in vivo studies. Consequently, it is a very flexible approach yielding results for a broad range of data situations. The application of the method is demonstrated for a transdermal patch (TD).
Action observation for sensorimotor learning in surgery
Authors: Harris D J , Vine S J , Wilson M R , McGrath J S , LeBel M-E , Buckingham G
Published: September 2018

Background

Acquiring new motor skills to learn complex movements and master the use of a diverse range of instruments is fundamental for developing expertise in surgery. Although aspects of skill development occur through trial and error, watching the performance of another individual (action observation) is an increasingly important adjunct for the acquisition of these complex skills before performing a procedure. The aim of this review was to examine the evidence in support of the use of action observation in surgery.

Methods

A narrative review of observational learning for surgical motor skills was undertaken. Searches of PubMed and PsycINFO databases were performed using the terms ‘observational learning’ OR ‘action observation’ AND ‘motor learning’ OR ‘skill learning’.

Results

Factors such as the structure of physical practice, the skill level of the demonstrator and the use of feedback were all found to be important moderators of the effectiveness of observational learning. In particular, observation of both expert and novice performance, cueing attention to key features of the task, and watching the eye movements of expert surgeons were all found to enhance the effectiveness of observation. It was unclear, however, whether repeated observations were beneficial for skill learning. The evidence suggests that these methods can be employed to enhance surgical training curricula.

Conclusion

Observational learning is an effective method for learning surgical skills. An improved understanding of observational learning may further inform the refinement and use of these methods in contemporary surgical training curricula.
A quality framework for the role of invasive, non‐interventional cardiologists in the present‐day cardiac catheterization laboratory: A multidisciplinary SCAI/HFSA expert consensus statement
Authors: Mulukutla Suresh R. , Babb Joseph D. , Baran David A. , Boudoulas Konstantinos Dean , Feldman Dmitriy N. , Hall Shelley A. , Jennings Henry S. , Kapur Navin K. , Rao Sunil V. , Reginelli Joel , Schussler Jeffrey M. , Yang Eric H. , Cigarroa Joaquin E.
Published: September 2018

The present‐day cardiac catheterization laboratory (CCL) is home to varied practitioners who perform both diagnostic, interventional, and complex invasive procedures. Invasive, non‐interventional cardiologists are performing a significant proportion of the work as the CCL environment has evolved. This not only includes those who perform diagnostic‐only cardiac catheterization but also heart failure specialists who may be involved in hemodynamic assessment and in mechanical circulatory support and pulmonary hypertension specialists and transplant cardiologists. As such, the training background of those who work in the CCL is varied. While most quality metrics in the CCL are directed towards evaluation of patients who undergo traditional interventional procedures, there has not been a focus upon providing these invasive, noninterventional cardiologists, hospital/CCL administrators, and CCL directors a platform for quality metrics. This document focuses on benchmarking quality for the invasive, noninterventional practice, providing this physician community with guidance towards a patient‐centered approach to care, and offering tools to the invasive, noninterventionalists to help their professional growth. This consensus statement aims to establish a foundation upon which the invasive, noninterventional cardiologists can thrive in the CCL environment and work collaboratively with their interventional colleagues while ensuring that the highest quality of care is being delivered to all patients.
Tuning Biphasic Catalysis Reaction with a Pickering Emulsion Strategy Exemplified by Selective Hydrogenation of Benzene
Authors: Zhang Yabin , Zhang Ming , Yang Hengquan
Published: September 2018

Although organic/aqueous biphasic catalysis reactions are widely used, it is difficult to effectively control their reaction process. Here we develop a solid particles‐stabilized emulsion (Pickering emulsion) strategy to address this limitation. A challenging biphasic reaction, selective hydrogenation of benzene to cyclohexene, was investigated as a case. The developed Pickering emulsion system exhibited higher catalysis efficiency and selectivity than the conventional biphasic reaction system even under mild stirring. The cyclohexene selectivity and yield in the Pickering emulsion system reached as high as 51.2 % and 43.3 %, respectively. More importantly, the findings presented here demonstrate the feasibility that the reaction rate and selectivity of challenging biphasic reactions can be regulated by the rational adjustment of Pickering emulsion parameters including emulsion droplet size, droplet distance as well as emulsion type, which is otherwise unattainable for conventional biphasic reaction systems.
POXC Laccase from Pleurotus ostreatus: A High‐Performance Multicopper Enzyme for Direct Oxygen Reduction Reaction Operating in a Proton‐Exchange Membrane Fuel Cell
Authors: Sorrentino Ilaria , Gentil Solène , Nedellec Yannig , Cosnier Serge , Piscitelli Alessandra , Giardina Paola , Le Goff Alan
Published: September 2018

In this work, POXC, a laccase from Pleurotus ostreatus, was immobilized on carbon nanotubes (CNTs) modified by electrografting anthraquinone and naphthoate diazonium salts. Thanks to a favorable interaction between laccase and covalently modified CNTs, this laccase exhibits high‐potential/high‐current oxygen reduction reaction (ORR) performances, surpassing the performances of the well‐known laccase from Trametes versicolor (TvLAC) immobilized on the same nanostructured electrodes. Furthermore, immobilized POXC demonstrates high ORR activity over a wide range of pH (2 to 8), being also highly active at a gas‐diffusion electrode. Finally, owing to these unique performances, this enzyme was able to operate at the interface of the microporous layer, humidified air and a polymer electrolyte, that is, Nafion®, in a conventional H2/air proton‐exchange membrane fuel.
Host–Guest‐Induced Environment Tuning of 3d Ions in a Polyoxopalladate Matrix
Authors: Stuckart Maria , Izarova Natalya V. , van Leusen Jan , Smekhova Alevtina , Schmitz‐Antoniak Carolin , Bamberger Heiko , van Slageren Joris , Santiago‐Schübel Beatrix , Kögerler Paul
Published: September 2018

A series of unprecedented supramolecular associates of phenylarsonate‐capped {MIIPdII12O8}‐type (M=Co, Ni and Zn) polyoxopalladates with α‐cyclodextrins (α‐CD) was obtained and characterized in the solid state (single‐crystal X‐ray diffraction (XRD), FT‐IR spectroscopy, elemental and thermogravimetric (TGA) analyses), in aqueous solution (1H and 13C NMR) and in the gas phase (ESI‐MS). The non‐covalent host–guest interactions between the organopolyoxoanions and α‐CD rings alter the O8 coordination environment of a 3d transition metal ion (MII) situated at the center of a cuboid polyoxododecapalladate shell. This synthetically controlled “chemical pressure” effectively induces axial distortion of the otherwise cubic polyoxopalladate environment between two trans‐positioned α‐CD moieties. Its effect on the magnetic properties and the electronic structure of the CoII derivative was assessed in a combined SQUID magnetometry, EPR, X‐ray magnetic circular/linear dichroism (XMCD/XMLD), and X‐ray absorption near‐edge structure (XANES) spectroscopy study.
Luminescence Vapochromism of a Dynamic Copper Iodide Mesocate
Authors: Benito Quentin , Balogh Cristina M. , El Moll Hani , Gacoin Thierry , Cordier Marie , Rakhmatullin Aydar , Latouche Camille , Martineau‐Corcos Charlotte , Perruchas Sandrine
Published: September 2018

A copper iodide complex coordinated by three phosphine ligands with the formula [Cu2I2(Ph2PC2(C6H4)C2PPh2)3] exhibits solvatochromic and vapochromic luminescence properties. A mechanism based on solvent‐dependent molecular motion appears to occur. The highly contrasted response observed upon THF solvent exposure makes this complex an appealing candidate for chemical sensor applications.
Sustainable Carbon Sources and Renewable Energy: Challenges and Opportunities at the Interface of Catalysis and Reaction Engineering
Authors: Palkovits Regina
Published: September 2018

Limited fossil resources and the need to reduce greenhouse gas emissions require the development of environmentally benign production processes. Economic, energy and carbon‐efficient value chains based on lignocellulosic biomass are essential for a sustainable and potentially CO2‐neutral chemical industry. Biomass presents a concentrated renewable carbon source for base and fine chemicals, polymers and liquid fuels of high energy density. Research studies have highlighted the need for novel process concepts to account for the high degree of functionality of lignocellulosic biomass. Major challenges include selective deoxygenation of the highly functionalized starting materials, energy‐intensive separation and processes bridging chemo‐catalysis, biotechnology and electro‐catalysis. In the following, these challenges are exemplarily discussed. The showcases are selected to illustrate concepts and not meant to provide a comprehensive overview of the field.
Atrial fibrillation and chronic kidney disease: A review of options for therapeutic anticoagulation to reduce thromboembolism risk
Authors: Bhatia Harpreet S. , Hsu Jonathan C. , Kim Robert J.
Published: September 2018

Atrial fibrillation and chronic kidney disease (CKD) commonly occur together, which poses a therapeutic dilemma due to increased risk of both systemic thromboembolism and bleeding. Chronic kidney disease also has implications for medication selection. The objective of this review is to evaluate the options for anticoagulation for thromboembolism prevention in patients with atrial fibrillation and chronic kidney disease. We searched PubMed for studies of patients with atrial fibrillation and CKD on warfarin or a direct oral anticoagulant (DOAC) for thromboembolism prevention through January 1 2018, in addition to evaluating major trials evaluating DOACs and warfarin use as well as society guidelines. For patients with mild to moderate chronic kidney disease, primarily observational data supports the use of warfarin, and high quality trial data and meta‐analyses support the use and possible superiority of DOACs. For patients with severe chronic kidney disease, there are limited data on warfarin which supports its use, and data for DOACs is limited primarily to pharmacologic studies which support dose reductions but lack information on patient outcomes. For patients with end‐stage renal disease, studies on warfarin are conflicting, but the majority suggest a lack of benefit and possible harm; studies in DOACs are very limited, but apixaban is the least renally cleared and may be both safe and effective. In conclusion, warfarin or DOACs may be used based on the degree of severity of chronic kidney disease, but further study in needed in patients with end‐stage renal disease.
An effective application of 3D cloud printing service quality evaluation in BM‐MOPSO
Authors: Wang Xinggang , Sheng Buyun , Zhang Chenglei , Xiao Zheng , Wang Hui , Zhao Feiyu
Published: September 2018

Addressing service control factors, rapid manufacturing environment change, difficulty of resource allocation evaluation, resource optimization of 3D cloud printing service in a cloud manufacturing environment, and other characteristics, this paper proposes an evaluation indicator system of innovative new product development 3D printing order task execution. The evaluation indicator has eight dimensional components, including Time (T), Quality of Service (Q), Matching (Mat), Reliability (R), Flexibility (Flex), Cost (C), Fault tolerance (Ft), and Satisfaction (Sa). It constructs a type of optimal selection model based on a Multi‐Agent 3D Cloud Printing Service Quality Evaluation and a framework of cloud service evaluation of an AHP‐TOPSIS evaluation model based on Pareto optimization, and it designs an algorithm involving hybrid multi‐objective particle swarm optimization (PSO) based on the Baldwin Effect Model. In addition, this paper verifies the effectiveness of the algorithm through an example and offers a case study designed to test its feasibility and effectiveness.
Growth and Morphology of Liquid Phase in Frozen Aqueous NaCl Probed by Voltammetry and Simulations
Authors: Fukui Yoshiharu , Miyagawa Akihisa , Qu Hui , Harada Makoto , Okada Tetsuo
Published: September 2018

Cyclic voltammograms (CVs) of Fe(CN)64− are measured using a microelectrode in frozen aqueous NaCl solutions to obtain morphological information on the liquid phase developed on the electrode surface. CVs in frozen solutions feature the radial diffusion similar to that measured in bulk solution in some cases but the linear diffusion in other cases. The former suggests the sufficient growth of the liquid phase, whereas the latter implies the diffusion paths in particular directions are hindered. Two parameters, i. e. a ratio of the maximum current to the steady‐state current (R) and current amplification (ramp), are extracted from CVs and compared with those of simulated ones. CV simulations are carried out for four geometrical models. From the relationship between ramp and R, the FCS developed on the electrode surface can be regarded as a thin layer developed in the direction parallel to the electrode surface or a cylinder running in the direction away from the electrode. Since solutes are concentrated in this liquid phase, highly sensitive voltammetric analysis would be possible if the growth of the FCS were successfully managed. The liquid phase morphology on the electrode, which cannot be probed by other methods, is useful information for designing such highly sensitive voltammetric analyses.
Establishment of a Human Blood‐Brain Barrier Co‐Culture Model Mimicking the Neurovascular Unit Using Induced Pluripotent Stem Cells
Authors: Appelt‐Menzel Antje , Cubukova Alevtina , Metzger Marco
Published: September 2018

Human blood‐brain barrier (BBB) in vitro models pose a promising tool in drug development and understanding of mechanistic regulations during health and disease. Human‐induced pluripotent stem cells (hiPS cells) represent an unlimited cell source to generate functional cells of the neurovascular unit (NVU), independent of variations or limitations during isolation and in vitro cultivation. This unit describes the standardized 2‐D differentiation of adherent hiPS cells into BBB endothelial cells and neuronal stem cells (NSCs). Both cell types are combined with primary astrocytes and pericytes to develop complex, physiological BBB in vitro models. The endothelial cells in the apical compartment of the transwell models are separated from the basolateral seeded co‐culture mixture by a synthetic membrane, simplifying analyses. The barrier integrity and functionality of the endothelium is improved by the specific mixture of NVU niche cells, determined here by decrease in the paracellular permeability of sodium‐fluorescein and transendothelial electrical resistance (TEER) measurement. © 2018 by John Wiley & Sons, Inc.
Solar Energy Harvesting with Carbon Nitrides and N‐Heterocyclic Frameworks: Do We Understand the Mechanism?
Authors: Domcke Wolfgang , Ehrmaier Johannes , Sobolewski Andrzej L.
Published: September 2018

The photocatalytic splitting of water into molecular hydrogen and molecular oxygen with sunlight is the dream reaction for solar energy conversion. For decades, transition metal oxide semiconductors and supramolecular organometallic structures have been extensively explored as photocatalysts for solar water splitting. More recently, polymeric materials consisting of triazine or heptazine building blocks have attracted considerable attention as hydrogen‐evolution photocatalysts. The mechanism of hydrogen evolution with these materials is discussed throughout the current literature in terms of the familiar concepts developed for photoelectrochemical water splitting with semiconductors since the 1970s. We discuss in this Minireview an alternative mechanistic paradigm for photoinduced water splitting with carbon nitrides, which focusses on the specific features of the photochemistry of aromatic N‐heterocycles in aqueous environments. Using ab initio electronic‐structure calculations, it is shown that a water molecule which is hydrogen‐bonded to an N‐heterocycle can be decomposed into hydrogen and hydroxyl radicals by two simple sequential photochemical reactions. This concept is illustrated by the discussion of excited‐state reaction paths and their energy profiles for hydrogen‐bonded complexes of pyridine, triazine and heptazine with a water molecule. It is shown that the excited‐state hydrogen‐transfer and hydrogen‐detachment reactions are essentially barrierless, in sharp contrast to water oxidation in the electronic ground state, where high barriers prevail. We also discuss in some detail the products of possible reactions of the highly reactive photogenerated hydroxyl radicals with the chromophores. We hypothesize that the challenge of efficient solar hydrogen generation with carbon nitride materials is less the decomposition of water as such, but rather the controlled recombination of the photogenerated radicals to the closed‐shell products H2 and H2O2.
Non‐Fullerene Organic Electron‐Transporting Materials for Perovskite Solar Cells
Authors: Jung Su‐Kyo , Lee David S. , Ann Myung Hyun , Im Sang Hyuk , Kim Jong H. , Kwon O‐Pil
Published: September 2018

Organic electron‐transporting materials (ETMs) with low‐temperature solution processability and high electron‐transfer/transport characteristics have received significant attention for their use in high‐performance perovskite solar cells (PSCs). In contrast to widely investigated fullerene‐based organic ETMs for PSCs, only a few types of non‐fullerene‐based ETMs have been developed. In this Concept article, a representative design concept for non‐fullerene ETMs is described for use in normal (n‐i‐p) and inverted (p‐i‐n) type PSCs. On the basis of a discussion on ETM requirements for PSCs, recently developed non‐fullerene polymeric and small‐molecule‐based ETMs for PSCs are highlighted, alongside various other approaches for enhancing PSC device performance, such as using additional dopants and introducing amine terminal groups in the ETMs and ETM‐based interlayers. This Concept provides a basic design concept for non‐fullerene‐based ETMs in PSCs.
F5N‐based unequal clustering protocol (F5NUCP) for wireless sensor networks
Authors: Arjunan Sariga , Pothula Sujatha , Ponnurangam Dhavachelvan
Published: September 2018

Wireless sensor networks (WSNs) became very popular and still remains an active research because of diverse applications. Minimizing the energy dissipation and maximizing the network lifetime is an important design issue in WSN. Clustering is the widely used energy effective technique to lessen the overall energy consumption of WSN. An appropriate selection of cluster heads (CHs) and cluster size is a crucial process in clustered WSN. The CHs nearer to base station (BS) suffer from hot spot problem and die earlier than the normal lifetime. This paper contributes a five input fuzzy‐based unequal clustering protocol (F5NUCP) for selecting CHs and determining the appropriate cluster size to prevent the network from hot spot problem. Unequal clusters eliminates the hot spot problem by producing smaller clusters for the nodes located near the BS and larger clusters for the nodes located far away from the BS. F5NUCP uses a nonprobabilistic approach for selecting tentative CHs by introducing a back‐off timer where the timer value is set using the remaining energy of the node. The proposed method uses five input parameters, namely, remaining energy, distance to BS, distance to its neighboring nodes, link quality, and node degree. The output fuzzy parameters used in this research are cluster size and the probability of becoming CHs. The proposed method is implemented in MATLAB. The simulation results show that F5NUCP performs well when compared with LEACH, DEEC, TEEN, and EAUCF in terms of network lifetime and reduced energy consumption.
Interactive effects of testosterone and the androgen receptor CAG repeat length polymorphism on cardiovascular‐renal events and mortality in men with diabetes
Authors: Wong Poon‐Wing , Lee Heung‐Man , Lau Eric S.H. , Lim Cadmon , Ma Ronald C.W. , Kong Alice P.S. , Chan Juliana C.N. , Luk Andrea O.Y.
Published: September 2018

Aim

Current evidence relating testosterone to cardiovascular disease and mortality is inconclusive. Cellular effects of testosterone are mediated by androgen receptor and longer receptor gene CAG repeat length correlates with reduced transcriptional activity. We investigated the independent and interactive association of total testosterone and CAG repeat length with incident cardiovascular disease (CVD), chronic kidney disease (CKD) and mortality in Chinese men with type 2 diabetes.

Materials and methods

From March 2008 and February 2009, 474 men with diabetes underwent structured clinical assessment including genotyping for CAG repeat length. Patients were followed for new‐onset CVD, CKD defined by estimated glomerular filtration rate <60 mL/min/1.73m2, and death until 31 May 2015.

Results

In this cohort (mean age: 58.6 years, disease duration: 15.4 years), CAG repeat number ranged from 11 to 32 with median of 23, and 9.3% had low testosterone. Over follow‐up of 5.8 years, 49 (10.3%) men had CVD, 139 (29.3%) had CKD, and 43 (9.1%) died. In multivariate Cox regression adjusted for age, duration of diabetes, and cardiometabolic risk factors, both total testosterone and interaction term of total testosterone × CAG repeat were associated with all‐cause death with respective hazard ratios 1.63 (P = 0.002) and 0.98 (P = 0.004). Total testosterone and CAG repeat were not related to incident CVD or CKD.

Conclusions

Among men with type 2 diabetes, high total testosterone was associated with increased mortality in the presence of shorter CAG repeat length but decreased mortality in those with long CAG repeats.
Taste receptor T1R1/T1R3 promotes the tumoricidal activity of hepatic CD49a+CD49b− natural killer cells
Authors: Liu Shaoping , Xu Min , Zhu Chengliang , Zhao Qiu , Zhou Feng
Published: September 2018

Natural Killer (NK) cell‐based immunotherapy is a promising approach to treat hepatocellular carcinoma (HCC). The mechanisms underlying the regulation of NK cell activity are not completely understood. In this research, we identified the expression of taste receptor type 1 member 1 (T1R1) and taste receptor type 1 member 3 (T1R3) in a subset of hepatic NK cells in a mouse HCC model. T1R1 and T1R3 were selectively expressed in CD49a+CD49b− NK cells in livers with HCC. In the in vitro cytotoxicity assay, amino acids promoted the tumoricidal effect of CD49a+CD49b− NK cells through increasing the production of perforin, granzyme B and IFN‐γ. Furthermore, using a lentivirus to induce the expression of exogenous T1R1 and T1R3 in normal hepatic NK cells, we found that amino acids enhanced NK cell‐mediated cytotoxicity on tumor cells through the T1R1/T1R3 receptor, as demonstrated by more tumor cell lysis, up‐regulation of perforin and granzyme B in comparison with control NK cells. In addition, amino acids activated Akt and mechanistic target of rapamycin complex 1 (mTORC1) signaling in NK cells through T1R1/T1R3 receptor. T‐bet expression in NK cells was also increased by amino acid treatment. Therefore, T1R1/T1R3 receptor promotes the tumoricidal activity of hepatic CD49a+CD49b− NK cells.
Comparative Study of Novel Phosphordiamidite and Phosphite Ligands Used in Alkene Hydroformylation; Synthesis, Characterization, Metalation, and Catalytic Evaluation
Authors: Hastings Samantha D. , Cagle Ethan C. , Totsch Timothy R. , Tyus Shakyra D. , Gray Gary M.
Published: September 2018

Three novel ligands have been prepared by the reactions of 1,1′‐(chlorophosphinediyl)bis(1H‐pyrrole) with either 2‐pyridinemethanol or 2,6‐pyridinedimethanol or the reaction of 1,1′‐biphenyl‐2,2′‐diyl phosphorochloridite with 2‐pyridinemethanol. Measurement of |1JP–Se| values demonstrate that the phosphite donor is less basic than the phosphoramidite donors. Coordination preferences of the ligands in octahedral cis‐tetracarbonylmolybdenum(0) and square planar cis‐dichloropalladium(II) complexes have been evaluated using multinuclear NMR and X‐ray crystallography. Rhodium(I) complexes of the bidentate ligands have been evaluated as catalysts for styrene hydroformylation, and their activities are nearly double those of catalysts containing traditional phosphites. The regioselectivities of the RhI complexes of the bidentate ligands are not significantly different at 80 °C and 20 atm and are not affected by the addition of a lithium salt. In contrast, changing reaction conditions causes the % n‐aldehyde to vary from 15 to 50 %. The regioselectivity of the catalyst containing the bidentate phosphoramidite/pyridine ligand was more sensitive to pressure than temperature with both effects being significant.
Electrochemical Intramolecular Dehydrogenative Coupling of N‐Benzyl(thio)amides: A Direct and Facile Synthesis of 4H‐1,3‐Benzoxazines and 4H‐1,3‐Benzothiazines
Authors: Yu Hui , Jiao Mingdong , Huang Ruohe , Fang Xiaowei
Published: September 2018

The electrochemical dehydrogenative cyclization of N‐benzylamides was investigated with a Pt plate anode and graphite rod cathode in an undivided cell at room temperature. The oxidative degradation of the products was suppressed successfully and 4H‐1,3‐benzoxazines were obtained regardless of the substituents at the benzylic position. This method also allowed for the preparation of 4H‐1,3‐benzothiazines.
PIDA/TBAB‐Promoted Oxidative Geminal Dibromofunctionalization of Alkynes: Direct Synthesis of Geminal Diazides
Authors: Arepally Sagar , Babu Venkata Nagarjuna , Polu Ashok , Sharada Duddu S.
Published: September 2018

PIDA/TBAB‐promoted oxidative geminal diazidofunctionalization of alkynes has been described for the first time. The transformation demonstrates a mechanistically distinctive approach to access geminal diazides, in which TBAB plays a crucial role as brominating agent and for the in situ generation of tetrabutylammonium azide. Furthermore, we have demonstrated here the first cycloaminative strategy by tactically employing the two azides groups leading to quinoxalines and synthesis of bis‐triazole derivatives via copper catalysis.
A Simple and Efficient One‐Pot Synthesis of 3‐Acylisoxazolines from Alcohols and α‐Nitro Ketones in the Presence of NaHSO4/SiO2
Authors: Aoyama Tadashi , Itoh Ken‐ichi , Hanzawa Takuya , Meguro Natsumi , Osanai Miki , Hayakawa Mamiko , Ouchi Akihiko
Published: September 2018

A simple and efficient method for the synthesis of 3‐acylisoxazolines has been developed using alcohols and α‐nitro ketones in the presence of NaHSO4/SiO2. The alcohols and α‐nitro ketones are initially converted into alkenes and nitrile oxides, respectively, and then react with one another to give 3‐acylisoxazolines. This procedure, using alcohols, gave the desired dihydroisoxazoles more effectively than the conventional procedure using alkenes as starting materials. The reaction proceeded through three pathways depending on the type of alcohol used; reactions between nitrile oxides and (I) endo and exo alkenes, (II) dimerized alkenes and (III) single alkenes. Most of the reactions proceeded efficiently and gave the corresponding 3‐acylisoxazolines in good to excellent yield.
An N,N′‐Bridged Corrole: First Example of a N21,N22‐Methylene‐Bridged Corrole Derivative
Authors: Patra Sajal Kumar , Sahu Kasturi , Patra Bratati , Mondal Sruti , Kar Sanjib
Published: September 2018

A new N,N′‐bridged corrole derivative has been prepared for the first time via the reaction of diiodomethane with 5,10,15‐tris(pentafluorophenyl)corrole. The new macrocycle has been thoroughly characterized by various spectroscopic techniques including single‐crystal X‐ray diffraction analysis.
Efficient Synthesis of Fluoroalkylated Imidazoles via a Metal‐Free Cascade Michael Addition/Azidation/Cycloamination Process
Authors: Wu Jun , Zhang Hui , Ding Xiao , Tan Xuefei , Shen Hong C. , Chen Jie , He Weimin , Deng Hongmei , Song Liping , Cao Weiguo
Published: September 2018

In the presence of KI and (diacetoxyiodo)benzene (PIDA), primary amines bearing an α‐hydrogen can be efficiently converted to fluoroalkylated imidazoles by reacting with fluoroalkylated alkynes and sodium azide via a cascade Michael addition/azidation/cycloamination process. KI plays a crucial role in this reaction by generating iodine(I) species to promote the cyclization. Substrate scope was explored, and the application of this protocol was demonstrated. Additionally, a plausible reaction mechanism was proposed.
Synthesis and Application of PHT‐TiO2 Nanohybrid for Amperometric Glucose Detection in Human Saliva Sample
Authors: Kadian Sachin , Arya Brahm Dutt , Kumar Sumit , Sharma Shailesh N. , Chauhan Rishi Pal , Srivastava Ananya , Chandra Pranjal , Singh Surinder P.
Published: September 2018

Nanoparticles and their composites are considered to play a significant role in the development of electrochemical biosensors. In the present work, we have synthesized titanium dioxide (TiO2) nanoparticles comprising poly (3‐hexylthiophene) (PHT) nanohybrid for the fabrication of glucose biosensor. The thin film of hybrid PHT/TiO2 nano‐composite was deposited onto indium‐tin‐oxide (ITO) glass substrate followed by immobilization of glucose oxidase (GOx). The developed sensor was characterized using X‐Ray Diffraction, Fourier Transform Infrared Spectroscopy, UV‐visible spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscopy. The electrochemical response of the nanocomposite coated electrode was studied which shows a quasi‐reversible electrochemical behavior. The experimental conditions for glucose detection were optimized in terms of GOx immobilization time, GOx concentrations, temperature, and pH, in order to obtain maximum sensitivity. Under the optimized experimental conditions, the ITO/TiO2/PHT/GOx sensor probe displays excellent catalytic activity towards glucose with the response time of <10.0 sec, showing its robustness for direct clinical analysis. Chronoamperometry was performed for the quantitative detection of glucose which displays the linear dynamic range between 1–310 mg/dL with the detection limit of 0.62±0.02 mg/dL. The developed biosensor was successfully applied to detect glucose in human saliva samples without any pre‐treatment step. Importantly, the detection range of the designed biosensor was in range of normal and clinical salivary glucose levels. Interferences due to nontarget biochemicals was investigated and long term stability of the sensor probe was evaluated.
Pulse‐like versus non‐pulse‐like ground motion records: Spectral shape comparisons and record selection strategies
Authors: Kohrangi Mohsen , Vamvatsikos Dimitrios , Bazzurro Paolo
Published: September 2018

Pulse‐like records are well recognized for their potential to impose higher demands on structures when compared with ordinary records. The increased severity of the structural response usually caused by pulse‐like records is commonly attributed to the spectral increment around the pulse period. By comparing the building response to sets of spectrally equivalent pulse‐like and ordinary records, we show that there are characteristics of pulse‐like records beyond the shape of the acceleration response spectrum that affect the results of nonlinear dynamic analysis. Nevertheless, spectral shape together with the ratio of pulse period to the first‐mode structural period, Tp/T1, are confirmed as “sufficient” predictors for deformation and acceleration response metrics in a building, conditioned on the seismic intensity. Furthermore, the average spectral acceleration over a period range, AvgSA, is shown to incorporate to a good proxy for spectral shape, and together with Tp/T1, form an efficient and sufficient intensity measure for response prediction to pulse‐like ground motions. Following this latter route, we propose a record selection scheme that maintains the consistency of Tp with the hazard of the site but uses AvgSA to account for the response sensitivity to spectral shape.
Quantifying sediment storage on the floodplains outside levees along the lower Yellow River during the years 1580–1849
Authors: Chen Yunzhen , Overeem Irina , Kettner Albert J. , Gao Shu , Syvitski James P. M. , Wang Yuanjian
Published: September 2018

The lower Yellow River channel was maintained by artificial levees between 1580 and 1849. During this period, 280 levee breaches occurred. To estimate sediment storage on the floodplains outside the levees, a regression model with a decadal time step was developed to calculate the outflow ratio for the years when levee breaching occurred. Uncertainty analysis was used to identify the likely outflow ratio. Key variables of the model include annual water discharge, a proxy for levee conditions, and potential bankfull discharge of the channel before flood season. Uncertainty analysis reveals an outflow ratio of 0.35–0.56. We estimate that during this period, 18.8–30.1% of the total ~312 Gt of sediment load was deposited on the floodplains outside the levees. Human‐accelerated erosion in the Loess Plateau caused a 4‐fold increase in sediment delivery to the lower Yellow River, which could not be accommodated by channel morphodynamic changes. As a result, 21.2–27.5% of the total sediment load was deposited within the levees, creating a super‐elevated channel bed that facilitated an uncommonly high breach outflow ratio. Hence, the factor of a large super‐elevation relative to the mean main channel depth should be considered when designing diversions to restore floodplains. © 2018 John Wiley & Sons, Ltd.
Geomorphological effectiveness of floods to rework gravel bars: Insight from hyperscale topography and hydraulic modelling
Authors: Reid H.E. , Williams R.D. , Brierley G.J. , Coleman S.E. , Lamb R. , Rennie C.D. , Tancock M.J.
Published: September 2018

Bars are key morphological units in river systems, fashioning the sediment regime and bedload transport processes within a reach. Reworking of these features underpins channel adjustment at larger scales, thereby acting as a key determinant of channel stability. Despite their importance to channel evolution, few investigations have acquired spatially continuous data on bar morphology and sediment‐size to investigate bar reworking. To this end, four bars along a 10 km reach of a wandering gravel‐bed river were surveyed with terrestrial laser scanning (TLS), comparing downstream changes in slope, bed material size and channel planform. Detrended standard deviations (σz) were extracted from TLS point clouds and correlated to underlying physically measured median grain‐size (D50), across a greater range of σz values than have hitherto been reported. The resulting linear regression model was used to create a 1 m resolution median grain‐size map. A fusion of airborne LiDAR and optical‐empirical bathymetric mapping was used to develop reach‐scale digital elevation models (DEMs) for rapid two‐dimensional hydraulic modelling using JFlow® software. The ratio of dimensionless shear stress over critical shear stress was calculated for each raster cell to calculate the effectiveness of a range of flood events (2.33–100 year recurrence intervals) to entrain sediment and rework bar units. Results show that multiple bar forming discharges exist, whereby frequent flood flows rework tail and back channel areas, while much larger, less frequent floods are required to mobilise the coarser sediment fraction on bar heads. Valley confinement is shown to exert a primary influence on patterns of bar reworking. Historical aerial photography, hyperscale DEMs and hydraulic modelling are used to explain channel adjustment at the reach scale. The proportion of the bar comprised of more frequently entrained units (tail, back channel, supra‐platform) relative to more static units (bar head) exerts a direct influence upon geomorphic sensitivity. © 2018 John Wiley & Sons, Ltd.
A new paper sensor method for field analysis of acid volatile sulfides in soils
Authors: Pellegrini Elisa , Contin Marco , Vittori Antisari Livia , Vianello Gilmo , Ferronato Chiara , De Nobili Maria
Published: September 2018

Monitoring of biogenic sulfide is important because acid volatile sulfides (AVS) represent a reactive pool responsible for immobilization of toxic metals. We propose a new sulfide paper sensor method for semiquantitative determination of AVS in which developed color is compared to a reference chart. The method was validated against the ion-selective microelectrode and the purge-and-trap methods. For fieldwork, readings should fall within 1 to 10 μmoles S2–. Considering that the volume of soil used ranged between 1 and 16 cm3, the corresponding soil sulfides concentration range spans from 0.06 to 10 mmoles S2– cm−3. The sulfide paper sensor method is highly suitable for field screening and has sensitivity levels comparable to laboratory methods. Environ Toxicol Chem 2018;37:3025–3031. © 2018 SETAC
Study on downward flame spread over extruded polystyrene foam in a vertical channel: Influence of opening area
Authors: An Weiguang , Yin Xiangwei , Chen Song , Zhang Guowei
Published: September 2018

Experimental methods and theoretical analysis are employed to investigate effects of channel opening area on downward flame spread characteristics of extruded polystyrene (XPS) thermal insulation materials on building facade. The average flame height first drops and then rises as dimensionless opening area (the ratio of sidewall opening area to sidewall area, ie, S*) increases. As S* rises, both the average and maximum temperature of the curtain wall decrease, and the decreasing of the average temperature is linear. XPS surface temperature history can be divided into four stages, ie, inapparent rising stage (preheating), significant rising stage (melting), dropping stage (pyrolysis), and rerising stage (ignition). The preheating length first rises and then drops as S* increases. The XPS flame spreads steadily at the early period while acceleration occurs at the later period. For different opening areas, the difference in spread distance history is not apparent in the early stage while this difference is significant in the later stage. The flame spread rate (Vf) first increases and then decreases as S* rises. A downward flame spread model for XPS in vertical channel with openings is built. The varied trend of Vf predicted using this model corresponds to the experimental result.
Investigation of Carbon Nanofiber‐supported Electrocatalysts with Ultra‐low Platinum Loading for the Use in PEM Fuel Cells
Authors: Podleschny P. , Rost U. , Muntean R. , Marginean G. , Heinzel A. , Peinecke V. , Radev I. , Muhler M. , Brodmann M.
Published: September 2018

The present study aims to investigate gas diffusion electrodes with ultra‐low platinum loading and increased durability, prepared by pulsed electrodeposition process, applicable for polymer electrolyte membrane fuel cells (PEMFC). Testing was performed both, in situ in a PEMFC test bench while prepared GDEs were compared to anodes and cathodes with commercially available catalysts by Johnson Matthey (JM), as well as ex situ regarding electrochemical properties and catalyst layer structure. High and stable performance of developed electrodes was achieved, while the Pt catalyst loading of investigated anodes and cathodes was reduced to 10 µgPt cm−2. The catalyst deposition was achieved via pulsed electrodeposition process from H2PtCl6‐containing electrolyte on an oxygen plasma‐pretreated corrosion‐stable carbon nanofiber (CNF) support. In situ performance tests show a similar operation behavior of the compared anodes, while activation losses of investigated cathodes are high due to the limited amount of catalyst material. However, Pt/CNF_c cathodes show significantly higher power densities than cathodes prepared with JM catalyst. Membrane electrode assemblies containing developed Pt/CNF_a anodes with 10 µgPt cm−2 reached a power density of 0.525 W cm−2 at a cell potential of 0.65 V, which was similar to anodes with commercially available HiSPEC 2000 catalysts by JM. Accelerated stress tests (AST) revealed that Pt/CNF_a anodes preserve their performance, whereas the commercial catalyst degraded severely. Cyclic voltammetry (CV) indicated a high electrochemical active surface area of Pt/CNF_a anodes. Moreover, the electrode characteristics, analyzed via electrochemical impedance spectroscopy after AST, showed marginal anode degradation.
Glio‐ and neuro‐protection by prosaposin is mediated by orphan G‐protein coupled receptors GPR37L1 and GPR37
Authors: Liu Beihui , Mosienko Valentina , Vaccari Cardoso Barbara , Prokudina Daria , Huentelman Mathew , Teschemacher Anja G. , Kasparov Sergey
Published: September 2018

Discovery of neuroprotective pathways is one of the major priorities for neuroscience. Astrocytes are natural neuroprotectors and it is likely that brain resilience can be enhanced by mobilizing their protective potential. Among G‐protein coupled receptors expressed by astrocytes, two highly related receptors, GPR37L1 and GPR37, are of particular interest. Previous studies suggested that these receptors are activated by a peptide Saposin C and its neuroactive fragments (prosaptide TX14(A)), which were demonstrated to be neuroprotective in various animal models by several groups. However, pairing of Saposin C or prosaptides with GPR37L1/GPR37 has been challenged and presently GPR37L1/GPR37 have regained their orphan status. Here, we demonstrate that in their natural habitat, astrocytes, these receptors mediate a range of effects of TX14(A), including protection from oxidative stress. The Saposin C/GPR37L1/GPR37 pathway is also involved in the neuroprotective effect of astrocytes on neurons subjected to oxidative stress. The action of TX14(A) is at least partially mediated by Gi‐proteins and the cAMP‐PKA axis. On the other hand, when recombinant GPR37L1 or GPR37 are expressed in HEK293 cells, they are not functional and do not respond to TX14(A), which explains unsuccessful attempts to confirm the ligand‐receptor pairing. Therefore, this study identifies GPR37L1/GPR37 as the receptors for TX14(A), and, by extension of Saposin C, and paves the way for the development of neuroprotective therapeutics acting via these receptors.

A video abstract of this article can be found at: https://www.youtube.com/watch?v=qTn13My9Sz8
Different effects of levodopa and subthalamic stimulation on emotional conflict in Parkinson's disease
Authors: Martínez‐Fernández Raul , Kibleur Astrid , Chabardès Stéphan , Fraix Valérie , Castrioto Anna , Lhommée Eugénie , Moro Elena , Lescoules Lucas , Pelissier Pierre , David Olivier , Krack Paul
Published: September 2018

Parkinson's disease impairs the decoding of emotional stimuli reflecting alterations of the limbic cortico‐subcortical network. The objective of this study was to assess and compare the behavioral and electrophysiological effects of both levodopa and subthalamic stimulation on emotional processing in Parkinson's disease. Operated patients (n =16) and matched healthy subjects performed an emotional Stroop task, in which the emotion expressed by a face must be recognized while ignoring an emotional distractive word and that includes a neutral control sub‐task. Patients were tested in the four possible treatment conditions (off stim/off med; on stim/off med; off stim/on med; and on stim/on med). High‐resolution electroencephalography was recorded while performing the task. Patients made significantly more mistakes in facial emotion recognition than healthy subjects (p < .005). Untreated patients performed worse in the emotional trials than in the control sub‐task (p < .05). Fearful faces induced significantly slower reaction times than happy faces in patients (p = .0002), but not in the healthy subjects. The emotional Stroop effect with levodopa was significantly higher than with subthalamic stimulation when fearful faces were assessed (p = .0243). Conversely, treatments did not modulate the Stroop effect of the control sub‐task. EEG demonstrated that, compared with the untreated state, levodopa but not subthalamic stimulation significantly increases the amplitude of the event‐related potential N170 (p = .002 vs. p = .1, respectively), an electrophysiological biomarker of early aspects of facial processing. The activity of the N170 cortical sources within the right fusiform gyrus was increased by levodopa (p < .05) but not by stimulation. While levodopa normalizes the recognition of emotional facial expression and early EEG markers of emotional processing, subthalamic stimulation does not. Thus, operated patients require dopaminergic medication in addition to stimulation to treat emotional symptoms of Parkinson's disease.