bluuebunny/crossref_metadata_2025 huggingface dataset:
ChemInform Abstract: A Four‐Step Route to Synthetic Equivalents of ortho‐Xylylenes: Doetz Benzannulation, Desilylation, Bromo‐Dehydroxylation, and Sultine Formation. A Concise Approach to Oxygenated Linearly Fused Polycyclic Aromatics.
Authors: Kotha Sambasivarao , Aswar Vikas R. , Manchoju Amarender
Published: July 2016

A new route is reported for the synthesis of densely oxygenated polycyclic aromatic compounds, such as (VII), (XI), and (XIII).
ChemInform Abstract: Nickel(II)‐Catalyzed Enantioselective Cyclopropanation of 3‐Alkenyl‐oxindoles with Phenyliodonium Ylide via Free Carbene.
Authors: Guo Jing , Liu Yangbin , Li Xiangqiang , Liu Xiaohua , Lin Lili , Feng Xiaoming
Published: July 2016

The title reaction affords spirocyclopropane‐oxindoles with contiguous tertiary and quaternary centers in high yields with excellent diastereo‐ and enantioselectivities through a stepwise biradical mechanism.
ChemInform Abstract: A One‐Pot Method for the Preparation of 2,5‐Diarylthiophene‐1‐oxides from Arylacetylenes.
Authors: Miller Robert W. , Dodge Nicholas J. , Dyer Adam M. , Fortner‐Buczala Eleanor M. , Whalley Adam C.
Published: July 2016

The title thiopheneoxides are prepared from readily available arylacetylene precursors via zirconacyclopentadiene intermediates in modest yields without over‐oxidation byproducts.
ChemInform Abstract: Synergistic Acid‐Catalyzed Synthesis of N‐Aryl‐Substituted Azacycles from Anilines and Cyclic Ethers.
Authors: Zhang Zhenbei , Miao Chengxia , Xia Chungu , Sun Wei
Published: July 2016

The environmentally benign metal‐free method produces water as the only side product.
ChemInform Abstract: Indole Synthesis Through Sequential Electrophilic N—H and C—H Bond Activation Using Iodine(III) Reactivity.
Authors: Fra Laura , Muniz Kilian
Published: July 2016

Four different conditions A)—D), which all contain an iodine agent in either stoichiometric or catalytic amount, are elaborated for the cyclization of aromatic sulfonamide precursors bearing an alkyne side chain, as is demonstrated for the examples (Ia) and (Ib).
ChemInform Abstract: Asymmetric Tandem Hemiaminal‐Heterocyclization‐Aza‐Mannich Reaction of 2‐Formylbenzonitriles and Amines Using Chiral Phase Transfer Catalysis: An Experimental and Theoretical Study
Authors: Capobianco Amedeo , Di Mola Antonia , Intintoli Valentina , Massa Antonio , Capaccio Vito , Roiser Lukas , Waser Mario , Palombi Laura
Published: July 2016

for the synthesis of 3‐amino‐substituted isoindolinones
ChemInform Abstract: CO2 Fixation at Atmospheric Pressure: Porous ZnSnO3 Nanocrystals as a Highly Efficient Catalyst for the Synthesis of Cyclic Carbonates.
Authors: Roy Susmita , Banerjee Biplab , Bhaumik Asim , Islam Sk. Manirul
Published: July 2016

The catalyst can be efficiently recycled and reused for five times without significant loss of activity.
ChemInform Abstract: Diastereoselective Passerini Reaction of Biobased Chiral Aldehydes: Divergent Synthesis of Various Polyfunctionalized Heterocycles.
Authors: Moni Lisa , Banfi Luca , Basso Andrea , Martino Elisa , Riva Renata
Published: July 2016

Noteworthy, the carboxylic component of the Passerini reaction is the acetic acid in situ formed as the side product by the reduction of diacetoxyiodobenzene.
ChemInform Abstract: A Synthesis of 1H‐Indazoles via a Cu(OAc)2‐Catalyzed N—N Bond Formation.
Authors: Chen Cheng‐yi , Tang Guangrong , He Fengxian , Wang Zhaobin , Jing Hailin , Faessler Roger
Published: July 2016

A variety of 1H‐indazoles is readily prepared by reaction of nitriles (I) with Grignard reagents followed by a copper‐catalyzed oxidative cyclization of intermediate ketimines.
ChemInform Abstract: A Strecker Approach to 2‐Substituted Ethyl 5‐Aminothiazole‐4‐carboxylates.
Authors: Cheng Ken , McClory Andrew , Walker Whitney , Xu Jie , Zhang Haiming , Angelaud Remy , Gosselin Francis
Published: July 2016

The three step sequence for the synthesis of the title thiazoles involves the 1,2‐addition of thioamides to glyoxylate (II), the treatment with acetyl chloride, and finally the Strecker addition‐cyclization reaction of the resulting imine precursors.
ChemInform Abstract: Visible‐Light Promoted Intermolecular Halofunctionalization of Alkenes with N‐Halogen Saccharins.
Authors: Song Lu , Luo Sanzhong , Cheng Jin‐Pei
Published: July 2016

The photoreaction of N‐bromosaccharin with a range of alkenes leads to a mixture of bromoamide (V) and bromoether (VI).
ChemInform Abstract: Orthogonal Dual‐Click Diyne for CuAAC and/or SPAAC Couplings.
Authors: Ramsubhag Ron R. , Dudley Gregory B.
Published: July 2016

Carbamate‐tethered propargyl and benzocyclononyne moieties within a single molecular unit undergo cycloaddition with azides under complementary copper‐catalyzed azide—alkyne cycloaddition and/or strain‐promoted azide—alkyne cycloaddition coupling conditions.
ChemInform Abstract: What Happens when the Terminal Aromatization Is Blocked? Construction of 1,2‐Dihydroquinoline Derivatives by (sp3) C—H Bond Oxidation of N‐Arylalaninates.
Authors: Lue Shiwei , Zhu Yingzu , Ma Xingge , Jia Xiaodong
Published: July 2016

Depending on the substrates′ functional groups 1,2‐dihydroquinolines are formed with moderate to very high yields.
ChemInform Abstract: Rhodium(II)‐Catalyzed Intramolecular Annulation of 1‐Sulfonyl‐1,2,3‐triazoles with Indoles: Facile Synthesis of Functionalized Tetrahydro‐β‐carbolines.
Authors: Shang Hai , Tian Yu , Luo Jun , Li Lingyu , Tang Yefeng , Zou Zhongmei
Published: July 2016

An efficient method for the synthesis of 4‐substituted tetrahydro‐β‐carbolines from readily available starting materials is demonstrated.
ChemInform Abstract: A One‐Pot Synthesis of Trichloromethylated Pyrimidines from Trichloroacetimidamides and Acetylenic Esters.
Authors: Yavari Issa , Malekafzali Alaleh , Eivazzadeh‐Keihan Reza , Skoulika Stavroula , Alivaisi Rahman
Published: July 2016

Trichloroacetimidamides generated in situ from guanidines and trichloroacetonitrile undergo an addition reaction with acetylenic esters to afford highly functionalized pyrimidine derivatives.
ChemInform Abstract: Synthesis of Fused Isoquinolines via Gold‐Catalyzed Tandem Alkyne Amination/Intramolecular O—H Insertion.
Authors: Pan Yuan , Chen Gui‐Wei , Shen Cang‐Hai , He Weimin , Ye Long‐Wu
Published: July 2016

A series of oxazinoisoquinolines is prepared by a tandem alkyne amination/intramolecular O—H insertion.
ChemInform Abstract: Copper‐Catalyzed Regio‐ and Enantioselective Aminoboration of Alkylidenecyclopropanes: The Synthesis of Cyclopropane‐Containing β‐Aminoalkylboranes.
Authors: Jiang Han‐Chun , Tang Xiang‐Ying , Shi Min
Published: July 2016

The reaction works well with cyclopropylidenetoluenes only.
ChemInform Abstract: Rhodium‐Catalyzed Cycloisomerization of 2‐Silylethynyl Phenols and Anilines via 1,2‐Silicon Migration
Authors: Kanno Hiroshi , Nakamura Kyosuke , Noguchi Keiichi , Shibata Yu , Tanaka Ken
Published: July 2016

affording silylbenzofurans and silylindoles
ChemInform Abstract: Regioselective and Stereoselective Route to N2‐β‐Tetrazolyl Unnatural Nucleosides via SN2 Reaction at the Anomeric Center of Hoffer′s Chlorosugar.
Authors: Bag Subhendu Sekhar , Talukdar Sangita , Anjali S. J.
Published: July 2016

12 N2‐β‐Tetrazolyl unnatural nucleosides of type (III)/(IV) are prepared via a SN2 regioselective and stereoselective reaction; only one of the four possible isomers is formed.
ChemInform Abstract: Norneolignans from the Roots of Clitoria ternatea L.
Authors: Vasisht Karan , Dhobi Mahaveer , Khullar Sadhika , Mandal Sanjay K. , Karan Maninder
Published: July 2016

Three new norneolignans, the clitorienolactones A—C along with a known triterpenoid, taraxerol, are isolated from the roots of Clitoria ternatea L.
ChemInform Abstract: Fabrication of Boron Nitride Nanosheets by Exfoliation
Authors: Zhi Chunyi , et al.
Published: July 2016

Review: [62 refs.
ChemInform Abstract: Quantum Kagome Frustrated Antiferromagnets: One Route to Quantum Spin Liquids
Authors: Mendels Philippe , Bert Fabrice
Published: July 2016

Review: 100 refs.
ChemInform Abstract: Metallosupramolecular Structures Derived from a Series of Diphosphine‐Bridged Digold(I) Metalloligands with Terminal D‐Penicillamine
Authors: Yoshinari Nobuto , Konno Takumi
Published: July 2016

Review: [156 refs.
ChemInform Abstract: Anionic N‐Heterocyclic Carbenes: Synthesis, Coordination Chemistry and Applications in Homogeneous Catalysis
Authors: Nasr Alexandre , Winkler Andrea , Tamm Matthias
Published: July 2016

Review: 304 refs.
ChemInform Abstract: Enantioselective Oxidative Boron Heck Reactions
Authors: Lee A.‐l.
Published: July 2016

Review: [39 refs.
ChemInform Abstract: Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry
Authors: Klankermayer Juergen , Wesselbaum Sebastian , Beydoun Kassem , Leitner Walter
Published: July 2016

Review: [253 refs.
ChemInform Abstract: Functional Arrays for Light Energy Capture and Charge Separation
Authors: Flamigni Lucia
Published: July 2016

Review: [typical procedures for the effective design and optimization of functional multicomponent structures for light to chemical energy conversion for a variety of examples based on corroles and terpyridyl metal complexes; 64 refs.
ChemInform Abstract: Genetic Optimization of Metalloenzymes: Enhancing Enzymes for Non‐Natural Reactions
Authors: Hyster Todd K. , Ward Thomas R.
Published: July 2016

Review: [71 refs.
ChemInform Abstract: Covalent Non‐Fused Tetrathiafulvalene—Acceptor Systems
Authors: Pop Flavia , Avarvari Narcis
Published: July 2016

Review: [117 refs.
ChemInform Abstract: Harnessing the Versatility of Continuous‐Flow Processes: Selective and Efficient Reactions
Authors: Mandity Istvan M. , Oetvoes Sandor B. , Szolosi Gyoergy , Fueloep Ferenc
Published: July 2016

Review: [such as (stereoselective) hydrogenations, deuterations, the copper‐catalyzed synthesis of triazoles and aromatic azo compounds, organocatalysis, and peptide syntheses; 79 refs.
ChemInform Abstract: Density Functional Theory in the Solid State
Authors: Hasnip Philip J. , Refson Keith , Probert Matt I. J. , Yates Jonathan R. , Clark Stewart J. , Pickard Chris J.
Published: July 2016

Review: 81 refs.
Rod‐cone crossover connectome of mammalian bipolar cells
Authors: Lauritzen J. Scott , Sigulinsky Crystal L. , Anderson James R. , Kalloniatis Michael , Nelson Noah T. , Emrich Daniel P. , Rapp Christopher , McCarthy Nicholas , Kerzner Ethan , Meyer Miriah , Jones Bryan W. , Marc Robert E.
Published: July 2016

The basis of cross‐suppression between rod and cone channels has long been an enigma. Using rabbit retinal connectome RC1, we show that all cone bipolar cell (BC) classes inhibit rod BCs via amacrine cell (AC) motifs (C1–6); that all cone BC classes are themselves inhibited by AC motifs (R1–5, R25) driven by rod BCs. A sparse symmetric AC motif (CR) is presynaptic and postsynaptic to both rod and cone BCs. ON cone BCs of all classes drive inhibition of rod BCs via motif C1 wide‐field GABAergic ACs (γACs) and motif C2 narrow field glycinergic ON ACs (GACs). Each rod BC receives ≈10 crossover AC synapses and each ON cone BC can target ≈10 or more rod BCs via separate AC processes. OFF cone BCs mediate monosynaptic inhibition of rod BCs via motif C3 driven by OFF γACs and GACs and disynaptic inhibition via motifs C4 and C5 driven by OFF wide‐field γACs and narrow‐field GACs, respectively. Motifs C4 and C5 form halos of 60–100 inhibitory synapses on proximal dendrites of AI γACs. Rod BCs inhibit surrounding arrays of cone BCs through AII GAC networks that access ON and OFF cone BC patches via motifs R1, R2, R4, R5 and a unique ON AC motif R3 that collects rod BC inputs and targets ON cone BCs. Crossover synapses for motifs C1, C4, C5, and R3 are 3–4× larger than typical feedback synapses, which may be a signature for synaptic winner‐take‐all switches. J. Comp. Neurol. 527:87–116, 2019. © 2016 The Authors The Journal of Comparative Neurology Published by Wiley Periodicals, Inc.
Multilayer hybrid strategy for phishing email zero‐day filtering
Authors: Chowdhury M. U. , Abawajy J. H. , Kelarev A. V. , Hochin T.
Published: July 2016

The cyber security threats from phishing emails have been growing buoyed by the capacity of their distributors to fine‐tune their trickery and defeat previously known filtering techniques. The detection of novel phishing emails that had not appeared previously, also known as zero‐day phishing emails, remains a particular challenge. This paper proposes a multilayer hybrid strategy (MHS) for zero‐day filtering of phishing emails that appear during a separate time span by using training data collected previously during another time span. This strategy creates a large ensemble of classifiers and then applies a novel method for pruning the ensemble. The majority of known pruning algorithms belong to the following three categories: ranking based, clustering based, and optimization‐based pruning. This paper introduces and investigates a multilayer hybrid pruning. Its application in MHS combines all three approaches in one scheme: ranking, clustering, and optimization. Furthermore, we carry out thorough empirical study of the performance of the MHS for the filtering of phishing emails. Our empirical study compares the performance of MHS strategy with other machine learning classifiers. The results of our empirical study demonstrate that MHS achieved the best outcomes and multilayer hybrid pruning performed better than other pruning techniques. Copyright © 2016 John Wiley & Sons, Ltd.
Transport vs. Metabolism: What Determines the Pharmacokinetics and Pharmacodynamics of Drugs? Insights From the Extended Clearance Model
Authors: Patilea‐Vrana G , Unadkat JD
Published: July 2016

The well‐stirred hepatic clearance model (WSHM) has been expanded to include drug transporters (i.e., extended clearance model [ECM]). However, the consequences of this expansion in understanding when transporters vs. metabolic enzymes will affect the pharmacokinetic (PK) and pharmacodynamic (PD) of drugs remains opaque. Identifying the rate‐determining step(s) in systemic or tissue drug PK/PD will allow accurate predictions of drug PK/PD and drug‐drug interactions (DDIs). Here, we clarify the implications of the ECM on PK/PD of drugs.
A view on the analytical design of future risk based residue control
Authors: van Ginkel Leendert A. , Sterk Saskia S.
Published: July 2016

The current laboratory network system in support of residue monitoring programmes within the EU formally started in the early 1990s. Since then, it has undergone a gentle evolution incorporating new techniques and methods for quality assurance and, in parallel to the extension of the European Union itself, was further extended. However, a paradigm shift from production‐based to risk‐based control now is foreseen. This will have a serious impact on the type of methodologies used and subsequently on the specific roles of EU reference laboratories also. Here, we present our view on the changes that will inevitably take place in the years to come. Copyright © 2016 John Wiley & Sons, Ltd.
Analysis of phenylbutazone residues in horse tissues with and without enzyme‐hydrolysis by LC‐MS/MS
Authors: Boison Joe O. , Dowling Trisha , Johnson Ron , Kinar Jana
Published: July 2016

Phenylbutazone (PBZ) is permitted to be used for the treatment of musculoskeletal pain and inflammation in race horses but it is not approved for use in horses destined for human consumption. In a recent study initiated in our laboratory to study the disposition of PBZ and its oxyphenbutazone (OXPBZ) metabolite in equine tissues, we compared the effect of an additional enzymatic hydrolysis step with ß‐glucuronidase on the results of the analysis for PBZ without enzymatic hydrolysis. Incurred tissue samples obtained from a female horse dosed with PBZ at 8.8 mg/kg for 3 days and sacrificed 6 days following the last administration were used for this study. Liver, kidney, and muscle tissues were collected, extracted, cleaned up on a silica‐based solid‐phase extraction (SPE) preceded by a weak‐anion exchange SPE and analyzed with our in‐house validated liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) method for PBZ and OXPBZ. Addition of the hydrolysis step resulted in a significant increase in recovery of both PBZ and OXPBZ residues. © 2016 Her Majesty the Queen in Right of Canada. Drug Testing and Analysis © 2016 John Wiley & Sons, Ltd.
An update discussion on the current assessment of the safety of veterinary antimicrobial drug residues in food with regard to their impact on the human intestinal microbiome
Authors: Cerniglia Carl E. , Pineiro Silvia A. , Kotarski Susan F.
Published: July 2016

The human gastrointestinal tract ecosystem consists of complex and diverse microbial communities that have now been collectively termed the intestinal microbiome. Recent scientific breakthroughs and research endeavours have increased our understanding of the important role the intestinal microbiome plays in human health and disease. The use of antimicrobial new animal drugs in food‐producing animals may result in the presence of low levels of drug residues in edible foodstuffs. There is concern that antimicrobial new animal drugs in or on animal‐derived food products at residue‐level concentrations could disrupt the colonization barrier and/or modify the antimicrobial resistance profile of human intestinal bacteria. Therapeutic doses of antimicrobial drugs have been shown to promote shifts in the intestinal microbiome, and these disruptions promote the emergence of antimicrobial‐resistant bacteria. To assess the effects of antimicrobial new animal drug residues in food on human intestinal bacteria, many national regulatory agencies and international committees follow a harmonized process, VICH GL36(R), which was issued by a trilateral organization of the European Union, the USA, and Japan called the International Cooperation on Harmonization of Technical Requirements for Veterinary Medicinal Products (VICH). The guidance describes a general approach currently used by national regulatory agencies and international committees to assess the effects of antimicrobial new animal drug residues in animal‐derived food on human intestinal bacteria. The purpose of this review is to provide an overview of this current approach as part of the antimicrobial new animal drug approval process in participating countries, give insights on the microbiological endpoints used in this safety evaluation, and discuss the availability of new information. Copyright © 2016 John Wiley & Sons, Ltd.
Habituation reverses fear‐based ecological effects in brown bears (Ursus arctos)
Authors: Wheat Rachel E. , Wilmers Christopher C.
Published: July 2016

Fear induced by human activity is increasingly becoming recognized to influence both behavior and population biology of wildlife. Exposure to human activity can cause animals to avoid human‐dominated areas or shift temporal activity patterns, but repeated, benign exposure can also result in habituation of individuals. Habituation is typically viewed as a negative potential consequence of human interactions with wildlife, with effects such as increased vulnerability of habituated animals to predation. Concurrently, the advancement of the understanding of the ecology of fear has shown reduced fitness in species because of behavioral changes in responses to fear of predators—including humans. Here, we test how habituation and fear drive the foraging ecology of brown bears (Ursus arctos) feeding on Pacific salmon (Oncorhynchus spp.) in Southeast Alaska, USA. We used motion‐detecting trail cameras at salmon spawning areas across a gradient of human disturbance to record human and bear activity at fine spatial and extended temporal scales. Higher human activity was associated with increased nocturnality of non‐habituated bears, likely leading to suboptimal foraging, but had no effect on habituated individuals. For the top 20% of sites for which human activity was greatest, an average of 78.7% of the activity of non‐habituated bears was nocturnal, compared with an average of only 10.2% of the activity of habituated individuals. Habituation of brown bears in this system alleviated perceived risk and avoidance of human activity, allowing habituated individuals to overcome their fear of human presence and maximize foraging opportunities. While habituation may lessen some of the deleterious effects of human activity on large carnivores, the long‐term effects of habituation may be negative, as habituated individuals may be at greater risk of depredation. Future research should examine whether habituated bears and their lower perceived risk of human activity ultimately experience smaller population‐level effects of human disturbance than non‐habituated individuals.
Temperature dependence of predation stress and the nutritional ecology of a generalist herbivore
Authors: Schmitz Oswald J. , Rosenblatt Adam E. , Smylie Meredith
Published: July 2016

Prey at risk of predation may experience stress and respond physiologically by altering their metabolic rates. Theory predicts that such physiological changes should alter prey nutrient demands from N‐rich to C‐rich macronutrients and shift the balance between maintenance and growth/reproduction. Theory further suggests that for ectotherms, temperature stands to exacerbate this stress. Yet, the interactive effects of predation stress and temperature stress on diet, metabolism, and survival of ectotherms are not well known. This knowledge gap was addressed with a laboratory study in which wild juvenile grasshoppers were collected, assigned to one of three groups, and raised at three different temperatures. All grasshoppers had access to equal quantities of two diets composed of opposite carbohydrate : protein ratios. Half of the individuals in each temperature group were exposed to predation risk cues from spider predators, while the other half were kept in risk free conditions. Grasshoppers consumed more carbohydrates when exposed to predation risk, but consumption favored greater protein intake as temperature increased. Moreover, the difference in carbohydrate intake between risk cue and risk free treatments diminished as temperature increased. Furthermore, variability between individual consumption patterns both within and between treatments decreased markedly as temperature increased, suggesting that higher temperatures promote more consistent individual consumption behaviors. Grasshoppers grew faster and larger as temperature increased, which translated into higher survival rates at higher temperatures. Warmer grasshoppers also did not alter their metabolic rates in response to predation risk cues, in contrast to colder grasshoppers. Digestive efficiency increased with temperature as well ‐‐ further indicating that lower temperatures were much more stressful than higher temperatures for grasshoppers. The study shows that physiological responses of ectothermic herbivores to predation stress are highly plastic and temperature dependent, with higher temperatures promoting increased protein intake, growth, development, survival, and digestive efficiency relative to colder temperatures. These findings help to reconcile why dietary responses (proportion of protein vs. carbohydrate intake) to predation stress may vary among different prey taxa studied previously.
Analysis of Dislocation Structures in 4H‐SiC by Synchrotron X‐Ray Topography
Authors: MATSUHATA HIROHUMI , YAMAGUCHI HIROTAKA , SEKIGUCHI TAKASHI , CHEN BIN , SASAKI MASAYUKI , OHNO TOSHIYUKI , SUZUKI TAKUMA , HATAKEYAMA TETSUO , TSUJI TAKASHI , YONEZAWA YOSHIYUKI , ARAI KAZUO
Published: July 2016

Current 4H‐SiC wafers contain certain amount of dislocations, stacking faults, and other lattice‐defects. These defect structures evolve during various processes for power device fabrication. It is very important to examine evolutions of dislocation structures during power device processes, as well as the effect of dislocations on performances of fabricated power devices. Since lattice defects can be observed at only subsurface regions selectively by Berg–Barrett X‐ray topography, we have applied this useful observation technique to 4H‐SiC technology to solve various technological issues. Appearances of scratch‐like surface morphology after epi‐film growth on very flat substrate surface by chemomechanically polish were examined by this technique, and the mechanism was discussed. Analyses of dislocation structure evolutions during epi‐film growth and also basal‐plane dislocation glide by recombination of electrons and holes were discussed. Effects of threading‐screw dislocations on reliability of MOS structures and on current leakage in pn‐junction under reversed bias condition were investigated and discussed. Various important suggestions for 4H‐Sic industries were obtained.
Kinetics and Thermodynamics of Constitutional Dynamic Coordination Systems Based on FeII, CoII, NiII, CuII, and ZnII
Authors: Neranon Kitjanit , Ramström Olof
Published: July 2016

The self‐adaptation of constitutional dynamic systems based on selective coordination between 5,5′‐dimethyl‐2,2′‐bipyridine and deuterium‐labeled 4,4′‐dimethyl‐2,2′‐bipyridine to FeII, CoII, NiII, CuII, or ZnII has been evaluated by ESI‐MS in methanol. The equilibration rates of the systems proved dependent on the metal species, following the order ZnII > CuII > CoII > NiII > FeII, where ZnII resulted in rapid rearrangement of the original homoleptic complexes. The heteroleptic complexes were favored in the systems with CoII, CuII and ZnII, whereas the homoleptic complexes were more pronounced with FeII and NiII.
The effect of ultrasound on the hydrolysis of soybean oil catalyzed by phospholipase
Authors: Awadallak Jamal Abd , Reinehr Thiago Olinek , Molinari Deise , Raizer Eduardo , Cardozo‐Filho Lucio , da Silva Edson Antonio , da Silva Camila
Published: July 2016

In this work, soybean oil enzymatic hydrolysis was studied in several operational and reactional conditions using a phospholipase as catalyst. In a first approach, different ultrasound configurations were evaluated and compared to a control reaction. Direct enzyme exposure to ultrasonic irradiation has shown an increment on initial hydrolysis rate but also led to a great enzymatic deactivation and a lower products yield. Reaction performed in two step has shown better results. In this methodology, substrate was pre‐emulsified under ultrasonic irradiation and after that the enzyme was add to start the reaction. In a second approach, surfactant concentration, pre‐emulsification time, enzyme fraction, and oil/water ratio were evaluated. An unexpected behavior was observed on the oil/water ratio experiments. There was a large decrease on the hydrolysis rate around 0.4 oil/water ratio. This phenomenon was thoroughly investigated and it was correlated to the inversion of the continuous phase on the emulsion.

Practical applications: Phospholipases can be used as an alternative to conventional lipases for oil modifications in the food/pharmaceutical industry. These reactions are usually slow and can take up days to complete conversion. Ultrasound technology can highly enhance lipase catalyzed oil reaction kinetics, but its application is not fully developed. This paper presents distinct methods to apply the ultrasound on phospholipase catalyzed oil hydrolysis reaction and evaluates several operational conditions. The results obtained in this study can be used to fix operational parameters and reduce the reaction time on the oil hydrolysis reaction.

Effect of ultrasound different treatments on the typical hydrolysis profile of soybean oil.
Construction of Isoxazolidines through Formal [3+2] Cycloaddition Reactions of in situ Generated Nitrosocarbonyls with Donor–Acceptor Cyclopropanes: Synthesis of α‐Amino γ‐Butyrolactones
Authors: Varshnaya Rohit Kumar , Banerjee Prabal
Published: July 2016

A straightforward approach for the synthesis of isoxazolidines through MgI2‐catalyzed [3+2] cycloaddition reactions of donor–acceptor cyclopropanes with in situ generated nitrosocarbonyls from hydroxycarbamates is described. This method facilitates one‐pot synthesis of α‐amino‐γ‐butyrolactone by deprotection, reductive cleavage of N–O bond, and successive lactonization.
Hierarchical, virtualised and distributed intelligence 5G architecture for low‐latency and secure applications
Authors: Siddiqui M.S. , Legarrea A. , Escalona E. , Parker M.C. , Koczian G. , Walker S.D. , Lyberopoulos G. , Theodoropoulou E. , Filis K. , Foglar A. , Ulbricht M. , Liu Y. , Point J.C. , Trouva E. , Rokkas Th. , Neokosmidis I. , Kritharidis D. , Katsaros K. , Spirou S. , Habel K. , Jungnickel V. , Canales C. , Lorenzo M.
Published: July 2016

CHARISMA aims to tackle low‐latency and end‐to‐end security for converged fixed/wireless 5G networks in order to meet the complex demands of emerging business paradigms, such as Smart Cities, eHealth and Industry 4.0. In this paper, we present the key drivers and requirements towards a hierarchical, distributed‐intelligence 5G architecture, supporting low latency, security and open access as features intrinsic to its design. We also investigate the business perspective of the proposed 5G solution and the changes that can be foreseen for the telecom ecosystem. Copyright © 2016 John Wiley & Sons, Ltd.
Free tissue transfer as a vascular source for the vessel‐depleted neck
Authors: Tsao Chung‐Kan , Loh Charles Yuen Yung , Barrera Joaquim Megias
Published: July 2016

Background

Reconstructing head and neck defects postoncologic resection can be challenging. This problem is further amplified when tackling the vessel‐depleted or hostile neck. Free flaps still provide the gold standard of reconstructing such defects. However, with increasing reconstructions, recipient vessel options rapidly diminish. This article provides a technique and strategy in managing such difficult cases using previous free flap pedicles. It also highlights the importance of flap selection in paving the way for future successful reconstructions.

Methods

We present a fifth sequential free flap reconstruction postoncologic buccal resection and mention the key steps taken to ensure the safe and successful reuse of previous free flap pedicles.

Results

Intraoperative and postoperative photographs are clearly presented with a particular focus on the management of the recipient pedicle.

Conclusion

Adequate planning and strategic selection of free flaps with long pedicles can provide the necessary vascular sources needed for future successful free flap head and neck reconstructions. © 2016 Wiley Periodicals, Inc. Head Neck 38: E2515–E2518, 2016
The Development of a Stereoselective Method for the Synthesis of Tetrasubstituted Derivatives of α,β‐Unsaturated Carboxylic Acids
Authors: Rzymkowski Jan , Piątek Anna
Published: July 2016

Alkenes possessing four different carbon‐linked substituents are the main structural motif of many biologically active compounds. The derivatives of (2E)‐3‐(3‐methoxyphenyl)‐2‐methylpent‐2‐enoic acid ((E)‐2c) are suitable precursors for the synthesis of Tapentadol, a novel centrally acting analgesic. It was found that the Ni‐carbometallation reaction of disubstituted alkyne 8 with CO2 and an Et2Zn allows for efficient and practical preparation of (E)‐2c as a single (E)‐regioisomer in 89% of isolated yield. The influence of the size of the aliphatic substituent of alkyne and the steric hindrance of the organozinc reagent on stereochemical course of the carbometallation reaction was evaluated. Finally, air‐stable Ni(dme)Cl2 was proposed as an alternative to widely used Ni(cod)2 catalyst.
A spatially distributed model for assessment of the effects of changing land use and climate on urban stream quality
Authors: Sun Ning , Yearsley John , Baptiste Marisa , Cao Qian , Lettenmaier Dennis P. , Nijssen Bart
Published: July 2016

While the effects of land use change in urban areas have been widely examined, the combined effects of climate and land use change on the quality of urban and urbanizing streams have received much less attention. We describe a modelling framework that is applicable to the evaluation of potential changes in urban water quality and associated hydrologic changes in response to ongoing climate and landscape alteration. The grid‐based spatially distributed model, Distributed Hydrology Soil Vegetation Model‐Water Quality (DHSVM‐WQ), is an outgrowth of DHSVM that incorporates modules for assessing hydrology and water quality in urbanized watersheds at a high‐spatial and high‐temporal resolution. DHSVM‐WQ simulates surface run‐off quality and in‐stream processes that control the transport of non‐point source pollutants into urban streams. We configure DHSVM‐WQ for three partially urbanized catchments in the Puget Sound region to evaluate the water quality responses to current conditions and projected changes in climate and/or land use over the next century. Here, we focus on total suspended solids (TSS) and total phosphorus (TP) from non‐point sources (run‐off), as well as stream temperature. The projection of future land use is characterized by a combination of densification in existing urban or partially urban areas and expansion of the urban footprint. The climate change scenarios consist of individual and concurrent changes in temperature and precipitation. Future precipitation is projected to increase in winter and decrease in summer, while future temperature is projected to increase throughout the year. Our results show that urbanization has a much greater effect than climate change on both the magnitude and seasonal variability of streamflow, TSS and TP loads largely because of substantially increased streamflow and particularly winter flow peaks. Water temperature is more sensitive to climate warming scenarios than to urbanization and precipitation changes. Future urbanization and climate change together are predicted to significantly increase annual mean streamflow (up to 55%), water temperature (up to 1.9 °C), TSS load (up to 182%) and TP load (up to 74%). Copyright © 2016 John Wiley & Sons, Ltd.
Preventing risk and promoting resilience in radiation health
Authors: Kurth Margaret H , Linkov Igor
Published: July 2016

Because risk assessment is fundamentally deficient in the face of unknown or unforeseeable events and disasters such as occurred in 2011 at the Fukushima Daiichi Nuclear Power Station in Japan, resilience thinking, which focuses on the ability of both natural and human-made systems to prepare for, absorb, and recover from an adverse event and to adapt to new conditions is an important additional consideration in decision making. Radiation contamination is an impediment to most critical functions of a community; resilience planning considers how those critical functions will be maintained in the event that radiation contamination does occur. Therefore, planning should begin with resilience-based thinking and should be complemented with risk assessment-based tools. Integr Environ Assess Manag 2016;12:677–679. Published 2016. This article is a U.S. Government work and is in the public domain in the USA.
Fracture Rates and Fracture Sites in Patients With Osteogenesis Imperfecta: A Nationwide Register-Based Cohort Study
Authors: Folkestad Lars , Hald Jannie Dahl , Ersbøll Annette Kjær , Gram Jeppe , Hermann Anne Pernille , Langdahl Bente , Abrahamsen Bo , Brixen Kim
Published: July 2016

Osteogenesis imperfecta (OI) is a hereditary, clinically heterogeneous, connective tissue disorder. The population prevalence of OI in Denmark is 10.6 in 100,000. A hallmark of the disease is frequent fractures that are often precipitated by minimal trauma. The aim of the current study was to compare the fracture rates across the lifespan of patients with OI with that of a reference population from the general population. The present study was a Danish nationwide, population-based, cohort study using register data. We identified 644 (55.6% females) patients in the OI cohort through the Danish National Patient Register and 3361 (55.2% females) persons, randomly selected from the Civil Registry System. A total of 416 patients with OI experienced a total of 1566 fractures during the observation period of median 17.9 years (interquartile range [IQR], 12.4 to 18.0 years), summing to 10137 person years. In comparison, 709 persons in the reference population experienced a total of 1018 fractures during follow-up. Both male and female patients with OI had an increased fracture rate throughout their life. The fracture rate ratio for participants aged 0 to 19 years was 10.7, for participants aged 20 to 54 years 17.2, and for participants aged 55 years and over 4.1 when compared to the reference population. The highest fracture rate was seen in males with OI aged 0 to 19 years (257 fractures per 1000 person-years). The fractures appear to follow the same pattern as in the general population, with a peak during the toddler and adolescent years (incidence rate [IR] 233.9 per 1000 person years), fewer fractures during adulthood (IR 84.5 per 1000 person years), and increased fracture rates in older women (IR 111.9 per 1000 person years). This is the largest register-based nationwide study on the fracture epidemiology of patients with OI. The risk of fractures seems largest in the childhood and adolescent years, and the relative risk of fracture declines with age in patients with OI compared to the general population. © 2016 American Society for Bone and Mineral Research.
A generalized operational formula based on total electronic densities to obtain 3D pictures of the dual descriptor to reveal nucleophilic and electrophilic sites accurately on closed‐shell molecules
Authors: Martínez‐Araya Jorge I.
Published: July 2016

By means of the conceptual density functional theory, the so‐called dual descriptor (DD) has been adapted to be used in any closed‐shell molecule that presents degeneracy in its frontier molecular orbitals. The latter is of paramount importance because a correct description of local reactivity will allow to predict the most favorable sites on a molecule to undergo nucleophilic or electrophilic attacks; on the contrary, an incomplete description of local reactivity might have serio us consequences, particularly for those experimental chemists that have the need of getting an insight about reactivity of chemical reagents before using them in synthesis to obtain a new compound. In the present work, the old approach based only on electronic densities of frontier molecular orbitals is replaced by the most accurate procedure that implies the use of total electronic densities thus keeping consistency with the essential principle of the DFT in which the electronic density is the fundamental variable and not the molecular orbitals. As a result of the present work, the DD will be able to properly describe local reactivities only in terms of total electronic densities. To test the proposed operational formula, 12 very common molecules were selected as the original definition of the DD was not able to describe their local reactivities properly. The ethylene molecule was additionally used to test the capability of the proposed operational formula to reveal a correct local reactivity even in absence of degeneracy in frontier molecular orbitals. © 2016 Wiley Periodicals, Inc.
Two‐dimensional shear wave elastography with propagation‐based reliability assessment for grading hepatic fibrosis and portal hypertension
Authors: Maruyama Hitoshi , Kobayashi Kazufumi , Kiyono Soichiro , Sekimoto Tadashi , Kanda Tatsuo , Yokosuka Osamu
Published: July 2016

Background

The aim of the present study was to examine the diagnostic ability of two‐dimensional shear wave elastography (2D‐SWE) with propagation‐based reliability for grading of hepatic fibrosis and portal hypertension.

Methods

This prospective study (UMIN000022838) consisted of 135 subjects. Phase I (n = 40) examined the effect of standard deviation (SD)/median as the reliability criterion of 2D‐SWE, and phase II (n = 95) compared the diagnostic ability of 2D‐SWE under the best SD/median value and transient elastography (TE).

Results

Phase I reported 0.49 as a best cut‐off SD/median value. In phase II, the elasticity showed a correlation between the 2D‐SWE and TE (r = 0.88, P < 0.001). The area under the receiver operating characteristic curve (AUROC) was comparable between the 2D‐SWE and TE (0.936 and 0.948 for chronic hepatitis, P = 0.34; 0.939 and 0.956 for cirrhosis, P = 0.25). The hepatic venous pressure gradient showed a positive correlation with the 2D‐SWE (r = 0.435, P = 0.043) and TE (r = 0.378, P = 0.083) in 22 patients. The AUROC was comparable between the 2D‐SWE (0.844 for ≥10 mmHg, 0.838 for ≥12 mmHg) and TE (0.781 for ≥10 mmHg, P = 0.484; 0.800 for ≥12 mmHg, P = 0.589).

Conclusions

2D‐SWE is promising for the assessment of the grade of hepatic fibrosis and portal hypertension, with the SD/median value as a reliability criterion.
Adding value through accelerator mass spectrometry‐enabled first in human studies
Authors: Seymour Mark A.
Published: July 2016

Accelerator mass spectrometry (AMS) is an ultra‐sensitive technique for the analysis of radiocarbon. It is applicable to bioanalysis of any 14C‐labelled analyte and any sample type. The increasing body of data generated using LC+AMS indicates that the methodology is robust and reliable, and capable of meeting the same validation criteria as conventional bioanalytical techniques. Because it is a tracer technique, AMS is capable of discriminating between an administered radiolabelled dose and endogenous compound or non‐radiolabelled compound administered separately. This paper discusses how it can be used to enhance the design of first in human (FIH) clinical studies and generate significant additional data, including: fundamental pharmacokinetics (CL and V), absolute bioavailability, mass balance, routes and rates of excretion, metabolic fate (including first‐pass metabolism, identification of biliary metabolites and quantitative data to address metabolite safety testing issues), and tissue disposition of parent compound and metabolites. Because the 14C‐labelled microtracer dose is administered at the same time as a pharmacologically relevant non‐radiolabelled dose, there is no concern about dose‐linearity. However the mass of the microtracer dose itself is negligible and therefore does not affect the outcome of the FIH study. The addition of microtracer doses to a FIH study typically requires little additional expense, apart from the AMS analytics, making the approach cost‐effective. It can also save significant time, compared to conventional approaches, and, by providing reliable human in vivo data as early as possible, prevent unnecessary expenditure later in drug development.
Differentiation of AB‐FUBINACA positional isomers by the abundance of product ions using electron ionization–triple quadrupole mass spectrometry
Authors: Murakami Takaya , Iwamuro Yoshiaki , Ishimaru Reiko , Chinaka Satoshi , Sugimura Natsuhiko , Takayama Nariaki
Published: July 2016

Mass spectrometric differentiation of structural isomers is important for the analysis of forensic samples. Presently, there is no mass spectrometric method for differentiating halogen positional isomers of cannabimimetic compounds. We describe here a novel and practical method for differentiating one of these compounds, N‐(1‐amino‐3‐methyl‐1‐oxobutan‐2‐yl)‐1‐(4‐fluorobenzyl)‐1H‐indazole‐3‐carboxamide (AB‐FUBINACA (para)), and its fluoro positional (ortho and meta) isomers in the phenyl ring by electron ionization–triple quadrupole mass spectrometry. It was found that the three isomers differed in the relative abundance of the ion at m/z 109 and 253 in the product ion spectra, while the detected product ions were identical. The logarithmic values of the abundance ratio of the ions at m/z 109 to 253 (ln(A109/A253)) were in the order meta < ortho < para and increased linearly with collision energy. The differences in abundances were attributed to differences in the dissociation reactivity between the indazole moiety and the fluorobenzyl group because of the halogen‐positional effect on the phenyl ring. Our methodology, which is based on the abundance of the product ions in mass spectra, should be applicable to determination of the structures of other newly encountered designer drugs. Copyright © 2016 John Wiley & Sons, Ltd.
Pain in autoimmune disorders
Authors: Mifflin Katherine A. , Kerr Bradley J.
Published: July 2016

Most autoimmune diseases are associated with pathological pain development. Autoimmune diseases with pathological pain include complex regional pain syndrome, rheumatoid arthritis, and Guillian‐Barré syndrome to name a few. The present Review explores research linking the immune system to the development of pathological pain in autoimmune diseases. Pathological pain has been linked to T‐cell activation and the release of cytokines from activated microglia in the dorsal horn of the spinal cord. New research on the role of autoantibodies in autoimmunity has generated insights into potential mechanisms of pain associated with autoimmune disease. Autoantibodies may act through various mechanisms in autoimmune disorders. These include the alteration of neuronal excitability via specific antigens such as the voltage‐gated potassium channel complexes or by mediating bone destruction in rheumatoid arthritis. Although more research must be done to understand better the role of autoantibodies in autoimmune disease related pain, this may be a promising area of research for new analgesic therapeutic targets. © 2016 Wiley Periodicals, Inc.
Tip‐enhanced Raman spectroscopy (TERS) on double perovskite La2CoMnO6 thin films: field enhancement and depolarization effects
Authors: Meyer Christoph , Hühn Sebastian , Jungbauer Markus , Merten Sebastian , Damaschke Bernd , Samwer Konrad , Moshnyaga Vasily
Published: July 2016

Polarization‐dependent tip‐enhanced Raman spectroscopy (TERS) was carried out on double perovskite La2CoMnO6 (LCMO) thin films to determine the contributions of the enhancement by the excitation of surface plasmon polariton and tip‐induced polarization effects. Due to B‐site ordering and the resulting monoclinic P121/n1 structure, the spectra exhibit a strong Ag mode around 644 cm−1 originated from (Co/Mn)O6 stretching vibrations. The TERS contrast C, defined as the ratio of the total‐field (the sum of the near field and the far field) to the far‐field intensity, up to C ~60–110 for a cross‐polarized configuration (incident light polarization perpendicular to the detected one), reveals a possible breakdown of polarization‐dependent selection rules for the Raman scattering due to a tip‐induced near‐field depolarization component. We disentangled a significant enhancement for all observed modes in a parallel configuration with a TERS contrast of C ~2–5 due to general near‐field amplification, strongly affected also by the film thickness. With B‐site ordering and highly dielectric behavior, LCMO therefore provides an excellent test system to study TERS phenomena on oxide surfaces. Copyright © 2016 John Wiley & Sons, Ltd.