bluuebunny/crossref_metadata_2025 huggingface dataset:
‘He is Quirky; He is the World's Greatest Psychologist’: On the Community of Those Who Have Nothing in Common
Authors: Bertelsen Bård , Bøe Tore Dag
Published: September 2016

In this article, we challenge the concept of the therapeutic relationship as an operationalisable entity. In contrast to this idea, we introduce Alphonso Lingis’ concept of community, and his distinction betweenthe rational communityandthe community of those who have nothing in common. This is done through speculative analysis of a transcribed sequence from a research interview with a boy who speaks about his experiences of receiving mental health care. This boy and his family were helped through a network‐oriented, dialogical approach. In the sequence highlighted here, the boy speaks of the significance of a particular mental health practitioner. The boy expresses appreciation for the help he has received, yet it is difficult to translate the boy's utterances into meaningful professional jargon. Although the paper makes use of an actual sequence from a research interview, the argument is not empirical in nature. The purpose of the paper is to elaborate on theory, and to examine some possible consequences for future practice.
Social Work Student Learning Experiences of Family Therapy: Improving Competency in Pedagogy Through Qualitative Research
Authors: Peterson Lance , Jones Ellie , Salscheider Kaitlin
Published: September 2016

The purpose of this qualitative study is to evaluate graduate social work student experiences of pedagogy intended to improve competency in family therapy practice. Students from two classes (N = 37) completed open‐ended surveys assessing: perceptions of most helpful pedagogical practices; understanding of needed competencies; and perceived opportunities offered to them during their graduate training for learning about work with couples and families. Results, analysed using grounded theory methodology, revealed that students: (1) believed that experiential activities were especially critical for learning how to do clinical practice with couples and families; (2) understood important competencies related to professional development, therapeutic engagement with the family, and how to approach family practice; and (3) believed they were ‘somewhat prepared’ for practice. Implications include improving understanding of abstract skills in practice with couples and families, and emphasising relationship dynamics more in graduate social work education and training.
Dialogical Research in Supervision: Practical Guidelines from Experienced Supervisors in Family Therapy, Child Protection, and Specialty Mental Health Services
Authors: Flåm Anna Margrete
Published: September 2016

This two‐year qualitative participatory research project examines practical guidelines for supervision. Sixteen experienced supervisors across professional settings of family therapy, child protection, and specialty mental health services in the geographical regions of Northern Norway and Northern Sweden outline four main practical guidelines in supervision based on their supervisory practices: (1) elaborating an agreed‐upon contract; (2) exploring potential formats; (3) exploring contents; (4) acknowledging responsibility for process and dilemmas. Participants summarised how they generated mutual growth in supervisory relationships, while being respectful of the first‐person perspective of supervisees. The study challenges pre‐dominating guidelines about deficit‐ or developmental stage‐oriented supervision. It illustrates reflecting processes and a polyphonic orientation in supervision by welcoming diversity, wondering, and tolerance for the not‐yet‐decided among involved persons in a mutual exploration and calibration of relevant knowledge. It outlines a dialogical research for sharing, exploring, and questioning knowledge as beneficial for whom, told by whom, and evaluated by whom.
Reflective Practice: An Exercise in Exploring Inner Dialogue and Vertical Polyphony
Authors: Mikes‐Liu Kristof , Goldfinch Margaret , MacDonald Chloe , Ong Ben
Published: September 2016

The dialogical notion of vertical polyphony, referring to multiple internal voices, is explored in relation to clinicians’ professional and personal selves. We describe an experiential training exercise developed to enhance clinicians’ awareness and understanding of their inner dialogue, and create space to practice what Schön terms ‘reflecting‐in‐action’ and ‘knowing‐in‐action.’ The exercise involves stages of personal reflection, discussion in groups of two or three, and shared learning by the group. A number of variations of the exercise are described. The invited commentaries following the article provide a sense of participants’ reactions to the exercises. Readers are invited to adapt the exercise to suit their own setting and to enhance reflective practice.
Meeting the Wharenui Shapes Teaching/Learning Therapy: Place Pedagogy, New Materialism, and Whakaaro Māori
Authors: Kotzé Elmarie , Crocket Kathie , Waititi (Ngāti Porou) Cheri
Published: September 2016

A cultural meeting house hosts a group of Master of Counselling students at the start of their studies. This article focuses on an exploratory study with one student group during their encounter with the house. We give a material‐discursive account of one student's narrative of family, belonging, and connection to the house. In the account we draw on whakaaro Māori (cultural thinking and understanding), new materialism, place‐space learning, and narrative therapy.
Constructing Personal and Couple Narratives in Late‐stage Cancer: Can a Typology Illuminate the Caring Partner Perspective?
Authors: Anthias Louise
Published: September 2016

There is a large body of work focusing on the well‐being and relationships of couples facing late‐stage cancer. The systemic study underpinning this paper explored a less researched topic: How do people caring for a partner with terminal cancer construct their experience and relationships through personal and couple narratives? ThisUK‐based study drew upon dialogical approaches to narrative analysis to focus on six caring partners and their care relationships. Following individual case analysis, two methods of cross‐narrative analysis were developed, and an analysis of narrative themes and a typology of archetypal narratives were drawn from the data. This paper focuses on the typology. The clinical implications of the study are considered, focusing on the contribution of a typology to this and future studies.
Post selection shrinkage estimation for high‐dimensional data analysis
Authors: Gao Xiaoli , Ahmed S. E. , Feng Yang
Published: September 2016

In high‐dimensional data settings wherep ≫ n, many penalized regularization approaches were studied for simultaneous variable selection and estimation. However, with the existence of covariates with weak effect, many existing variable selection methods, including Lasso and its generations, cannot distinguish covariates with weak and no contribution. Thus, prediction based on a subset model of selected covariates only can be inefficient. In this paper, we propose a post selection shrinkage estimation strategy to improve the prediction performance of a selected subset model. Such a post selection shrinkage estimator (PSE) is data adaptive and constructed by shrinking a post selection weighted ridge estimator in the direction of a selected candidate subset. Under an asymptotic distributional quadratic risk criterion, its prediction performance is explored analytically. We show that the proposed post selection PSE performs better than the post selection weighted ridge estimator. More importantly, it improves the prediction performance of any candidate subset model selected from most existing Lasso‐type variable selection methods significantly. The relative performance of the post selection PSE is demonstrated by both simulation studies and real‐data analysis. Copyright © 2016 John Wiley & Sons, Ltd.
Wood property relationships and survival models in reliability
Authors: Cheng Yan , Wu Lang , Lum Conroy , Zidek Jim , Yu Tingting
Published: September 2016

We study the relationship between lumber strength properties and their visual grading characteristics. This topic is central to the analysis of the reliability of lumber products in that it underlies the calculation of structural design values. The approaches described in the paper are adaptations of survival analysis methods commonly used in medical studies. Because each piece of lumber can only be tested to destruction with one method (i.e., each piece cannot be broken twice), modeling these strengths distributions simultaneously can be challenging. In the past, this kind of problem has been solved by subjectively matching pieces of lumber, but the quality of this approach is then an issue. The objective of our analysis is to build a predictive model that relates the strength properties to the recorded characteristics. The paper concludes that type of wood defect (knot), a lumber grade status (off‐grade: yes/no), and a lumber's module of elasticity have statistically significant effects on wood strength. We find that the Weibull accelerated failure time model provides a better fit than the Cox proportional hazards model in our dataset. Copyright © 2016 John Wiley & Sons, Ltd.
Model selection of a switching mechanism for financial time series
Authors: Truong Buu‐Chau , Chen Cathy W. S. , So Mike K. P.
Published: September 2016

The threshold autoregressive model with generalized autoregressive conditionally heteroskedastic (GARCH) specification is a popular nonlinear model that captures the well‐known asymmetric phenomena in financial market data. The switching mechanisms of hysteretic autoregressive GARCH models are different from threshold autoregressive model with GARCH as regime switching may be delayed when the hysteresis variable lies in a hysteresis zone. This paper conducts a Bayesian model comparison among competing models by designing an adaptive Markov chain Monte Carlo sampling scheme. We illustrate the performance of three kinds of criteria by comparing models with fat‐tailed and/or skewed errors: deviance information criteria, Bayesian predictive information, and an asymptotic version of Bayesian predictive information. A simulation study highlights the properties of the three Bayesian criteria and the accuracy as well as their favorable performance as model selection tools. We demonstrate the proposed method in an empirical study of 12 international stock markets, providing evidence to strongly support for both models with skew fat‐tailed innovations. Copyright © 2016 John Wiley & Sons, Ltd.
The evolution of mating‐type switching for reproductive assurance
Authors: Nieuwenhuis Bart P. S. , Immler Simone
Published: September 2016

Alternative ways to ensure mate compatibility, such as hermaphroditism and the breakdown of self‐incompatibility, evolved repeatedly when finding a mating partner is difficult. In a variety of microorganisms where compatibility is determined by mating‐types, a highly regulated form of universal compatibility system called mating‐type switching has evolved several times. This sophisticated system allows for the genetic adjustment of the mating type during asexual growth, and it most likely evolved for reproductive assurance of immotile species under low densities. In this review, we compare the switching strategy to other universal compatibility systems such as “unisexual mating” and homothallism. We identify the costs of switching, including genome instability, and mechanistic costs, as well as the benefits, mainly the maintenance of important mating‐type functions. Given the potential benefits of mating‐type switching, we speculate that switching is likely to have evolved many times independently, and may be more common in groups where genetic mating types regulate mate compatibility than assumed so far.
Simultaneous determination of epalrestat and puerarin in rat plasma by UHPLC–MS/MS: Application to their pharmacokinetic interaction study
Authors: Sun Hong , Bo Yunhai , Zhang Mingjie , Wu Xiao , Zhou Mingyang , Zhao Longshan , Xiong Zhili
Published: September 2016

In the present study, a simple, rapid and reliable ultrahigh‐performance liquid chromatography–tandem mass spectrometric (UHPLC–MS/MS) method was developed and validated to determine simultaneously epalrestat (EPA) and puerarin (PUE) in rat plasma for evaluation of the pharmacokinetic interaction of these two drugs. Both the analytes and glipizide (internal standard, IS) were extracted using a protein precipitation method. The separation was performed on a C18 reversed phase column using acetonitrile and 5 mmol/L ammonium acetate in water as the mobile phase with a gradient elution program. The analytes, including IS, were quantified with multiple reaction monitoring under negative ionization mode. The optimized mass transition ion pairs (m/z) were 318.1 → 274.0 for EPA, 415.1 → 266.9 for PUE and 444.2 → 166.9 for IS. The linear calibration curves for EPA and PUE were obtained in the concentration ranges of 10–4167 and 20–8333 ng/mL, respectively (r > 0.99). The current method was successfully applied for the pharmacokinetic interaction study in rats following administration of EPA and PUE alone or co‐administration (EPA 15 mg/kg, oral; PUE 30 mg/kg, intravenous). The results showed that the combination of EPA and PUE could increase t1/2 of EPA and reduce Tmax of EPA. These changes indicated that EPA and PUE might cause drug–drug interactions when co‐administrated.
Recombinant canstatin inhibits VEGF‐A‐induced lymphangiogenesis and metastasis in an oral squamous cell carcinoma SCC‐VII animal model
Authors: Hwang‐Bo Jeon , Park Jong‐Hwa , Bae Mun Gyeong , Chung In Sik
Published: September 2016

We describe the inhibitory effects of recombinant canstatin on tumor growth and lymphangiogenesis induced by an oral squamous cell carcinoma (SCC) using an orthotropic oral SCC animal model. Recombinant canstatin treatment decreased final tumor volumes and weights, as well as densities of blood and lymphatic vessels. Lung metastasis of oral SCC was significantly reduced in recombinant canstatin‐treated animals. Recombinant canstatin reduced vascular endothelial growth factor (VEGF)‐A expression in SCC‐VII cells treated with the hypoxia mimetic agent, CoCl2. VEGF‐A induced in vivo lymphatic vessel formation in a Matrigel plug, but this was remarkably reduced in a recombinant canstatin‐treated Matrigel. Recombinant canstatin suppressed the expression of vascular endothelial growth factor receptors (VEGFR)‐1 and ‐2 stimulated by VEGF‐A. Based on immunohistochemical analysis, recombinant canstatin significantly reduced the expression of VEGF‐A, VEGFR‐1, and ‐2 in SCC‐VII‐induced tumors. Recombinant canstatin did not affect the expression of VEGF‐C or VEGFR‐3. In addition, recombinant canstatin suppressed the VEGF‐A‐induced phosphorylation of VEGFR‐1 and ‐2. Our results indicate that recombinant canstatin exhibits antitumoral and antilymphangiogenic activities against oral SCC cells. Antilymphangiogenic signaling by recombinant canstatin is probably mediated by the suppression of the integrin αvβ3/VEGFR‐1 and/or ‐2 signaling induced by VEGF‐A. Our results also suggest that recombinant canstatin has a high potential to inhibit oral SCC‐induced tumors and lymphatic metastasis.
Structure and Substrate Recognition of the Bottromycin Maturation Enzyme BotP
Authors: Mann Greg , Huo Liujie , Adam Sebastian , Nardone Brunello , Vendome Jeremie , Westwood Nicholas James , Müller Rolf , Koehnke Jesko
Published: September 2016

The bottromycins are a family of highly modified peptide natural products, which display potent antimicrobial activity against Gram‐positive bacteria, including methicillin‐resistant Staphylococcus aureus. Bottromycins have recently been shown to be ribosomally synthesized and post‐translationally modified peptides (RiPPs). Unique amongst RiPPs, the precursor peptide BotA contains a C‐terminal “follower” sequence, rather than the canonical N‐terminal “leader” sequence. We report herein the structural and biochemical characterization of BotP, a leucyl‐aminopeptidase‐like enzyme from the bottromycin pathway. We demonstrate that BotP is responsible for the removal of the N‐terminal methionine from the precursor peptide. Determining the crystal structures of both apo BotP and BotP in complex with Mn2+ allowed us to model a BotP/substrate complex and to rationalize substrate recognition. Our data represent the first step towards targeted compound modification to unlock the full antibiotic potential of bottro‐ mycin.
A Second, Druggable Binding Site in UDP‐Galactopyranose Mutase from Mycobacterium tuberculosis?
Authors: Shi Yun , Colombo Cinzia , Kuttiyatveetil Jijin R. A. , Zalatar Nataliya , van Straaten Karin E. , Mohan Sankar , Sanders David A. R. , Pinto B. Mario
Published: September 2016

UDP‐galactopyranose mutase (UGM), a key enzyme in the biosynthesis of mycobacterial cell walls, is a potential target for the treatment of tuberculosis. In this work, we investigate binding models of a non‐substrate‐like inhibitor, MS‐208, with M. tuberculosis UGM. Initial saturation transfer difference (STD) NMR experiments indicated a lack of direct competition between MS‐208 and the enzyme substrate, and subsequent kinetic assays showed mixed inhibition. We thus hypothesized that MS‐208 binds at an allosteric binding site (A‐site) instead of the enzyme active site (S‐site). A candidate A‐site was identified in a subsequent computational study, and the overall hypothesis was supported by ensuing mutagenesis studies of the A‐site. Further molecular dynamics studies led us to propose that MS‐208 inhibition occurs by preventing complete closure of an active site mobile loop that is necessary for productive substrate binding. The results suggest the presence of an A‐site with potential druggability, opening up new opportunities for the development of novel drug candidates against tuberculosis.
Impact of proton pump inhibitors and dual antiplatelet therapy cessation on outcomes following percutaneous coronary intervention: Results From the PARIS Registry
Authors: Chandrasekhar Jaya , Bansilal Sameer , Baber Usman , Sartori Samantha , Aquino Melissa , Farhan Serdar , Vogel Birgit , Faggioni Michela , Giustino Gennaro , Ariti Cono , Colombo Antonio , Chieffo Alaide , Kini Annapoorna , Saporito Richard , Michael Gibson C. , Witzenbichler Bernhard , Cohen David , Moliterno David , Stuckey Thomas , Henry Timothy , Pocock Stuart , Dangas George , Gabriel Steg P. , Mehran Roxana
Published: September 2016

Background

Proton pump inhibitors (PPI) may decrease the availability of clopidogrel by competitive antagonism, leading to a potential increase in ischemic events.

Methods

We evaluated patients from the all‐comer PARIS registry treated with dual antiplatelet therapy (DAPT) with aspirin and clopidogrel following coronary stenting for outcomes stratified by PPI use. Two‐year major adverse cardiovascular events (MACE), composite of cardiac death, myocardial infarction, definite or probable stent thrombosis or target lesion revascularization (TLR), and net adverse cardiac events (NACE), composite of MACE or Bleeding Academic Research consortium (BARC) type 3 or 5 bleeding were assessed. We also explored associations between PPI use and patterns of 2‐year DAPT cessation.

Results

The cohort comprised 4635 patients (23% PPI users) with mean age 64.4 ±11.4 years. Two year adjusted risk of MACE (HR: 1.27, 95% CI: 1.04–1.55), NACE (HR: 1.21, 95% CI: 1.01–1.44) and TLR (HR: 1.33, 95% CI: 1.04–1.71) were significantly higher in PPI users vs. non‐users, without a difference in bleeding. Although the incidence of 2‐year DAPT discontinuation and interruption was similar, DAPT disruption was significantly lower among PPI users vs. non‐users (10.0% vs. 14.7%, P <0.0001). Compared to non‐PPI users on continued DAPT, disruption was associated with higher MACE in both PPI users (HR: 2.34, 95% CI: 1.38–3.97) and non‐users (HR: 1.41, 95% CI: 1.02–1.94) but greater BARC 3,5 bleeding only in non‐PPI users (HR: 2.06, 95% CI: 1.21–3.51).

Conclusions

In clopidogrel treated PCI patients, the 2‐year adjusted risk of MACE and NACE was significantly higher in PPI users driven by higher TLR compared to non‐PPI users, without a difference in bleeding. PPI use was associated with lower incidence of DAPT disruption without an increase in disruption related bleeding compared to non‐PPI users on DAPT. © 2016 Wiley Periodicals, Inc.
Clinical outcomes of percutaneous coronary intervention in patients turned down for surgical revascularization
Authors: Sukul Devraj , Seth Milan , Dixon Simon R. , Zainea Mark , Slocum Nicklaus K. , Pielsticker Elizabeth J. , Gurm Hitinder S.
Published: September 2016

Objectives

We examined clinical outcomes following percutaneous coronary intervention (PCI) in patients turned down for surgical revascularization across a broad population.

Background

Prior studies suggest that surgical ineligibility is associated with increased mortality in patients with unprotected left main or multivessel coronary artery disease undergoing PCI.

Methods

This study included consecutive patients who underwent PCI in a multicenter registry in Michigan from January 2010 to December 2014. Surgical ineligibility required documentation indicating that a cardiac surgeon deemed the patient ineligible for surgery. In‐hospital outcomes included mortality (primary outcome), cardiogenic shock, cerebrovascular accident, contrast‐induced nephropathy (CIN), and a new requirement for dialysis (NRD).

Results

Of 99,370 patients at 33 hospitals with on‐site surgical backup, 1,922 (1.9%) were surgically ineligible. The rate of ineligibility did not vary by hospital (range: 1.5–2.5%; P = 0.79). Overall, there were no major differences in baseline characteristics or outcomes between surgically ineligible patients and the rest (i.e., nonineligible patients): mortality (0.52% vs. 0.52%; P > 0.5), cardiogenic shock (0.68% vs. 0.73%; P > 0.5), cerebrovascular accident (0.05% vs. 0.19%; P = 0.28), NRD (0.16% vs. 0.19%; P > 0.5), CIN (2.7% vs. 2.3%; P = 0.27). Among 1,074 patients who underwent unprotected left main PCI, 20 (1.9%) were surgically ineligible and experienced increased rates of mortality (20.0% vs. 5.3%; P = 0.022; adjusted OR = 7.38; P < 0.001) and other complications as compared to the remainder.

Conclusions

PCI in a broad population of surgically ineligible patients is generally safe. However, among patients who underwent unprotected left main PCI, those deemed surgically ineligible experienced significantly worse outcomes as compared to the rest. © 2016 Wiley Periodicals, Inc.
Chemoselective Transfer Hydrogenation of Aldehydes with HCOONH4 Catalyzed by RuCl(CNNPh)(PP) Pincer Complexes
Authors: Baldino Salvatore , Facchetti Sarah , Nedden Hans Günter , Zanotti‐Gerosa Antonio , Baratta Walter
Published: September 2016

Aldehydes were chemoselectively reduced to primary alcohols by using HCOONH4 as the hydrogen donor through transfer hydrogenation catalyzed by benzo[h]quinoline pincer complexes RuCl(CNNPh)(PP) at substrate to catalyst molar ratios of 2000 to 20 000. This practical reaction performed with aldehydes of commercial‐grade purity in a water/toluene biphasic system afforded alcohols without the formation of condensation or amination side products.
Preparation of a New Carbon Nanofiber as a High‐Capacity Air Electrode for Nonaqueous Lithium–Oxygen Batteries
Authors: Xu Chunyang , Dai Jicui , Teng Xiangguo , Zhu Yongming
Published: September 2016

A new carbon nanofiber codoped with nitrogen and phosphorus (NPCNF) that has a high specific surface area and good electrocatalytic properties for the oxygen reduction reaction (ORR) was synthesized using a template‐free method. The fabrication process involves the pyrolysis of phytic acid doped polyaniline aerogel. A nonaqueous Li‐O2 battery with a specific capacity as high as 12 607 mA h g−1 was constructed by using an oxygen electrode based on NPCNFs supported by Ni foam. The NPCNF electrode showed a lower overpotential than pure carbon. The observed excellent electrochemical performance could be because of the unique foamlike N‐ and P‐codoped carbon microstructure, which had a high ORR catalytic activity. These results indicate that the use of NPCNF as a cathode material could be a feasible approach to obtain a high‐capacity Li–O2 battery.
Electrochemical Impedance Spectroscopy at Well‐Controlled dc Bias for Nanoporous Platinum Microelectrodes in Rat Embryo Brain
Authors: Kim Beom Jin , Kim Yang‐Rae , Seo Minjee , Kim Eun Joong , Jeon Joohee , Chung Taek Dong
Published: September 2016

Nanoporous Pt with extremely small (1–2 nm) and uniform nanopores, L2‐ePt, is electrochemically investigated in rat embryo brain. In a comparative study under precise control of electrochemical potential, an electrochemical cell beneath the brain surface is constructed by introducing flat and nanoporous Pt twisted wires around which Ag/AgCl is wound. L2‐ePt and flat Pt in the brain are compared with each other by conventional voltammetry and electrochemical impedance spectroscopy at the dc bias, which is carefully selected to minimize faradaic interference. The electrochemical behavior at L2‐ePt implanted into embryo brain is immune to severe passivation and is closer to an ideal capacitor than flat Pt. A lower electrode impedance of L2‐ePt leads to less potential drop at the interface between the electrode and the extracellular solution, protecting the implanted system from unwanted faradaic reactions. Various aspects, including the low electrode impedance and electrochemical stability in embryo brain, suggest that L2‐ePt is a promising electrode material for effectively stimulating distant neuronal cells and recording local field potential signals.
Dynamical Bifurcation in Gas‐Phase XH− + CH3Y SN2 Reactions: The Role of Energy Flow and Redistribution in Avoiding the Minimum Energy Path
Authors: Proenza Yaicel G. , de Souza Miguel A. F. , Longo Ricardo L.
Published: September 2016

The gas‐phase reactions of XH− (X=O, S) + CH3Y (Y=F, Cl, Br) span nearly the whole range of SN2 pathways, and show an intrinsic reaction coordinate (IRC) (minimum energy path) with a deep well owing to the CH3XH⋅⋅⋅Y− (or CH3S−⋅⋅⋅HF) hydrogen‐bonded postreaction complex. MP2 quasiclassical‐type direct dynamics starting at the [HX⋅⋅⋅CH3⋅⋅⋅Y]− transition‐state (TS) structure reveal distinct mechanistic behaviors. Trajectories that yield the separated CH3XH+Y− (or CH3S−+HF) products directly are non‐IRC, whereas those that sample the CH3XH⋅⋅⋅Y− (or CH3S−⋅⋅⋅HF) complex are IRC. The IRCIRC/non‐IRC ratios of 90:10, 40:60, 25:75, 2:98, 0:100, and 0:100 are obtained for (X, Y)=(S, F), (O, F), (S, Cl), (S, Br), (O, Cl), and (O, Br), respectively. The properties of the energy profiles after the TS cannot provide a rationalization of these results. Analysis of the energy flow in dynamics shows that the trajectories cross a dynamical bifurcation, and that the inability to follow the minimum energy path arises from long vibration periods of the X−C⋅⋅⋅Y bending mode. The partition of the available energy to the products into vibrational, rotational, and translational energies reveals that if the vibrational contribution is more than 80 %, non‐IRC behavior dominates, unless the relative fraction of the rotational and translational components is similar, in which case a richer dynamical mechanism is shown, with an IRC/non‐IRC ratio that correlates to this relative fraction.
Selective P4 Activation by a Highly Reduced Cobaltate: Synthesis of Dicobalt Tetraphosphido Complexes
Authors: Pelties Stefan , Maier Thomas , Herrmann Dirk , de Bruin Bas , Rebreyend Christophe , Gärtner Stefanie , Shenderovich Ilya G. , Wolf Robert
Published: September 2016

Although the chemistry of transition metal polyphosphide anions has attracted significant attention, there are few reports of studies in which such species have been synthesized directly from white phosphorus. [K(OEt2)2{Co(BIAN)(cod)}] (1, BIAN=1,2‐bis(2,6‐diisopropylphenylimino)acenaphthene, cod=1,5‐cyclooctadiene), which is readily prepared by ligand exchange from [K(thf)x{Co(cod)2}], reacts with P4 to afford [{K(thf)}2{(BIAN)Co}2(μ‐η4:η4‐P4)] (2 a) in 61 % yield (isolated product). [{K(OEt2)}2{(BIAN)Co}2(μ‐η4:η4‐P4)] (2 b) and [K([18]crown‐6)(MeCN)]2[{(BIAN)Co}2(μ‐η4:η4‐P4)] (2 c) were obtained by recrystallizing 2 a from diethyl ether and acetonitrile (and using [18]crown‐6 in case of 2 c). Oxidation of 2 a with [Cp2Fe]BArF4 (one equivalent) and subsequent recrystallization of the product from different solvents gave [K(OEt2){(BIAN)Co}2(μ‐η4:η4‐P4)] (3 a) and [K(dme)4][{(BIAN)Co}2(μ‐η4:η4‐P4)] (3 b; dme=1,2‐dimethoxyethane). Neutral [{(BIAN)Co}2(μ‐η4:η4‐P4)] (4) was obtained in moderate yield by oxidizing 2 a with two equivalents of [Cp2Fe]BArF4. The new complexes were characterized by NMR, EPR (in the case of 3 a), and UV/Vis spectroscopy, and elemental analysis. The molecular structures revealed by X‐ray crystallography display planar cyclic or open‐chain P44− units sandwiched between {(BIAN)Co} fragments.
The Copper(II)‐Catalyzed Oxidation of Glutathione
Authors: Ngamchuea Kamonwad , Batchelor‐McAuley Christopher , Compton Richard G.
Published: September 2016

The kinetics and mechanisms of the copper(II)‐catalyzed GSH (glutathione) oxidation are examined in the light of its biological importance and in the use of blood and/or saliva samples for GSH monitoring. The rates of the free thiol consumption were measured spectrophotometrically by reaction with DTNB (5,5′‐dithiobis‐(2‐nitrobenzoic acid)), showing that GSH is not auto‐oxidized by oxygen in the absence of a catalyst. In the presence of Cu2+, reactions with two timescales were observed. The first step (short timescale) involves the fast formation of a copper–glutathione complex by the cysteine thiol. The second step (longer timescale) is the overall oxidation of GSH to GSSG (glutathione disulfide) catalyzed by copper(II). When the initial concentrations of GSH are at least threefold in excess of Cu2+, the rate law is deduced to be −d[thiol]/dt=k[copper–glutathione complex][O2]0.5[H2O2]−0.5. The 0.5th reaction order with respect to O2 reveals a pre‐equilibrium prior to the rate‐determining step of the GSSG formation. In contrast to [Cu2+] and [O2], the rate of the reactions decreases with increasing concentrations of GSH. This inverse relationship is proposed to be a result of the competing formation of an inactive form of the copper–glutathione complex (binding to glutamic and/or glycine moieties).
General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand
Authors: Erbing Elis , Vázquez‐Romero Ana , Bermejo Gómez Antonio , Platero‐Prats Ana E. , Carson Fabian , Zou Xiaodong , Tolstoy Päivi , Martín‐Matute Belén
Published: September 2016

Remarkably simple IrIII catalysts enable the isomerization of primary and sec‐allylic alcohols under very mild reaction conditions. X‐ray absorption spectroscopy (XAS) and mass spectrometry (MS) studies indicate that the catalysts, with the general formula [Cp*IrIII], require a halide ligand for catalytic activity, but no additives or additional ligands are needed.
Motoneuron glutamatergic receptor expression following recovery from cervical spinal hemisection
Authors: Gransee Heather M. , Gonzalez Porras Maria A. , Zhan Wen‐Zhi , Sieck Gary C. , Mantilla Carlos B.
Published: September 2016

Cervical spinal hemisection at C2 (SH) removes premotor drive to phrenic motoneurons located in segments C3–C5 in rats. Spontaneous recovery of ipsilateral diaphragm muscle activity is associated with increased phrenic motoneuron expression of glutamatergic N‐methyl‐D‐aspartate (NMDA) receptors and decreased expression of α‐amino‐3‐hydroxy‐5‐methylisoxazole‐4‐proprionic acid (AMPA) receptors. Glutamatergic receptor expression is regulated by tropomyosin‐related kinase receptor subtype B (TrkB) signaling in various neuronal systems, and increased TrkB receptor expression in phrenic motoneurons enhances recovery post‐SH. Accordingly, we hypothesize that recovery of ipsilateral diaphragm muscle activity post‐SH, whether spontaneous or enhanced by adenoassociated virus (AAV)‐mediated upregulation of TrkB receptor expression, is associated with increased expression of glutamatergic NMDA receptors in phrenic motoneurons. Adult male Sprague‐Dawley rats underwent diaphragm electromyography electrode implantation and SH surgery. Rats were injected intrapleurally with AAV expressing TrkB or GFP 3 weeks before SH. At 14 days post‐SH, the proportion of animals displaying recovery of ipsilateral diaphragm activity increased in AAV–TrkB‐treated (9/9) compared with untreated (3/5) or AAV–GFP‐treated (4/10; P < 0.027) animals. Phrenic motoneuron NMDA NR1 subunit mRNA expression was approximately fourfold greater in AAV–TrkB‐ vs. AAV–GFP‐treated SH animals (P < 0.004) and in animals displaying recovery vs. those not recovering (P < 0.005). Phrenic motoneuron AMPA glutamate receptor 2 (GluR2) subunit mRNA expression decreased after SH, and, albeit increased in animals displaying recovery vs. those not recovering, levels remained lower than control. We conclude that increased phrenic motoneuron expression of glutamatergic NMDA receptors is associated with spontaneous recovery after SH and enhanced recovery after AAV–TrkB treatment. J. Comp. Neurol. 525:1192–1205, 2017. © 2016 Wiley Periodicals, Inc.
Outer synchronization between two hybrid‐coupled delayed dynamical networks via aperiodically adaptive intermittent pinning control
Authors: Cai Shuiming , Lei Xuqiang , Liu Zengrong
Published: September 2016

This article is concerned with the problem of pinning outer synchronization between two complex delayed dynamical networks via adaptive intermittent control. At first, a general model of hybrid‐coupled dynamical network with time‐varying internal delay and time‐varying coupling delay is given. Then, an aperiodically adaptive intermittent pinning‐control strategy is introduced to drive two such delayed dynamical networks to achieve outer synchronization. Some sufficient conditions to guarantee global outer‐synchronization are derived by constructing a novel piecewise Lyapunov function and utilizing stability analytical method. Moreover, a simple pinned‐node selection scheme determining what kinds of nodes should be pinned first is provided. It is noted that the adaptive pinning control type is aperiodically intermittent, where both control period and control width are non‐fixed. Finally, a numerical example is given to illustrate the validity of the theoretical results. © 2016 Wiley Periodicals, Inc. Complexity 21: 593–605, 2016
Disclosing the High Activity of Ceramic Metallics in the Oxygen Evolution Reaction: Nickel Materials as a Case Study
Authors: Ledendecker Marc , Yang Xiaofei , Antonietti Markus , Shalom Menny
Published: September 2016

Here, we elucidate the activity origin of ceramic nickel electrocatalysts in the oxygen evolution reaction (OER), ranging from nitrides, sulfides, and phosphides, as a case study that may be projected on almost any ceramic metallic. Our results show that regardless of the starting material, the formation of an active (oxy)hydroxide layer, acting as the real electrocatalyst during the OER, is unavoidable. Nevertheless, the in situ transformation into highly active (oxy)hydroxides leads to the formation of active catalysts for various applications.
Fractional‐order electronically controlled generalized filters
Authors: Tsirimokou Georgia , Psychalinos Costas , Elwakil Ahmed S.
Published: September 2016

Novel topologies of fractional‐order generalized filters are introduced in this paper. These offer the following benefits: (1) realization of lowpass, highpass, bandpass, allpass, or bandstop filter functions by the same topology; (2) resistorless realizations; (3) electronic adjustment of their frequency characteristics as well as their order; and (4) employment of only grounded capacitors. All the above have been achieved using Operational Transconductance Amplifiers as active elements and appropriate multi‐feedback topologies. The behavior of the proposed designs is verified through simulation results using the Cadence IC design suite and the Design Kit provided by the Austrian Micro Systems 0.35‐µm complementary metal–oxide–semiconductor process. Copyright © 2016 John Wiley & Sons, Ltd.
Analysis and improvement of the Internet‐Draft IKEv3 protocol
Authors: Cheng Qingfeng , Lu Siqi , Ma Jianfeng
Published: September 2016

Internet protocol (IP) is the kernel of the TCP/IP protocol family. Because IP is the only one that is shared by all high‐level protocols in TCP/IP. So the security of the IP is particularly important to the whole communication network. Fortunately, IPsec provides excellent protection for the kIP security. As a part of the IPsec, Internet Key Exchange (IKE) protocol can achieve security association negotiation, key generation, and identity authentication. The study of IKEv2, both in its application and security analysis, has been relatively mature. When the Internet Engineering Task Force published the Internet‐Draft IKEv3 protocol, there is not much attention and research on it. In this paper, we analyze the security and authentication of IKEv3 by formal verification and show that IKEv3 is susceptible to reflection attack and DoS attack. Then we propose a new variant of the IKEv3 protocol, which both resists reflection attack and mitigates the impact of the DoS attack.
Rapid and sensitive screening and confirmation of thirty‐four aminocarbonyl/carboxamide (NACA) and arylindole synthetic cannabinoid drugs in human whole blood
Authors: Tynon Marykathryn , Homan Joseph , Kacinko Sherri , Ervin Annette , McMullin Matthew , Logan Barry K.
Published: September 2016

We describe the development and validation of a method for the screening and confirmation of a range of chemically diverse synthetic cannabinoid drugs in human whole blood. The method targets the better known arylindole compounds as well as the emerging aminocarbonyl/ carboxamide (NACA) compounds. The approach consists of two separate extraction procedures designed to optimize recovery of each of these two classes, followed by analysis by liquid chromatography‐tandem mass spectrometry (LC‐MS/MS). The most significant novel compounds added were AB‐FUBINACA, ADBICA, 5 F‐ADBICA, ADB‐PINACA, ADB‐FUBINACA, ADB‐FUBINACA, 5 F‐ADB‐PINACA, 5 F‐ADB‐PINACA, AB‐PINACA, AB‐CHMINACA, and ADB‐CHMINACA. A third procedure is described for the quantitative confirmation of those compounds for which deuterated internal standards permitted quantitative analysis, including JWH‐018, JWH‐122, JWH‐081, JWH‐210, AM‐2201, XLR‐11, and UR‐144. The methods were successfully validated according to Scientific Working Group in Forensic Toxicology (SWGTOX) protocol for 34 compounds in common use in the United States in the period of 2014 and 2015, although other substances, unknown at the time may have been introduced to the market over the same time period. The method was determined to be free from carry‐over between samples, and no interference was found from other common therapeutic abused or novel psychoactive drugs. The methods were applied to the analysis of 1142 blood samples from forensic investigations, including post‐mortem examinations and driving impairment cases. The drugs most frequently detected were AB‐CHMINACA (18.6%), ADB‐CHMINACA (15%), XLR‐11 (5.5%), AB‐FUBINACA (4.5%), AB‐PINACA (3.9%), and ADB‐FUBINACA (2.3%). Copyright © 2016 John Wiley & Sons, Ltd.
Invasion in patchy landscapes is affected by dispersal mortality and mate‐finding failure
Authors: Walter Jonathan A. , Firebaugh Ariel L. , Tobin Patrick C. , Haynes Kyle J.
Published: September 2016

Range expansions are a function of population growth and dispersal, and nascent populations often must overcome demographic Allee effects (positive density dependence at low population densities) driven by factors such as mate‐finding failure. Given the importance of individual movement to mate finding, links between landscape structure and movement may be critical to range expansion; however, landscape effects on other factors including mortality may be equally or more important. In one of the most comprehensive investigations of the interactions of these processes to date, we combined field experiments, simulation modeling, and analysis of empirical spread patterns to investigate how landscape structure affected the spread of the gypsy moth in Virginia and West Virginia. In experiments designed to assess how landscape attributes affect mate finding, we found adult males resisted leaving forest patches and the probability of locating a pheromone source declined more rapidly over distance in non‐forest matrix than in forest. We used these findings to develop individual‐based simulation models of gypsy moth population dynamics and spread in complex patch‐matrix landscapes. The models produced an Allee effect that strengthened with reductions in forested area, but owing more so to dispersal mortality than to effects on mate location. Predicted maximum rates of population spread grew with increases in forest area due to increasing success of long‐distance transport events. Evaluations of empirical data showed relationships between spread rates and landscape structure largely consistent with model predictions. We conclude rates of spread were largely driven by long‐distance dispersal events, the success of which was influenced primarily by dispersal mortality of larvae in unsuitable matrix, and that landscape effects on mate location played a secondary role. Though influences of landscape structure on mate location appear to be unimportant to the spread of the gypsy moth, we predict they would have stronger effects on more dispersive species.
Gemcitabine induced cardiomyopathy: a case of multiple hit cardiotoxicity
Authors: Mohebali Donya , Matos Jason , Chang James Ducksoon
Published: September 2016

Gemcitabine is a commonly used antineoplastic agent used to treat a variety of cancers with rarely reported cardiac side effects. We describe a case of a 67‐year‐old woman with follicular lymphoma who experienced a rarely reported side effect of gemcitabine: cardiomyopathy. This case highlights a multiple hit mechanism of myocyte damage that may occur following the use of multiple cardio‐toxic agents despite their administration in doses not associated with cardiotoxicity.
Platinum Complexes Bearing a Tripodal Germyl Ligand
Authors: Herrmann Roy , Wittwer Philipp , Braun Thomas
Published: September 2016

The reaction of the germane [Ge(H)(2‐C6H4PPh2)3] (1) and the platinum precursor complex [Pt(nbe)3] (nbe = norbornene) gave a racemic mixture of the germyl complex [Pt(nor){Ge(2‐C6H4PPh2)3}] (2; nor =exo‐2‐norbornyl,exo‐2‐bicyclo[2.2.1]heptyl). Mechanistic studies showed that the hydrido complex [Pt(H){Ge(2‐C6H4PPh2)3}] (3) is not formed as an intermediate during the formation of2. Further studies revealed that in contrast to the chlorido complex [Pt(Cl){Ge(2‐C6H4PPh2)3}] (4), the methyl compound [Pt(CH3){Ge(2‐C6H4PPh2)3}] (5) is an efficient starting compound for accessing cationic platinum species. Complex5was converted into the triflato complex [Pt(OTf){Ge(2‐C6H4PPh2)3}] (6) as well as the complexes [Pt(L){Ge(2‐C6H4PPh2)3}][B{3,5‐C6H3(CF3)2}4] [L = thf (7), toluene (8), CH2Cl2(9), PPh3(10)].
Versatile Electrochemical Platform for the Determination of Phenol‐like Compounds Based on Laccases from Different Origins
Authors: Borón Ignacio , Wirth Sonia , Battaglini Fernando
Published: September 2016

Simple and fast methods for the monitoring of phenol‐like compounds are relevant in diverse fields ranging from waste management to neurosciences. Laccases are copper‐containing enzymes, which, depending on their origin, are able to oxidize different phenol compounds at different pH conditions. Through adequate laccase immobilization, disposable screen printed electrodes can be used as interphase to build amperometric phenol sensors. In this work three different laccases were studied for the determination of phenol‐like compounds, two of them are isoenzymes from Trametes trogii and the third one from Rhus vernicifera. Their immobilization on screen printed electrodes is presented for the construction of amperometric sensors. The electrode substrate is composed by graphite screen printed electrodes modified with carbon nanotubes and silica microspheres where, depending on the application, one of the three laccases is adsorbed. As each laccase shows an optimum working pH, they were conveniently selected to determine dopamine at physiological pH and catechol at acid pH. Determinations in the micromolar range were possible in both cases. Chronoamperometry shows to be an effective technique for their determinations, simpler than other electrochemical methods already presented in the literature.
Boron and Nitrogen Doped Graphene via Microwave Exfoliation for Simultaneous Electrochemical Detection of Ascorbic Acid, Dopamine and Uric Acid
Authors: Thearle Rozi Alice , Latiff Naziah Mohamad , Sofer Zdenek , Mazánek Vlastimil , Pumera Martin
Published: September 2016

Boron and nitrogen doped graphenes show opposite effect on the electronic structure, one with electron withdrawing and another one with electron donating effects. It is of high importance to investigate the influence of B or N doping on biomarkers detection and compare it to non‐doped graphene. Here we show that B‐doped graphene shows significant enhancement in detection currents in the cyclic voltammetry of the above mentioned compounds.
Heteroatom Doping Combined with Microstructured Carbon to Enhance the Performance of Sodium‐Ion Batteries
Authors: Liu Yang , Gao Zhiqiang
Published: September 2016

A simple and effective procedure for the synthesis of nitrogen (N) and sulfur (S) co‐doped carbon accompanied by the formation of favorable microstructure is developed. The synthesized N and S co‐doped carbon materials are thoroughly investigated by electron microscopy, X‐ray diffractometry, X‐ray photoelectron spectroscopy, and nitrogen adsorption measurements. When applied as anodes in sodium‐ion batteries, high sodium storage capacities and excellent cyclic stability are obtained. It is observed that the contents of N and S atoms and the microstructure of the carbon have a significant effect on the performance of sodium‐ion battery. Under optimized synthetic conditions, the N and S co‐doped carbon materials have a specific capacity of 287.2 mA h g−1 in the second cycle and a stable specific capacity of 232.6 mA h g−1 even after 500 cycles at 0.5 A g−1. Moreover, the simple and facile procedure can be conventionally adopted for the preparation of other heteroatom‐doped carbon materials.
High‐performance Li‐ion Battery based on Cr‐Substituted Lithium Manganite and Lithium Titanate Spinels: Influence of Mass Balance on its Electrochemistry
Authors: Aklalouch Mohamed , Amarilla José Manuel , Rojo José María , Solhy Abderrahim , Rojas Rosa María , Saadoune Ismael
Published: September 2016

The influence of mass balance in the LiCr0.2Ni0.4Mn1.4O4//Li4Ti5O12 (LCrNMO//LTO) full cell on its electrochemical performance at different rates is described. The effect of the variation of the molar fraction of LTO to LCrNMO (χ) at different rates is described in detail. The full cell showed a reversible working potential at about 3 V. For every rate tested, the discharge capacity, normalized to total mass of both electrode materials (Qdch), reached a maximum value approximately at the stoichiometric value of χ=1. When χ<1, Qdch is limited by an incomplete electrochemical reaction of the LCrNMO cathode and when χ>1 Qdch decreases due to the increase in the total weight of active electrode materials. When the discharge rates were increased to ≥1 C (1 C=147.5 mA g−1 or 0.260 mA cm−2), the maximum Qdch delivered by the full cell was shifted slightly beyond the stoichiometry (χ=1.1). Furthermore, the LCrNMO//LTO full cell exhibited an outstanding ultralong cycling behavior: with a capacity retention of 93 % after 1000 cycles. Its cyclability is as high as 99.994 %. The LiCrNMO//LTO full cell is a promising lithium‐ion battery for practical applications, especially for plug‐in hybrid electric vehicles, for which a long cycle life and reasonable power are required. However, it is demonstrated that the optimization of anode to cathode materials is one of the most important parameters to take into account to achieve high energy and power densities.