bluuebunny/crossref_metadata_2025 huggingface dataset:
Free‐Energy Landscape and Proton Transfer Pathways in Oxidative Deamination by Methylamine Dehydrogenase
Authors: Zelleke Theodros , Marx Dominik
Published: November 2016

The rate‐determining step in the reductive half‐reaction of the bacterial enzyme methylamine dehydrogenase, which is proton abstraction from the native substrate methylamine, is investigated using accelerated QM/MM molecular dynamics simulations at room temperature. Generation of the multidimensional thermal free‐energy landscape without restriction of the degrees of freedom beyond a multidimensional reaction subspace maps two rather similar pathways for the underlying proton transfer to one of two aspartate carboxyl oxygen atoms, termed OD1 and OD2, which hydrogen bond with Thr122 and Trp108, respectively. Despite significant large‐amplitude motion perpendicular to the one‐dimensional proton transfer coordinate, due to fluctuations of the donor–acceptor distance of about 3 Å, it is found that the one‐dimensional proton transfer free‐energy profiles are essentially identical to the minimum free‐energy pathways on the multidimensional free‐energy landscapes for both proton transfer channels. Proton transfer to one of the acceptor oxygen atoms—the OD2 site—is slightly favored in methylamine dehydrogenase by approximately 2 kcal mol−1, both kinetically and thermodynamically. Mechanistic analyses reveal that the hydrogen bond between Thr122β and OD1 is always present in the transition state independently of the proton transfer channel. Population analysis confirms that the electronic charge gained upon oxidation of the substrate is delocalized within the ring systems of the tryptophan tryptophylquinone cofactor.
Proton‐Gated Photoisomerization of Amino‐Substituted Dibenzofulvene Rotors
Authors: Jayasundara Udaya K. , Kim HyunJong , Sahteli Krishna P. , Cline Joseph I. , Bell Thomas W.
Published: November 2016

Derivatives of 9‐(2,2,2‐triphenylethylidene)‐fluorene (TEF) undergo E/Z photoisomerization and are candidates for light‐powered molecular actuators and switches. The 2‐substituted derivatives bearing an amino group (ATEF) or a dimethylamino group (DTEF) are weakly photoactive in the absence of acids, but protonation increases photoisomerization quantum yields by factors of 30–60. Such compounds may be useful for incorporation into pH‐switchable photoactive devices.
Flexible Metal–Porphyrin Dimers (M=MnIIICl, CoII, NiII, CuII): Synthesis, Spectroscopy, Electrochemistry, Spectroelectrochemistry, and Theoretical Calculations
Authors: Li Minzhi , Zhang Qian , Xu Li , Zhu Weihua , Mack John , May Aviwe K. , Nyokong Tebello , Kobayashi Nagao , Liang Xu
Published: November 2016

Four metalloporphyrin dimers linked by bridging amide‐bonded xanthene moieties and that contain either MnIII, CoII, NiII, or CuII metal centers were synthesized. Various spectroscopic, electrochemical, and spectroelectrochemical methods were used to study trends in their properties. Their electronic structure and optical properties were analyzed through a comparison of the electronic absorption and magnetic circular dichroism (MCD) spectral data with the results of time‐dependent (TD)‐DFT calculations.
Adaptive Biomedical Innovation
Authors: Honig PK , Hirsch G
Published: November 2016

Adaptive Biomedical Innovation (ABI) is a multistakeholder approach to product and process innovation aimed at accelerating the delivery of clinical value to patients and society. ABI offers the opportunity to transcend the fragmentation and linearity of decision‐making in our current model and create a common collaborative framework that optimizes the benefit and access of new medicines for patients as well as creating a more sustainable innovation ecosystem.
Fast Degradation for High Activity: Oxygen‐ and Nitrogen‐Functionalised Carbon Nanotubes in Solid‐Acid Fuel‐Cell Electrodes
Authors: Naumov Olga , Naumov Sergej , Flyunt Roman , Abel Bernd , Varga Aron
Published: November 2016

Similar to polymer electrolyte membrane fuel cells, the widespread application of solid acid fuel cells (SAFCs) has been hindered partly by the necessity of the use of the precious‐metal catalyst Pt in the electrodes. Here we investigate multi‐walled carbon nanotubes (MWCNTs) for their potential catalytic activity by using symmetric cell measurements of solid‐acid‐based electrochemical cells in a cathodic environment. For all measurements, the carbon nanotubes were Pt free and subject to either nitrogen or oxygen plasma treatment. AC impedance spectroscopy of the electrochemical cells, with and without a DC bias, was performed and showed significantly lower initial impedances for oxygen‐plasma‐treated MWCNTs compared to those treated with a nitrogen plasma. In symmetric cell measurements with a DC bias, the current declines quickly for oxygen‐plasma‐treated MWCNTs and more slowly, over 12 days, for nitrogen‐plasma‐treated MWCNTs. To elucidate the degradation mechanisms of the oxygen‐plasma‐treated MWCNTs under SAFC operating conditions, theoretical calculations were performed using DFT. The results indicate that several degradation mechanisms are likely to occur in parallel through the reduction of the surface oxygen groups that were introduced by the plasma treatment. This finally leads to an inert MWCNT surface and a very low electrode performance. Nitrogen‐plasma‐treated MWCNTs appear to have a higher stability and may be worthwhile for future investigations.
Graphite Recycling from Spent Lithium‐Ion Batteries
Authors: Rothermel Sergej , Evertz Marco , Kasnatscheew Johannes , Qi Xin , Grützke Martin , Winter Martin , Nowak Sascha
Published: November 2016

The present work reports on challenges in utilization of spent lithium‐ion batteries (LIBs)—an increasingly important aspect associated with a significantly rising demand for electric vehicles (EVs). In this context, the feasibility of anode recycling in combination with three different electrolyte extraction concepts is investigated. The first method is based on a thermal treatment of graphite without electrolyte recovery. The second method additionally utilizes a subcritical carbon‐dioxide (subcritical CO2)‐assisted electrolyte extraction prior to thermal treatment. And the final investigated approach uses supercritical carbon dioxide (scCO2) as extractant, subsequently followed by the thermal treatment. It is demonstrated that the best performance of recycled graphite anodes can be achieved when electrolyte extraction is performed using subcritical CO2. Comparative studies reveal that, in the best case, the electrochemical performance of recycled graphite exceeds the benchmark consisting of a newly synthesized graphite anode. As essential efforts towards electrolyte extraction and cathode recycling have been made in the past, the electrochemical behavior of recycled graphite, demonstrating the best performance, is investigated in combination with a recycled LiNi1/3Co1/3Mn1/3O2 cathode.
Characterization of a BODIPY Dye as an Active Species for Redox Flow Batteries
Authors: Kosswattaarachchi Anjula M. , Friedman Alan E. , Cook Timothy R.
Published: November 2016

An all‐organic redox flow battery (RFB) employing a fluorescent boron‐dipyrromethene (BODIPY) dye (PM567) was investigated. In a RFB, the stability of the electrolyte in all charged states is critically linked to coulombic efficiency. To evaluate stability, bulk electrolysis and cyclic voltammetry (CV) experiments were performed. Oxidized and reduced, PM567 does not remain intact; however, the products of bulk electrolysis evolve over time to show stable redox behavior, making the dye a precursor for the active species of an RFB. A theoretical cell potential of 2.32 V was predicted from CV experiments with a working discharge voltage of approximately 1.6 V in a static test cell. Mass spectrometry was used to identify the products of bulk electrolysis. Related experiments were carried out using ferrocene and cobaltocenium hexafluorophosphate as redox‐stable benchmarks to further explain the stability results. The coulombic efficiency of a model cell using PM567 as a precursor for charge carriers stabilized around 73 %.
Organocatalytic Coupling of CO2 with Oxetane
Authors: Alves Margot , Grignard Bruno , Boyaval Amélie , Méreau Raphael , De Winter Julien , Gerbaux Pascal , Detrembleur Christophe , Tassaing Thierry , Jérôme Christine
Published: November 2016

The organocatalytic coupling of CO2 with oxetanes is investigated under solvent‐free conditions. The influence of the main reaction parameters (type of organocatalytic system, pressure, and temperature) on the yield, the product formed, and the selectivity of the reaction are discussed. An onium salt combined with a fluorinated alcohol promotes the efficient and selective organocatalytic synthesis of α,ω‐hydroxyl oligocarbonates by coupling CO2 with oxetanes at 130 °C and at a CO2 pressure as low as 2 MPa. NMR characterizations were correlated with matrix‐assisted laser desorption/ionization with time‐of‐flight mass spectrometer (MALDI‐TOF) analyses for elucidating the structure of the oligomers. Online FTIR studies under pressure, NMR titrations, and DFT calculations allowed an in‐depth understanding of the reaction mechanism. Finally, CO2‐based poly(carbonate‐co‐urethane)s were synthesized by step‐growth polymerization of hydroxyl telechelic oligocarbonates with 4,4′‐methylene diphenyl diisocyanate (MDI). The organocatalytic system described herein constitutes an innovative sustainable route to the selective preparation of hydroxyl telechelic carbonates of high interest for many applications, notably for the polyurethane business (especially for coatings or foams).
Carbocation/Polyol Systems as Efficient Organic Catalysts for the Preparation of Cyclic Carbonates
Authors: Rulev Yuri A. , Gugkaeva Zalina T. , Lokutova Anastasia V. , Maleev Victor I. , Peregudov Alexander S. , Wu Xiao , North Michael , Belokon Yuri N.
Published: November 2016

Carbocation/polyol systems are shown to be highly efficient catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide at 50 °C and 5 MPa CO2 pressure. The best activity was shown by the combination of crystal violet and 1,1′‐bi‐2‐naphthol (BINOL), which could be recycled five times with no loss of activity. The presence of specific interactions between the amino groups of the carbocation and the hydroxyl protons was confirmed by NMR experiments. The Job plots for the crystal violet iodide/BINOL and brilliant green iodide/BINOL systems showed that the catalytic systems consist of one molecule of the carbocation and one molecule of BINOL. Mechanistic studies using a deuterated epoxide indicate that there was some loss of epoxide stereochemistry during the reaction, but predominant retention of stereochemistry is observed. On this basis, a catalytic cycle is proposed.
Evaluation of the Effect of Sulfur on the Performance of Nickel/Gadolinium‐Doped Ceria Based Solid Oxide Fuel Cell Anodes
Authors: Riegraf Matthias , Yurkiv Vitaliy , Costa Rémi , Schiller Günter , Friedrich K. Andreas
Published: November 2016

The focus of this study is the measurement and understanding of the sulfur poisoning phenomena of Ni/gadolinium‐doped ceria (CGO) based solid oxide fuel cells (SOFC). Cells with Ni/CGO10 and NiCu5/CGO40 anodes were characterized by using impedance spectroscopy at different temperatures and H2/H2O fuel ratios. The short‐term sulfur poisoning behavior was investigated systematically at temperatures of 800–950 °C, current densities of 0–0.75 A cm−2, and H2S concentrations of 1–20 ppm. A sulfur poisoning mitigation effect was observed at high current loads and temperatures. The poisoning behavior was reversible for short exposure times. It was observed that the sulfur‐affected processes exhibited significantly different relaxation times that depend on the Gd content in the CGO phase. Moreover, it was demonstrated that the capacitance of Ni/CGO10 anodes is strongly dependent on the temperature and gas‐phase composition, which reflects a changing Ce3+/Ce4+ ratio.
Spatiotemporal differences in otoconial gene expression
Authors: Xu Yinfang , Zhang Yan , Lundberg Yunxia Wang
Published: November 2016

Otoconia are minute biocrystals composed of glycoproteins, proteoglycans, and CaCO3, and are indispensable for sensory processing in the utricle and saccule. Otoconia abnormalities and degeneration can cause or facilitate crystal dislocation to the ampulla, leading to vertigo and imbalance in humans. In order to better understand the molecular mechanism controlling otoconia formation and maintenance, we have examined the spatial and temporal expression differences of otoconial genes in the mouse inner ear at developmental, mature and aging stages using whole transcriptome sequencing (RNA‐Seq) and quantitative RT‐PCR. We show that the expression levels of most otoconial genes are much higher in the utricle and saccule compared with other inner ear tissues before postnatal stages in C57Bl/6J mice, and the expression of a few of these genes is restricted to the embryonic utricle and saccule. After the early postnatal stages, expression of all otoconial genes in the utricle and saccule is drastically reduced, while a few genes gain expression dominance in the aging ampulla, indicating a potential for ectopic debris formation in the latter tissue at old ages. The data suggest that the expression of otoconial genes is tightly regulated spatially and temporally during developmental stages and can become unregulated at aging stages. Birth Defects Research (Part A) 106:613–625, 2016. © 2016 Wiley Periodicals, Inc.
The Impact of DSM‐5 on Eating Disorder Diagnoses
Authors: Vo Megen , Accurso Erin C. , Goldschmidt Andrea B. , Le Grange Daniel
Published: November 2016

Objective

Eating disorder diagnostic criteria were revised from the fourth to the fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM‐IV and −5, respectively). This study examines the impact of these revisions on rates of eating disorder diagnoses in treatment‐seeking youth.

Method

Participants were 651 youth, ages 7–18 years, presenting to an outpatient eating disorders program who met criteria for a DSM‐IV eating disorder diagnosis on intake. Patients completed well‐validated semi‐structured interviews to assess eating disorder psychopathology and psychiatric comorbidity.

Results

Participants were predominantly female (n = 588; 90.3%) with an average age of 15.28 years (SD = 2.21), mean percent of median Body Mass Index (mBMI) of 101.91 (SD = 31.73), and average duration of illness of 16.74 months (SD = 17.63). Cases of DSM‐IV Eating Disorder Not Otherwise Specified (EDNOS), now most consistent with DSM‐5 Other Specified Feeding or Eating Disorder, decreased from 47.6% to 39.0%, Anorexia Nervosa increased from 29.6% to 33.5%, and Bulimia Nervosa increased from 22.7% to 24.7%.

Discussion

Consistent with previous studies, and in keeping with the aims of the DSM‐5 for eating disorders, the revised diagnostic criteria reduced cases of DSM‐IV EDNOS and increased cases of specified eating disorders. © 2016 Wiley Periodicals, Inc.(Int J Eat Disord 2017; 50:578–581)
Application of structural equation mixture modeling to characterize the latent structure of eating pathology
Authors: Forbush Kelsie T. , Wildes Jennifer E.
Published: November 2016

Objective

Several theoretical models describe the structure of eating disorders (EDs), and a burgeoning empirical literature has sought to identify whether eating pathology is conceptualized best as categorical (presence or absence of disorder), dimensional (continuous), or a hybrid of categories and dimensions.

Methods

This study used structural equation mixture modeling (SEMM) to identify the latent structure of EDs. Items from the Eating Pathology Symptoms Inventory (EPSI) were administered to individuals with EDs (N = 344). Select EPSI scales and body mass index were indicators in subsequent SEMM analyses. The Inventory of Depression and Anxiety Symptoms (IDAS), ED diagnoses, and select demographic variables were used as validators using chi‐square or MANOVA.

Results

Categorical models fit the data better than latent dimensional or hybrid models. Latent profile 1 (LP1) was non‐fat‐phobic restricting anorexia nervosa; LP2, an obese, binge‐eating class; LP3, non‐purging bulimia nervosa; LP4, fat‐phobic restricting anorexia nervosa; and LP5, multiple purging bulimia nervosa. External validation analyses indicated that LP4 and LP5 had the highest non‐ED‐related psychopathology.

Discussion

These findings indicate that there is substantial variability in the phenomenology of traditional DSM‐based ED categories across latent profiles, and highlight the salience of certain ED phenotypes that have been debated in the literature. © 2016 Wiley Periodicals, Inc.(Int J Eat Disord 2017; 50:542–550)
Host‐plant associated genetic divergence of two Diatraea spp. (Lepidoptera: Crambidae) stemborers on novel crop plants
Authors: Joyce Andrea L. , Sermeno Chicas Miguel , Serrano Cervantes Leopoldo , Paniagua Miguel , Scheffer Sonja J. , Solis M. Alma
Published: November 2016

Diatraea lineolata and Diatraea saccharalis (Lepidoptera: Crambidae) are moths with stemboring larvae that feed and develop on economically important grasses. This study investigated whether these moths have diverged from a native host plant, corn, onto introduced crop plants including sorghum, sugarcane, and rice. Diatraea larvae were collected from these four host plants throughout the year in El Salvador and were reared on artificial diet until moths or parasitoids emerged. Adult moths were subsequently identified to species. Amplified fragment length polymorphisms (AFLPs) and mitochondrial DNA cytochrome oxidase I (COI) were used to examine whether or not there was genetic divergence of D. lineolata or D. saccharalis populations on the four host plants. Percent parasitism was also determined for each moth on its host plants. D. lineolata was collected from corn in the rainy season and sorghum in the dry season. D. saccharalis was most abundant on sugarcane in the rainy season and sorghum in the dry season. The AFLP analysis found two genetically divergent populations of both D. lineolata and D. saccharalis. Both moths had high levels of parasitism on their dominant host plant in the rainy season, yet had low levels of parasitism on sorghum in the dry season. The presence of two genotypes of both Diatraea spp. on sorghum suggest that host‐associated differentiation is occurring on this novel introduced crop plant.
Wind estimation based on thermal soaring of birds
Authors: Weinzierl Rolf , Bohrer Gil , Kranstauber Bart , Fiedler Wolfgang , Wikelski Martin , Flack Andrea
Published: November 2016

The flight performance of birds is strongly affected by the dynamic state of the atmosphere at the birds' locations. Studies of flight and its impact on the movement ecology of birds must consider the wind to help us understand aerodynamics and bird flight strategies. Here, we introduce a systematic approach to evaluate wind speed and direction from the high‐frequency GPS recordings from bird‐borne tags during thermalling flight. Our method assumes that a fixed horizontal mean wind speed during a short (18 seconds, 19 GPS fixes) flight segment with a constant turn angle along a closed loop, characteristic of thermalling flight, will generate a fixed drift for each consequent location. We use a maximum‐likelihood approach to estimate that drift and to determine the wind and airspeeds at the birds' flight locations. We also provide error estimates for these GPS‐derived wind speed estimates. We validate our approach by comparing its wind estimates with the mid‐resolution weather reanalysis data from ECMWF, and by examining independent wind estimates from pairs of birds in a large dataset of GPS‐tagged migrating storks that were flying in close proximity. Our approach provides accurate and unbiased observations of wind speed and additional detailed information on vertical winds and uplift structure. These precise measurements are otherwise rare and hard to obtain and will broaden our understanding of atmospheric conditions, flight aerodynamics, and bird flight strategies. With an increasing number of GPS‐tracked animals, we may soon be able to use birds to inform us about the atmosphere they are flying through and thus improve future ecological and environmental studies.
Linking modern coexistence theory and contemporary niche theory
Authors: Letten Andrew D. , Ke Po‐Ju , Fukami Tadashi
Published: November 2016

Modern coexistence theory and contemporary niche theory represent parallel frameworks for understanding the niche's role in species coexistence. Despite increasing prominence and shared goals, their compatibility and complementarity have received little attention. This paucity of overlap not only presents an obstacle to newcomers to the field, but it also precludes further conceptual advances at their interface. Here, we present a synthetic treatment of the two frameworks. We review their main concepts and explore their theoretical and empirical relationship, focusing on how the resource supply ratio, impact niche, and requirement niche of contemporary niche theory translate into the stabilizing and equalizing processes of modern coexistence theory. We show, for a general consumer–resource model, that varying resource supply ratios reflects an equalizing process; varying impact niche overlap reflects a stabilizing process; and varying requirement niche overlap may be both stabilizing and equalizing, but has no qualitative effect on coexistence. These generalizations provide mechanistic insight into modern coexistence theory, while also clarifying the role of contemporary niche theory's impacts and requirements in mediating coexistence. From an empirical perspective, we recommend a hierarchical approach, in which quantification of the strength of stabilizing mechanisms is used to guide more focused investigation into the underlying niche factors determining species coexistence. Future research that considers alternative assumptions, including different forms of species interaction, spatiotemporal heterogeneity, and priority effects, would facilitate a more complete synthesis of the two frameworks.
Direct benefits and indirect costs of warm temperatures for high‐elevation populations of a solitary bee
Authors: Forrest Jessica R. K. , Chisholm Sarah P. M.
Published: November 2016

Warm temperatures are required for insect flight. Consequently, warming could benefit many high‐latitude and high‐altitude insects by increasing opportunities for foraging or oviposition. However, warming can also alter species interactions, including interactions with natural enemies, making the net effect of rising temperatures on population growth rate difficult to predict. We investigated the temperature‐dependence of nesting activity and lifetime reproductive output over 3 yr in subalpine populations of a pollen‐specialist bee, Osmia iridis. Rates of nest provisioning increased with ambient temperatures and with availability of floral resources, as expected. However, warmer conditions did not increase lifetime reproductive output. Lifetime offspring production was best explained by rates of brood parasitism (by the wasp Sapyga), which increased with temperature. Direct observations of bee and parasite activity suggest that although activity of both species is favored by warmer temperatures, bees can be active at lower ambient temperatures, while wasps are active only at higher temperatures. Thus, direct benefits to the bees of warmer temperatures were nullified by indirect costs associated with increased parasite activity. To date, most studies of climate‐change effects on pollinators have focused on changing interactions between pollinators and their floral host‐plants (i.e., bottom‐up processes). Our results suggest that natural enemies (i.e., top‐down forces) can play a key role in pollinator population regulation and should not be overlooked in forecasts of pollinator responses to climate change.
Non‐random food‐web assembly at habitat edges increases connectivity and functional redundancy
Authors: Peralta Guadalupe , Frost Carol M. , Didham Raphael K. , Rand Tatyana A. , Tylianakis Jason M.
Published: November 2016

Habitat fragmentation dramatically alters the spatial configuration of landscapes, with the creation of artificial edges affecting community structure and dynamics. Despite this, it is not known how the different food webs in adjacent habitats assemble at their boundaries. Here we demonstrate that the composition and structure of herbivore‐parasitoid food webs across edges between native and plantation forests are not randomly assembled from those of the adjacent communities. Rather, elevated proportions of abundant, interaction‐generalist parasitoid species at habitat edges allowed considerable interaction rewiring, which led to higher linkage density and less modular networks, with higher parasitoid functional redundancy. This was despite high overlap in host composition between edges and interiors. We also provide testable hypotheses for how food webs may assemble between habitats with lower species overlap. In an increasingly fragmented world, non‐random assembly of food webs at edges may increasingly affect community dynamics at the landscape level.
Rationale for and design of the TRUE‐AHF trial: the effects of ularitide on the short‐term clinical course and long‐term mortality of patients with acute heart failure
Authors: Packer Milton , Holcomb Richard , Abraham William T. , Anker Stefan , Dickstein Kenneth , Filippatos Gerasimos , Krum Henry , Maggioni Aldo P. , McMurray John J.V. , Mebazaa Alexandre , O'Connor Christopher , Peacock Frank , Ponikowski Piotr , Ruschitzka Frank , van Veldhuisen Dirk J. , Holzmeister Johannes ,   on behalf of the TRUE‐AHF Investigators and Committees
Published: November 2016

The TRUE‐AHF is a randomized, double‐blind, parallel‐group, placebo‐controlled trial which is evaluating the effects of a 48‐h infusion of ularitide (15 ng/kg/min) on the short‐ and long‐term clinical course of patients with acute heart failure. Noteworthy features of the study include the early enrolment of patients following their initial clinical presentation (within 12 h), and entry blood pressure criteria and thresholds for the adjustment of drug infusion rates, which aim to minimize the risk of hypotension. The trial has two primary endpoints: (i) cardiovascular mortality during long‐term follow‐up; and (ii) the clinical course of patients during their index hospitalization. Cardiovascular mortality is evaluated in this event‐driven trial by following all randomized patients for the occurrence of death until the end of the entire study without truncation at an arbitrarily determined early time point. The clinical course during the index hospitalization is evaluated using the hierarchical clinical composite endpoint, which combines information regarding changes in symptoms and the occurrence of in‐hospital worsening heart failure events and death into a single ranked metric that captures interval clinical events and minimizes the likelihood of missing data and confounding due to intensification of background therapy. The design of the TRUE‐AHF trial capitalizes on lessons learned from earlier trials and aims to evaluate definitively the potential benefit of ularitide in patients with acute heart failure.

Trial registration: NCT01661634
B‐cell‐intrinsic function of TAPP adaptors in controlling germinal center responses and autoantibody production in mice
Authors: Jayachandran Nipun , Landego Ivan , Hou Sen , Alessi Dario R. , Marshall Aaron J.
Published: November 2016

Control of B‐cell signal transduction is critical to prevent production of pathological autoantibodies. Tandem PH domain containing proteins (TAPPs) specifically bind PI(3,4)P2, a phosphoinositide product generated by PI 3‐kinases and the phosphatase SHIP. TAPP KI mice bearing PH domain‐inactivating mutations in both TAPP1 and TAPP2 genes, uncoupling them from PI(3,4)P2, exhibit increased BCR‐induced activation of the kinase Akt and develop lupus‐like characteristics including anti‐DNA antibodies and deposition of immune complexes in kidneys. Here, we find that TAPP KI mice develop chronic germinal centers (GCs) with age and show abnormal expression of B‐cell activation and memory markers. Upon immunization with T‐dependent Ag, TAPP KI mice develop functional but abnormally large GCs, associated with increased GC B‐cell survival. Disruption of chronic GCs in TAPP KI mice by deletion of the costimulatory molecule ICOS abrogate anti‐DNA and anti‐nuclear antibody production in TAPP KI mice, indicating an essential role for GCs. Moreover, TAPP KI B cells are sufficient to drive chronic GC responses and recapitulate the autoimmune phenotype in BM chimeric mice. Our findings demonstrate a B‐cell‐intrinsic role of TAPP–PI(3,4)P2 interaction in regulating GC responses and autoantibody production and suggest that uncontrolled Akt activity in B cells can drive autoimmunity.
CD103+CD11b− salivary gland dendritic cells have antigen cross‐presenting capacity
Authors: Lu Lu , Tanaka Yukinori , Ishii Naoto , Sasano Takashi , Sugawara Shunji
Published: November 2016

Dendritic cells (DCs) in lymphoid and non‐lymphoid tissues are professional antigen‐presenting cells that are essential for effective immunity and tolerance. However, the presence and characteristics of DCs in steady‐state salivary glands (SGs) currently remain unknown. We herein identified CD64−CD11c+ classical DCs (cDCs) as well as CD64+ macrophages among CD45+MHC class II+ antigen‐presenting cells in steady‐state murine SGs. SG cDCs were divided into CD103+CD11b− and CD103−CD11b+ cDCs. CD103+CD11b− cDCs expressed XCR1, CLEC9A, and interferon regulatory factor 8, whereas CD103−CD11b+ cDCs strongly expressed CD172a. Both cDC subsets in SGs markedly expanded in response to the Flt3 ligand (Flt3L), were replenished by bone marrow‐derived precursors, and differentiated from common DC precursors, but not monocytes. Furthermore, ovalbumin‐pulsed SG CD103+CD11b− cDCs induced the proliferation of naïve ovalbumin‐specific CD8+ T cells and production of interferon‐γ from proliferating T cells. SG CD103+CD11b− cDCs expanded by Flt3L in vivo exhibited the same properties. These results indicate that bona fide cDCs reside in steady‐state murine SGs and cDCs with the CD103+CD11b− phenotype possess antigen cross‐presenting capacity. Moreover, Flt3L enhances protective immunity by expanding cDCs. Taken together, SG cDCs might play an important role in maintaining immune homeostasis in the tissues.
Photocatalytic Properties of 1D TiO2 Nanostructures Prepared from Polyacrylamide Gel–TiO2 Nanopowders by Hydrothermal Synthesis
Authors: Shahrezaei Mahdi , Babaluo Ali Akbar , Habibzadeh Sajjad , Haghighi Mohammad
Published: November 2016

In the present study, the polyacrylamide gel (PAG) route was employed to synthesize a nanosized TiO2 powder (PAG–TiO2). The resultant PAG–TiO2 and commercial TiO2 (P25‐TiO2) nanopowders were then used as the starting materials to hydrothermally synthesize one‐dimensional (1D) TiO2 nanostructures (nanotubes and nanorods). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) analysis, X‐ray diffraction (XRD), and thermogravimetric analysis (TGA) were used to characterize the synthesized TiO2 nanostructures. The TiO2 nanopowders, calcined at 400 °C, were further examined for their photocatalytic performance in the decomposition of formic acid as an organic pollutant. The results demonstrate a superior quality of nanotubes synthesized from the PAG–TiO2 nanoparticles as well as enhanced photocatalytic activity compared to the nanotubes synthesized from commercial P25‐TiO2. For the first time, the effect of PAG–TiO2 nanoparticles as starting material of the hydrothermal reaction on morphology and photocatalytic performance of the resulting nanostructures was investigated.
First‐Principles Calculations and Optical Absorption Spectrum of a Light‐Colored Aluminum‐Substituted ε‐Iron Oxide Magnet
Authors: Nasu Tomomichi , Yoshikiyo Marie , Tokoro Hiroko , Namai Asuka , Ohkoshi Shin‐ichi
Published: November 2016

In this paper, we report the electronic structure and optical properties of Al‐substituted ε‐Fe2O3. First‐principles calculations of the periodic structure of ε‐Al0.5Fe1.5O3 reveal that the band gaps (Eg) are 2.6 (480 nm) and 2.5 eV (500 nm) for the up‐spin and down‐spin transitions, respectively. To investigate the electronic structure, a highly dispersed polymer solution composed of ε‐Al0.66Fe1.34O3 nanoparticles was prepared. This solution is light orange in color; the absorption coefficients (ε) are small with values of 810 and 260 dm3 mol–1 cm–1 at 3.1 (400 nm) and 2.6 eV (480 nm), respectively. The reason why Al‐substituted ε‐Fe2O3 is so light in color can be understood by the disappearance of the energy states in the conduction and valence bands, which originates from the tetrahedral D site. Such a light‐colored magnetic material should be useful for colored magnetic toners for color printing.
Native Serine Peptide Assembly – Scope and Utility
Authors: Pirrung Michael C. , Schreihans Ryan S.
Published: November 2016

This work develops serine peptide assembly (SPA), which complements and contrasts with classic native chemical ligation (NCL). Advances in reagentless peptide‐bond formation have been applied to serine (and serine models) and a range of C‐terminal amino acids, including bulky residues that are not amenable to NCL. The particular appeal of SPA is preparative‐scale segment condensations with zero racemization risk and favorable process mass intensity (PMI). Mechanistic studies support a previously proposed reaction pathway via an initial transesterification step. An understanding of the factors favoring this pathway relies on hard–soft acid–base theory, according to which mildly activated esters with the largest carbonyl positive charge are most reactive with hydroxyamines. Novel C‐terminal activators have been discovered that enhance reactivity and give harmless byproducts.
Convenient Synthesis of Thieno[3,2‐b]indoles and Thieno[3,4‐b]indoles by Sequential Site‐Selective Suzuki and Double C–N Coupling Reactions
Authors: Pham Ngo Nghia , Parpart Silvio , Grigoryan Sevak , Ngo Thang Ngoc , Dang Tuan Thanh , Ghochikyan Tariel V. , Saghyan Ashot S. , Ehlers Peter , Langer Peter
Published: November 2016

A convenient synthesis of thieno[3,2‐b]indoles and thieno[3,4‐b]indoles has been developed. The protocol involves a site‐selective Suzuki reaction, followed by a double C–N coupling reaction using anilines, benzylamines, or alkylamines. The yields range from good to excellent.
Aromatic Esters, Carbinols, and Derivatives Thereof with Perfluorohexyl Residues as Alternatives to Perfluoroalkanecarboxylic and ‐sulfonic Acids
Authors: Alpers Torben , Muesmann Thomas W. T. , Temme Oliver , Christoffers Jens
Published: November 2016

Four perfluorohexyl carbinols have been prepared from the corresponding Grignard reagent and benzaldehyde, terephthalaldehyde, isophthalaldehyde, and trimesaldehyde. The corresponding secondary alcohols were then transformed by alkylation and acylation reactions to form a total of 14 ethers (methyl, ethyl, propyl, and n‐hexyl ethers) and esters (acetyl and 2‐ethylhexanoyl), respectively. Furthermore, 11 perfluoroalkyl carboxylates were prepared from aromatic, heteroaromatic, and aliphatic mono‐, di‐, tri‐, and tetracarboxylic acids and tridecafluorooctanol. The wettability of all 29 materials was investigated by the water contact angle measurements of thin films on glass surfaces. In up to six cases, contact angles greater than 130° were observed, which indicates that the products might be suitable candidates for the impregnation of surfaces. With their relatively short perfluoroalkyl side‐chains and therefore low bioaccumulativity, the target compounds might be beneficial alternatives to established products.
RhIII‐Catalyzed Regioselective Synthesis of Phthalides with Water as the Solvent
Authors: Zhu You‐Quan , Li Jun‐Xian , Han Ting‐Feng , He Jing‐Li , Zhu Kun
Published: November 2016

Under rhodium(III)‐catalyzed conditions, a broad range of benzoic acids reacted with acrylates successfully to provide phthalides through the direct functionalization of a C–H bond followed by β‐hydride elimination and intramolecular Michael addition. The reaction provides an alternative strategy for the construction of diverse and useful phthalide derivatives from readily available starting materials. In most cases, high regioselectivity was obtained, and this is the first report of the rhodium‐catalyzed synthesis of phthalides in water.
User‐independent assessment of conditioning pain modulation by cuff pressure algometry
Authors: Graven‐Nielsen T. , Izumi M. , Petersen K.K. , Arendt‐Nielsen L.
Published: November 2016

Background

The use of conditioning pain modulation (CPM) is hampered by poor reproducibility and lack of user‐independent paradigms. This study refined the CPM paradigm by applying user‐independent cuff algometry.

Methods

In 20 subjects, the CPM effect of conditioning with cuff stimulation on the arm was investigated by pain test stimuli on the contralateral leg before and in parallel with different cuff conditionings (10, 30, 60 kPa/60 s; 30, 60 kPa/10 s). As test stimulus, another cuff was inflated (1 kPa/s) until the subjects detected the pain tolerance threshold (PTT) during which the pain detection threshold (PDT) and the pressure at a pain intensity of 6 cm on a 10‐cm visual analogue scale (PVAS6) were extracted. For comparison, pressure pain thresholds (PPTs) as test stimuli were recorded by the user‐dependent handheld pressure algometry. Combinations of cuff locations for conditioning (pain intensity standardized) and contralateral test stimuli were additionally evaluated (leg–arm, leg–leg, arm–thigh). The test–retest reliability in two sessions 1 month apart was assessed in five CPM protocols.

Results

In all protocols, the PDT, PVAS6 and PTT increased during conditioning compared with baseline (p < 0.05). The CPM effect (i.e. conditioning minus baseline) for PVAS6, PTT and PPT increased for increasing conditioning intensities (p < 0.05). The CPM effects were not significantly different for changes in conditioning durations or conditioning/test stimulus locations. In two sessions, the CPM effects for PVAS6 and PTT assessed after 60 s of conditioning on the leg/thigh showed the highest intra‐class correlations (0.47–0.73), where they were 0.04–0.6 for PPTs.

Conclusions

The user‐independent cuff algometry is reliable for CPM assessment and for supra‐pain threshold test stimuli better than the user‐dependent technology.

Significance

A user‐independent CPM technique where the conditioning is controlled by one cuff stimulation, and the test‐stimulus is provided by another cuff stimulation. This study shows that cuff algometry is reliable for CPM assessment.
Key Factors of Ternary Monolayers to Improve DNA Sensors Performance
Authors: Aufartova Jana , López Marta Sánchez‐Paniagua , Martín‐Fernández Begoña , López‐Ruiz Beatriz
Published: November 2016

An important factor affecting the performance of electrochemical genosensors is the immobilization strategy used to anchor the capture probes (CP) on the electrode surface. One of the most common immobilization systems involves the formation of self‐assembled monolayers of thiolated probes on gold surfaces, mainly due to its simplicity and effectiveness. Recent studies have shown that in two‐component thiolated DNA and mercaptohexanol (MCH) monolayers, there is incomplete backfilling that leads to defective surface blockage, producing unspecific background signal. In order to solve these problems, ternary monolayers have been proposed, in which besides MCH as primary diluent, a second diluent is added to enhance the hybridization efficiency and anti‐fouling properties of the surface. Herein, we report a thorough evaluation of different surface chemistries using two different sensors, one for the detection of a peanut allergen encoding sequence and the other one targeting a gluten‐encoding sequence. We assessed the relationship between CP length and the chemical characteristics of the diluents. Factors such as concentration, nature of the functional groups and chain length of the second diluent were evaluated. We found that length of diluents affects primarily the hybridization efficiency, while the type of functional groups, e.g. hydroxyl, carboxyl or a second thiol group, influences the degree of surface coverage. Results diverged between the two sensors evaluated.
Feasibility of magnetoencephalographic source imaging in patients with thalamic deep brain stimulation for epilepsy
Authors: Wennberg Richard , del Campo J. Martin , Shampur Nat , Rowland Nathan C. , Valiante Taufik , Lozano Andres M. , Garcia Dominguez Luis
Published: November 2016

Source localization of interictal spikes in patients with medically refractory epilepsy is the most common clinical application of magnetoencephalography (MEG). In recent decades, many patients with intractable epilepsy have been treated with various forms of neurostimulation, including thalamic deep brain stimulation (DBS). Patients with suboptimal seizure control after DBS might in some cases benefit from further investigations for resective epilepsy surgery, including MEG source imaging (MSI). We sought to determine the feasibility and accuracy of MSI in the setting of active thalamic DBS. Simultaneous EEG/MEG was obtained in a patient using an Elekta 306‐channel MEG system, with high‐frequency (100 Hz) DBS of the thalamic anterior nuclei cycling between on and off states. Magnetic artifacts associated with the DBS apparatus were successfully suppressed using the spatiotemporal signal space separation (tSSS) method. Electrical stimulation artifact was removed by standard digital low‐pass filtering. Dipole source modeling results for spike foci in frontal and posterior temporal regions were comparable between stimulation on and stimulation off states, and the source solutions corresponded well to the localization of spikes documented by intracranial EEG. MSI is thus feasible and source solutions can be accurate when performed in patients with active thalamic DBS for epilepsy.
Predictors, Moderators, and Mediators of Treatment Outcome Following Manualised Cognitive‐Behavioural Therapy for Eating Disorders: A Systematic Review
Authors: Linardon Jake , de la Piedad Garcia Xochitl , Brennan Leah
Published: November 2016

This systematic review synthesised the literature on predictors, moderators, and mediators of outcome following Fairburn's CBT for eating disorders. Sixty‐five articles were included. The relationship between individual variables and outcome was synthesised separately across diagnoses and treatment format. Early change was found to be a consistent mediator of better outcomes across all eating disorders. Moderators were mostly tested in binge eating disorder, and most moderators did not affect cognitive‐behavioural treatment outcome relative to other treatments. No consistent predictors emerged. Findings suggest that it is unclear how and for whom this treatment works. More research testing mediators and moderators is needed, and variables selected for analyses need to be empirically and theoretically driven. Future recommendations include the need for authors to (i) interpret the clinical and statistical significance of findings; (ii) use a consistent definition of outcome so that studies can be directly compared; and (iii) report null and statistically significant findings. Copyright © 2016 John Wiley & Sons, Ltd and Eating Disorders Association.
An effective discriminator for differentiating the root causes of packet transmission failures in indoor WSNs
Authors: Huang Tingpei , Chen Haiming , Cui Li , Li Shibao
Published: November 2016

It is well known that there are 2 kinds of causes, namely, channel errors and collisions, which lead to high probability of packet transmission failures in wireless networks. The ability of discriminating the above causes provides many opportunities for implementing high efficient networking protocols in wireless sensor networks. This paper presents EasiPLED, an effective discriminator that can accurately and timely predict these causes. EasiPLED has 3 salient features. First, it investigates frame‐level bit error rate (F‐BER) patterns and statistic characteristics of received signal strength indicator (RSSI) and link quality indicator through extensive indoor experiment studies. The F‐BER is measured at the receiver side by a coarse‐grained method without incurring any overhead. An adaptive RSSI estimator based on error‐based filter is proposed to mitigate effects of environment noises and hardware limitations on RSSI readings. Second, EasiPLED designs an off‐line classifier using machine learning method, which takes a combination of F‐BER and RSSI features as input and outputs the probability of dominant factor that causes transmission failures. Finally, it presents an on‐line discriminator to diagnose the cause of a failed transmission when it occurs at the receiver side, which achieves an accuracy by up to 95.4%. We evaluate the effectiveness of EasiPLED by applying it to link‐layer retransmission scheme and probabilistic polling protocol. Experimental results demonstrate that our method yields a reduction of single‐hop transmission delay by up to 47% and provides high packet delivery ratios as compared to the existing retransmission methods. The EasiPLED‐based probabilistic polling protocol achieves by up to 41.4% throughput gain over the existing method.
Effect of aluminum trihydrate as flame retardant on properties of a thermoplastic rubber nanocomposite
Authors: Khattab M. A. , Feteha Feteha Abdel Halim , Sadik W. A. , Abdel‐Bary E. M.
Published: November 2016

In this work, different concentrations, per hundred rubber (phr), of aluminum trihydrate (ATH) were added to thermoplastic rubber nanocomposite based on ethylene propylene diene monomer and linear low‐density polyethylene. The effect of the added compound on the flammability, rheological, mechanical properties, and electrical conductivity of the composite was studied. The results of the cone calorimeter showed a significantly reduction in the flammability of the composites occurred when the composite was treated with ATH. The peak heat release rate was reduced by about 66% when the composite was loaded with 180 phr of ATH. Moreover, the time to ignition prolonged up to 160%. The total smoke released decreased significantly as the concentrations of the ATH were increased. A reduction of about 69% in the total smoke released was observed when the composite was treated with 180 phr. The thermogravimetric analysis showed a reduction in the overall weight loss as the concentrations of ATH were increased. A reduction of about 50% of the original weight was observed when 180 phr of ATH was used. An appreciable decrease in tensile stress and strain with increasing ATH contents had been observed. The addition of ATH markedly reduced the conductivity of the thermoplastic rubber nanocomposite. Copyright © 2016 John Wiley & Sons, Ltd.
Field assisted sintering technology. Part I: Experiments, constitutive modeling and parameter identification
Authors: Rothe Steffen , Kalabukhov Sergei , Frage Nachum , Hartmann Stefan
Published: November 2016

Field‐assisted sintering technology (FAST), also well‐known under the term spark‐plasma sintering (SPS), is a grown process technology to produce parts made of a powder material. The process itself has the advantage of carrying out compaction, sintering and cooling with high temperature rates in one process step. This is done using an electrical current, which heats the graphite tools and, accordingly, the powder within the die itself. The theoretical description itself is very complicated caused by the fact of having electro‐thermomechanical coupling effects, large deformations, contact problems for each field, but the essential point are the amount of experiments required to determine the parameters of the model. In this article, the required experiments to obtain the electrical, thermal and mechanical properties of both materials are discussed, a constitutive model of compressible thermo‐viscoplasticity for copper powder is proposed, and aspects of material parameter identification are addressed. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)