bluuebunny/crossref_metadata_2025 huggingface dataset:
Stenotrophomonas maltophilia OleC‐Catalyzed ATP‐Dependent Formation of Long‐Chain Z‐Olefins from 2‐Alkyl‐3‐hydroxyalkanoic Acids
Authors: Kancharla Papireddy , Bonnett Shilah A. , Reynolds Kevin A.
Published: May 2016

The bacterial pathway of olefin biosynthesis starts with OleA catalyzed “head‐to‐head” condensation of two CoA‐activated long‐chain fatty acids to generate (R)‐2‐alkyl‐3‐ketoalkanoic acids. A subsequent OleD‐catalyzed reduction generates (2R,3S)‐2‐alkyl‐3‐hydroxyalkanoic acids. We now show that the final step in the pathway is an OleC‐catalyzed ATP‐dependent decarboxylative dehydration to form the corresponding Z olefins. Higher kcat/Km values were seen for substrates with longer alkyl chains. All four stereoisomers of 2‐hexyl‐3‐hydroxydecanoic acid were shown to be substrates, and GC‐MS and NMR analyses confirmed that the product in each case was (Z)‐pentadec‐7‐ene. LC‐MS analysis supported the formation of AMP adduct as an intermediate. The enzymatic and stereochemical course of olefin biosynthesis from long‐chain fatty acids by OleA, OleD and OleC is now established.
Mutations Closer to the Active Site Improve the Promiscuous Aldolase Activity of 4‐Oxalocrotonate Tautomerase More Effectively than Distant Mutations
Authors: Rahimi Mehran , van der Meer Jan‐Ytzen , Geertsema Edzard M. , Poddar Harshwardhan , Baas Bert‐Jan , Poelarends Gerrit J.
Published: May 2016

The enzyme 4‐oxalocrotonate tautomerase (4‐OT), which catalyzes enol–keto tautomerization as part of a degradative pathway for aromatic hydrocarbons, promiscuously catalyzes various carbon–carbon bond‐forming reactions. These include the aldol condensation of acetaldehyde with benzaldehyde to yield cinnamaldehyde. Here, we demonstrate that 4‐OT can be engineered into a more efficient aldolase for this condensation reaction, with a >5000‐fold improvement in catalytic efficiency (kcat/Km) and a >107‐fold change in reaction specificity, by exploring small libraries in which only “hotspots” are varied. The hotspots were identified by systematic mutagenesis (covering each residue), followed by a screen for single mutations that give a strong improvement in the desired aldolase activity. All beneficial mutations were near the active site of 4‐OT, thus underpinning the notion that new catalytic activities of a promiscuous enzyme are more effectively enhanced by mutations close to the active site.
Preparation of Silver‐Modified Nickel Foams by Galvanic Displacement and Their Use as Cathodes for the Reductive Dechlorination of Herbicides
Authors: Verlato Enrico , He Wenyan , Amrane Abdeltif , Barison Simona , Floner Didier , Fourcade Florence , Geneste Florence , Musiani Marco , Seraglia Roberta
Published: May 2016

New 3D electrodes are prepared and tested in reductive herbicide dechlorination as the first step of an environmental remediation process. Commercial nickel foams are modified through the spontaneous deposition of silver nanoparticles. Some of the solutions of Ag+ ions employed in the galvanic displacement reactions contain complexing agents, such as thiosulfate or thiocyanate, and a capping agent, polyvinylpyrrolidone (PVP), which influences the morphology and growth kinetics of the silver deposits. Modified foams are used as cathodes for the reductive dechlorination of AlachlorTM, a common chloroacetanilide herbicide, in a series of tests that confirm the catalytic activity of silver. Electrodes prepared in a thiosulfate solution containing PVP allow extensive reduction of AlachlorTM to give deschloroalachlor as the only dechlorinated product.
β,β‐(1,4‐Dithiino)subporphyrin Dimers Capturing Fullerenes with Large Association Constants
Authors: Yoshida Kota , Osuka Atsuhiro
Published: May 2016

β,β‐(1,4‐Dithiino)subporphyrin dimers 7‐syn and 7‐anti were synthesized by the nucleophilic aromatic substitution reaction of 2‐bromo‐3‐(4‐methoxyphenylsulfonyl)subporphyrin 4 with 2,3‐dimercaptosubporphyrin 5 under basic conditions followed by axial arylation. Additions of C60 or C70 to a dilute solution of 7‐anti (ca. 10−6 m) in toluene did not cause appreciable UV/Vis spectral changes, while similar additions to a concentrated solution (ca. 10−3 m) resulted in precipitation of complexes. In contrast, dimer 7‐syn captured C60 and C70 in different complexation stoichiometries in toluene; a 1:1 manner and a 2:1 manner, respectively, with large association constants; Ka=(1.9±0.2)×106 m−1 for C60@7‐syn, and K1=(1.6±0.5)×106 and K2=(1.8±0.9)×105 m−1 for C70@(7‐syn)2. These association constants are the largest for fullerenes‐capture by bowl‐shaped molecules reported so far. The structures of C60@7‐anti, C70@7‐anti, C60@7‐syn, and C70@7‐syn have been determined by single‐crystal X‐ray diffraction analysis.
Generalization of the Copper to Late‐Transition‐Metal Transmetallation to Carbenes beyond N‐Heterocyclic Carbenes
Authors: Bidal Yannick D. , Santoro Orlando , Melaimi Mohand , Cordes David B. , Slawin Alexandra M. Z. , Bertrand Guy , Cazin Catherine S. J.
Published: May 2016

Carbene transition‐metal complexes have become a prevalent family of catalysts enabling numerous organic transformations. Their facile synthetic access is a matter of great importance. To this end, the CuI‐NHC transfer methodology has emerged as a powerful alternative presenting attractive advantages over other methods. Herein, we report the remarkable ability of copper to transfer not only NHCs but also other types of carbenes such as abnormal NHCs (aNHCs), cyclic (alkyl)(amino)carbenes (CAACs), and mesoionic carbenes (MICs) to various transition metal precursors.
Herstellung von Wirkstoffnanosuspensionen in Blasensäulen bei gleichzeitiger Partikel‐Abscheidung und Agglomeration
Authors: Weber Alfred P. , Stender Mathias , Koch Dagmar , Türk Michael
Published: May 2016

Stabile Nanosuspensionen können durch Abscheidung von gasgetragenen organischen Wirkstoffpartikeln in Blasensäulen mit tensidhaltigen Lösungen hergestellt werden. Bei hohen Konzentrationen, wie sie beim RESSAS‐Prozess (rapid expansion of supercritical solution into aqueous solution) vorliegen, wird der Transfer der Nanopartikeln vom Gas in die Suspension von der Agglomeration in der Gasphase überlagert. Ein Modell zur Erfassung der beiden Vorgänge und ein Ansatz für dessen Übertragung auf die komplexe Strömung in einer RESSAS‐Anlage für die Herstellung von Naproxen‐Nanosuspensionen werden vorgestellt.
Group‐Based Compassion‐Focused Therapy as an Adjunct to Outpatient Treatment for Eating Disorders: A Pilot Randomized Controlled Trial
Authors: Kelly Allison Catherine , Wisniewski Lucene , Martin‐Wagar Caitlin , Hoffman Ellen
Published: May 2016

The current study sought to assess the acceptability and feasibility of a compassion‐focused therapy (CFT) group as an adjunct to evidence‐based outpatient treatment for eating disorders, and to examine its preliminary efficacy relative to treatment as usual (TAU). Twenty‐two outpatients with various types of eating disorders were randomly assigned to 12 weeks of TAU (n = 11) or TAU plus weekly CFT groups adapted for an eating disorder population (CFT + TAU; n = 11). Participants in both conditions completed measures of self‐compassion, fears of compassion, shame and eating disorder pathology at baseline, week 4, week 8 and week 12. Additionally, participants receiving the CFT group completed measures assessing acceptability and feasibility of the group. Results indicated that the CFT group demonstrated strong acceptability; attendance was high and the group retained over 80% of participants. Participants rated the group positively and indicated they would be very likely to recommend it to peers with similar symptoms. Intention‐to‐treat analyses revealed that compared to the TAU condition, the CFT + TAU condition yielded greater improvements in self‐compassion, fears of self‐compassion, fears of receiving compassion, shame and eating disorder pathology over the 12 weeks. Results suggest that group‐based CFT, offered in conjunction with evidence‐based outpatient TAU for eating disorders, may be an acceptable, feasible and efficacious intervention. Furthermore, eating disorder patients appear to see benefit in, and observe gains from, working on the CFT goals of overcoming fears of compassion, developing more self‐compassion and accessing more compassion from others. Copyright © 2016 John Wiley & Sons, Ltd.
Changes in Object Relations over the Course of Psychodynamic Psychotherapy
Authors: Mullin A. S. J. , Hilsenroth M. J. , Gold J. , Farber B. A.
Published: May 2016

This study explores whether object relations (OR) functioning improves over the course of psychodynamic psychotherapy, and whether this improvement is related to symptom decrease as well as therapist technique. The sample consisted of 75 outpatients engaged in short‐term psychodynamic psychotherapy at a university‐based psychological service clinic. OR functioning was assessed pre‐ and post‐treatment by independent raters using the Social Cognition and Object Relations Scale from in‐session patient relational narratives. The Comparative Psychotherapy Process Scale was used to assess therapist activity and psychotherapy techniques early in treatment. Independent clinical ratings of global OR and psychotherapy techniques were conducted, and rater agreement was found to be in the excellent range. Regarding the results, global OR (overall quality and level of interpersonal functioning) significantly improved with large effect size after psychodynamic therapy. Change in global OR functioning was significantly and positively related to the incidence of psychodynamic techniques in early sessions, as were number of psychotherapy sessions attended. Patient self‐reported reliable change in symptomatology and reliable change in global OR were significantly related as well. Multilevel model analyses confirmed pairwise correlations accounting for therapist effects on a variety of process–outcome measures, number of sessions attended, initial levels of psychiatric symptoms, employment of therapeutic techniques as well overall OR functioning at outcome. Limitations of the present study, future research directions and implications for clinical practice are also discussed. Copyright © 2016 John Wiley & Sons, Ltd.

Key Practitioner Message

Psychodynamic psychotherapy seems to be effective in improving object relations functioning.

Consider use of psychodynamic techniques early in treatment with patients expressing more pathological object representations.

Improvements in object relations functioning during psychodynamic psychotherapy are also related to adaptive changes in patient self‐reported symptomatology.

Therapist effects were also present for the study. As such therapists should be mindful to assess patient change and their use of technique at several points in treatment and flexibly adjust their approach as necessary.
LC‐MS/MS detection of unaltered glucuronoconjugated metabolites of metandienone
Authors: Esquivel Argitxu , Pozo Oscar J. , Garrostas Lorena , Balcells Georgina , Gómez Cristina , Kotronoulas Aristotelis , Joglar Jesús , Ventura Rosa
Published: May 2016

The aim of this study was to evaluate the direct detection of glucuronoconjugated metabolites of metandienone (MTD) and their detection times. Metabolites resistant to enzymatic hydrolysis were also evaluated. Based on the common mass spectrometric behaviour of steroid glucuronides, three liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) strategies were applied for the detection of unpredicted and predicted metabolites: precursor ion scan (PI), neutral loss scan (NL), and theoretical selected reaction monitoring (SRM) methods. Samples from four excretion studies of MTD were analyzed for both the detection of metabolites and the establishment of their detection times. Using PI and NL methods, seven metabolites were observed in post‐administration samples. SRM methods allowed for the detection of 13 glucuronide metabolites. The detection times, measured by analysis with an SRM method, were between 1 and 22 days. The metabolite detected for the longest time was 18‐nor‐17β‐hydroxymethyl‐17α‐methyl‐5β‐androsta‐1,4,13‐triene‐3‐one‐17‐glucuronide. One metabolite was resistant to hydrolysis with β‐glucuronidase; however it was only detected in urine up to four days after administration. The three glucuronide metabolites with the highest retrospectivity were identified by chemical synthesis or mass spectrometric data, and although they were previously reported, this is the first time that analytical data of the intact phase II metabolites are presented for some of them. The LC‐MS/MS strategies applied have demonstrated to be useful for detecting glucuronoconjugated metabolites of MTD, including glucuronides resistant to enzymatic hydrolysis which cannot be detected by conventional approaches. Copyright © 2016 John Wiley & Sons, Ltd.
Residential yards as designer ecosystems: effects of yard management on land snail species composition
Authors: Bergey Elizabeth A. , Figueroa Laura L.
Published: May 2016

Residential yards comprise the majority of green space in urban landscapes, yet are an understudied system because of access issues and because yards may be considered biologically depauperate. Yards are purposely created and managed and, hence, qualify as designer ecosystems, a term borrowed from restoration ecology. We investigated whether yard management (watering regime, mulching, and chemical use) or dog presence affected land snail assemblage composition and described the pattern of native vs. nonnative species among yards. Land snails form an appropriate model system for yard‐scale studies because snails are speciose, common, and have limited mobility. We found 32 land snail species in our survey of 61 yards in Norman, Oklahoma, USA (population size of 118,000). Snail richness in individual yards averaged nine species, with a range of three to 14 species. Native snails were found in all yards and nonnative snails were found in all but one yard. Although some of the nine nonnative species were rare, the most frequently encountered species was the nonnative Triodopsis hopetonensis. All encountered nonnative species also occur in Oklahoma plant nurseries, indicating possible introduction through the plant trade. Yard‐scale watering regime and the presence of dogs were associated with differences in snail species composition but not species richness. Pesticide use and mulch type had little, if any, association with snail composition. Effects may have been diluted by treating yards as units, whereas snails were concentrated in specific microhabitats, such as under shrubs. Soil type also influenced snail assemblages and acted at a scale larger than individual yards. Considering yards as designer ecosystems facilitates investigation of how local variation in management affects biota within yards and across the residential landscape, and highlights the importance of variation among residential yards in understanding patterns of urban biodiversity.
Effects of Ligand Halogenation on the Electron Localization, Geometry and Spin State of Low‐Coordinate (β‐Diketiminato)iron Complexes
Authors: Bellows Sarina M. , Brennessel William W. , Holland Patrick L.
Published: May 2016

This contribution explores the influences of incorporating electron‐withdrawing CF3 and halide groups into (β‐diketiminato)iron complexes of tetrazene and isocyanide. The synthesis of a new halogenated β‐diketimine (LCF3,ClH) was accomplished by two different methods, including a novel microwave‐assisted synthesis that improves the yield of the difficult condensation. Treatment of an iron(II) complex of this ligand with reductant and azide gives two diiron complexes with novel tetrazenes as bridging ligands. Structural and Mössbauer data show that the bridging tetrazene is a radical anion. The halogenation of the supporting ligand also influences iron(I) complexes of the type [LFe(CNtBu)2], which are low‐spin and square‐planar with alkyl substituents but high‐spin and pseudotetrahedral with halogen substituents. DFT calculations suggest that the changes from halogenation come from a combination of steric and electronic effects, and that the electronic influence of ligand halogenation is minor.
Luminescent Metal–Organic Framework Mixed‐Matrix Membranes from Lanthanide Metal–Organic Frameworks in Polysulfone and Matrimid
Authors: Dechnik Janina , Mühlbach Friedrich , Dietrich Dennis , Wehner Tobias , Gutmann Marcus , Lühmann Tessa , Meinel Lorenz , Janiak Christoph , Müller‐Buschbaum Klaus
Published: May 2016

Metal–organic framework/polymer (MOF–polymer) mixed‐matrix membranes (MMMs) have been prepared by embedding the luminescent lanthanide (Ln) MOFs 3∞[Sr0.9Eu0.1Im2] and 2∞[Tb2Cl6(bipy)3]·2bipy (Im– = imidazolate, bipy = 4,4′‐bipyridine) into polysulfone (PSF, Ultrasonî S) and Matrimidî polymer films. The successful embedding of the Sr and Eu MOFs has been achieved for both matrixes, and the original MOF luminescence is maintained. The defect‐free nature of the membranes was proven by the slightly lower gas permeation of the MMMs with the dense filler particles. For the Tb–bipy MOF, successful embedding is possible for polysulfone only. For the preparation of the MOF polymer membranes, the influence of different mass fractions of the luminescent MOFs ranging from 8–16 wt.‐% and preparation from suspensions with and without ultrasonic radiation were studied. The influence of the MOF fraction is different for both membrane materials. For the polysulfone, lower amounts of MOF are preferable and lead to an increase of the overall luminescence intensity, whereas the opposite was observed for Matrimid. Altogether, the parity‐allowed emission of the Eu2+ ions is apparently stronger than the Tb3+ emission and leads to membranes with strong emission that is visible to the naked eye under normal daylight. Thereby, the Ln MOF polymer membranes open new options for the handling of luminescent MOFs.
Hybrid Cyclometalated Iridium Coumarin Complex as a Sensitiser of Both n‐ and p‐Type DSSCs
Authors: Sinopoli Alessandro , Wood Christopher J. , Gibson Elizabeth A. , Elliott Paul I. P.
Published: May 2016

The preparation and characterisation of a hybrid biscyclometalated coumarin/iridium complex is presented which exhibits intense visible absorption (ε ≈ 43800 dm3 mol–1 cm–1) and sensitises both n‐ and p‐type dye‐sensitised solar cells (DSSCs).
Binuclear Highly Distorted Iron(III) Porphyrins Bridged by the Dianions of Hydroquinones: Role of the Bridge in Electronic Communication
Authors: Sahoo Dipankar , Singh Akhil Kumar , Rath Sankar Prasad
Published: May 2016

A family of binuclear highly substituted and distorted ferric porphyrins bridged through a variety of p‐hydroquinone dianions is reported. Two iron(II) porphyrins are oxidized with a consequence of 2 e reduction of the p‐benzoquinone unit, which produces the binuclear ferric complex bridged with dianions of hydroquinone. The electronic structures of the dimeric complexes have been confirmed by using UV/Vis, IR, 1H NMR, EPR and Mössbauer spectroscopy as well as single‐crystal X‐ray diffraction studies. The hydroquinone plane is remarkably tilted to form a Fe–O–C angle of approximately 132° and a dihedral angle of approximately 53° with the porphyrin mean plane. Variable‐temperature magnetic susceptibility measurements were carried out between 5 and 300 K in the solid state and the iron centres are found to be involved in a weak antiferromagnetic exchange interaction through the bridge. The coupling constant, J, varies between –6.46 and –14.12 cm–1 for the complexes reported here just upon changing the substituent on the bridge. It was observed that an increase in the electron‐withdrawing property of the substituent on the p‐benzoquinone ring reduces the antiferromagnetic coupling between the two iron centres whereas electron‐donating substituents increase it. The exchange interactions between two iron centres, thus, depend on the electronic nature of the bridge.
Atropoisomerism in Mono‐ and Diaryl‐Substituted 4‐Amino‐2,6‐lutidines
Authors: Górecki Marcin , Roszkowski Piotr , Błachut Dariusz , Maurin Jan K. , Budzianowski Armand , Frelek Jadwiga , Czarnocki Zbigniew
Published: May 2016

The Suzuki–Miyaura reaction of 4‐amino‐3,5‐dibromo‐2,6‐lutidine with various ortho‐substituted phenylboronic acids resulted in the formation of a series of mono‐ and diarylated lutidines in the form of atropisomers. The absolute stereochemistry of the chiral compounds was established, in some cases, by X‐ray crystal structure analysis and HPLC‐ECD (ECD = electronic circular dichroism) in combination with time‐dependent density functional theory (TDDFT) calculations.
Synthesis of Dicyano‐Substituted Benzo[c]fluorenes from Tetraaryl[3]cumulenes
Authors: Gawel Przemyslaw , Halabi Elias A. , Schweinfurth David , Trapp Nils , Ruhlmann Laurent , Boudon Corinne , Diederich François
Published: May 2016

We have developed a one‐step synthesis of 5,6‐dicyano‐7‐(diphenylvinyl)‐7H‐benzo[c]fluorenes, starting from easily accessible tetraaryl[3]cumulenes and 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ). In the proposed mechanism, this transformation is initiated by single‐electron transfer from the cumulene to DDQ with subsequent ring closure. In the next step, [4+2] cycloaddition of an additional DDQ molecule is followed by transformation of the formed cycloadducts, which provides new 5,6‐dicyanobenzo[c]fluorene derivatives in fair to good yields. Isolated intermediates and time‐resolved EPR spectroscopy measurements support our mechanistic proposal. Furthermore, X‐ray crystallographic proof for the postulated structures as well as for the reaction intermediates is provided. The optoelectronic properties of these new chromophores were derived from UV/Vis spectroscopy, electrochemical, and computational studies. Additionally, the aromaticity of the new polycyclic aromatic backbone was analyzed by using nucleus‐independent chemical shift (NICS)‐XY‐scans.
High Sensitivity and Fast Oxidation of Caffeine in Coffee and Theophylline at Nanostructured Electrodes
Authors: Reskety Atiye Ahmadi , Chamjangali Mansour Arab , Boujnane Mehdi , Brajter‐Toth Anna
Published: May 2016

Significantly higher than previously reported sensitivity was achieved in the electrochemical determinations of caffeine (CA) and theophylline (TP) at a nanostructured carbon fiber electrode (CFE) sensor by fast scan voltammetry (FSV), where apparent catalysis of the oxidation was observed. For CA the oxidation was reversible and the oxidation potential in aqueous solutions was similar to the potentials reported from cyclic voltammetry (CV) in aprotic solvents, indicating similar oxidation pathways, forming CA radicals. For TP, the reversible oxidation potential was higher, in agreement with TP structure. Formal potentials in aqueous solutions that have been previously unavailable from electrochemistry of CA and TP were thus obtained. In the determinations of CA and TP, sensitivity and linear dynamic range (LDR) in FSV were 1.84 mA cm−2 µM−1 and 0.20–22.0 µmol L−1 and 1.46 mA cm−2 µM−1 and 0.50–30.0 µmol L−1, respectively. FSV determination of CA in coffee sample is demonstrated and the results are in agreement with the results obtained by HPLC‐UV.
Polymer‐coated Boron Doped Diamond Optically Transparent Electrodes for Spectroelectrochemical Sensors
Authors: Rusinek Cory A. , Becker Michael F. , Rechenberg Robert , Kaval Necati , Ojo Kolade , Heineman William R.
Published: May 2016

Spectroelectrochemical sensors combine electrochemistry, spectroscopy, and partitioning into a film to provide improved selectivity for the target analyte. The sensor usually consists of an optically transparent electrode (OTE) coated with a charge selective polymer film. The polymer film is chosen to pre‐concentrate analyte at the OTE surface to improve the sensitivity and provide selectivity against like charged interferences. OTEs such as Indium Tin Oxide (ITO) have been used extensively for spectroelectrochemical sensors, but little is known about the applicability of such sensors using other OTE materials, such as Boron Doped Diamond (BDD). One distinct advantage of BDD OTEs over ITO OTEs is their significant increase in sensitivity for organic compounds, such as 4‐aminophenol and hydroquinone. We have developed absorption and fluorescence‐based sensing methods with a BDD OTE coated with a sulfonated ionomer film, Nafion. This is demonstrated with tris(2,2′‐bipyridyl)ruthenium(II) ion [Ru(bpy)32+] using an attenuated total reflectance (ATR) flow cell setup for both absorption and fluorescence. With a Nafion coated BDD optically transparent thin layer electrode (OTTLE), we developed a fluorescence based sensor for a common polyaromatic hydrocarbon (PAH), 1‐hydroxypyrene (1‐pyOH), achieving a detection limit of 80 nM (17 ppb). This work manifests new sensing applications while broadening the use of spectroelectrochemistry, OTEs, and BDD as an electrode material.
Multiple hazard incidents lifecycle cost assessment of structural systems considering state‐dependent repair times and fragility curves
Authors: Fereshtehnejad Ehsan , Shafieezadeh Abdollah
Published: May 2016

The performance and serviceability of structural systems during their lifetime can be significantly affected by the occurrence of extreme events. Despite their low probability, there is a potential for multiple occurrences of such hazards during the relatively long service life of systems. This paper introduces a comprehensive framework for the assessment of lifecycle cost of infrastructures subject to multiple hazard events throughout their decision‐making time horizon. The framework entails the lifecycle costs of maintenance and repair, as well as the salvage value of the structure at the end of the decision‐making time horizon. The primary features of the proposed framework include accounting for the possibility of multiple hazard occurrences, incorporating effects of incomplete repair actions on the accumulated damage through damage state‐dependent repair times, and requiring limited resources in terms of input data and computational costs. A dynamic programming procedure is proposed to calculate the expected damage condition of the structure for each possibility of the number of hazard incidents based on state‐dependent fragility curves. The proposed framework is applied to a moment‐frame building located in a region with high seismicity, and lifecycle costs are evaluated for six retrofit plans. The results displayed variation in the ranking of the retrofit actions with respect to decision‐making time horizon. Furthermore, the sensitivity analyses demonstrated that disregarding repair time in the lifecycle cost analysis can result in false identification of unsafe retrofit actions as optimal and reliable strategies. Copyright © 2016 John Wiley & Sons, Ltd.
Thermal weathering of granite spheroidal boulders in a dry‐temperate climate, Northern Dobrogea, Romania
Authors: Vasile Mirela , Vespremeanu‐Stroe Alfred
Published: May 2016

Weathering microforms associated with exfoliation were investigated on 40 granitic spheroidal boulders identified on Pricopan Ridge (Măcin Mountains) in order to establish a spatial distribution pattern. Continuous thermal monitoring allowed the frequency and intensity distribution assessment of short‐term temperature changes triggered by summer storms, of intense day–night amplitudes and frost cycles across a uniform rounded boulder. Rock strength estimated by Schmidt hammer tests differentiates a significantly weaker resistance on the southern face of the boulders (rebound values of 27 to 33) in comparison with the northern face (43–50). The lowest resistance of the north–south cross‐boulder profile corresponds to the southern gentle slopes (0°–45°) thus defining the most susceptible area to exfoliation and other weathering processes. It is argued that this low‐resistant sector fits well with the maximum frequency and intensity of thermal processes recorded on the low and mid slopes (0°–45°) of the boulders south side, with small differences from one process to another, whilst the sector of 20° to 30° south corresponds to the peak activity of all. In accordance, the overlay map of exfoliated surfaces places the high frequency area on a spherical cap developed similarly (between 5° north and 45° south). The smallest exfoliated surfaces normally appear around 30° south and are inferred to extend in time both to the boulder top and downslope. The correlations between the frequency/intensity maps of thermal processes and the frequency map of exfoliated surfaces point to a complementary action in the exfoliated surfaces development of the short‐term temperature changes and diurnal cooling and heating due to the directional insolation effect, as similarly inferred in the development of meridional cracks. Copyright © 2016 John Wiley & Sons, Ltd.
Phase‐field modelling of fracture in single crystal plasticity
Authors: De Lorenzis L. , McBride A. , Reddy B.D.
Published: May 2016

We propose a phase‐field model for ductile fracture in a single crystal within the kinematically linear regime, by combining the theory of single crystal plasticity as formulated in Gurtin et al. [1] and the phase‐field formulation for ductile fracture proposed by Ambati et al. [2]. The model introduces coupling between plasticity and fracture through the dependency of the socalled degradation function from a scalar global measure of the accumulated plastic strain on all slip systems. A viscous regularization is introduced both in the treatment of plasticity and in the phase‐field evolution equation. Testing of the model on two examples for face centred cubic single crystals indicates that fracture is predicted to initiate and develop in the regions of the maximum accumulated plastic strain, which is in agreement with phenomenological observations. A rotation of the crystallographic unit cell is shown to affect the test results in terms of failure pattern and corresponding global and local response. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Modeling and numerical simulation of crack growth and damage with a phase field approach
Authors: Weinberg Kerstin , Dally Tim , Schuß Stefan , Werner Marek , Bilgen Carola
Published: May 2016

Phase field methods allow for convenient and efficient moving interface simulations. In this paper phase field approaches of different order are presented, and applied to simulate damage in solids of temperature dependent and non‐linear elastic materials. The numerical framework provides a NURBS based finite element method which minimizes the numerical and computational effort without impairing the smoothness required by the problem.

In order to demonstrate the possibilities of such general phase field approaches a series of different models from material science and fracture mechanics is investigated. Specifically, a priori unknown crack propagation in different fracture modes is studied, simulations of thermomigration in a technical alloy and of void growth are presented and an inverse analysis of a dynamic fracture experiment is performed. The examples show the versatility of the presented low‐order and high‐order phase field approaches. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Modeling of crack propagation on a mesoscopic length scale
Authors: Nestler Britta , Schneider Daniel , Schoof Ephraim , Huang Yunfei , Selzer Miachael , Nachname Vorname
Published: May 2016

Modeling of crack propagation in materials has long been a challenge in solid‐state physics and materials science. The phase‐field method is basically developed for modeling solidification processes and has now established as one of the tools for the description of crack propagation. The applied models are thermodynamically consistent and predict crack propagation in homogeneous materials under the consideration of different loading types, multiple physical fields, geometrical and physical nonlinearities. One of the open challenges is the modeling of crack propagation on a mesoscopic length scale in multiphase or multi‐grain systems. In this work, we summarize our preliminary work to get closer to the goal of describing crack propagation on a mesoscopic length scale. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Phase field modeling of electrochemically induced fracture in Li‐ion battery with large deformation and phase segregation
Authors: Xu Bai‐Xiang , Zhao Ying , Stein Peter
Published: May 2016

A finite strain phase field fracture model is presented which treats phase segregation, fracture and the related electrochemical reaction in rechargeable Li‐ion battery electrodes in a systematic manner. In particular, a regularized electrochemical reaction model is proposed to account for the reaction on the freshly generated diffusive fracture surface. It is shown that this model is equivalent to the reaction model on a sharp surface. With this regularized formulation, the reaction induced source term is added into the Cahn‐Hilliard type evolution equation. Moreover, to ensure that hydrostatic pressure makes no contribution to fracture, a decomposition of the elastic strain energy is proposed. The fracture model is implemented with isogeometric finite element method and used to numerically study the interaction among phase interface, fracture and electrochemical reaction. Simulations show that phase interface can induce crack branching. The electrochemical reaction induced crack formation from micro pores is also observed. Detailed analysis demonstrates that the model takes reasonably into account phase segregation, fracture, electrochemical reaction, and especially their interplay. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Factors determining the balance between the wish to die and the wish to live in older adults
Authors: Bonnewyn Anke , Shah Ajit , Bruffaerts Ronny , Demyttenaere Koen
Published: May 2016

Background

The “Internal Struggle Hypothesis” (Kovacs and Beck, ) suggests that suicidal persons may have both a wish to live (WTL) and a wish to die (WTD). The current study investigates whether the three‐group typology – “WTL”, “ambivalent (AMB)”, and “WTD” – is determined by common correlates of suicidality and whether these groups can be ordinally ranked.

Methods

The sample comprised 113 older inpatients. Discriminant analysis was used to create two functions (combining social, psychiatric, psychological, and somatic variables) to predict the assignment of older inpatients into the groups WTL, AMB, and WTD.

Results

The functions “Subjective Well‐being” and “Social Support” allowed us to assign patients into these three distinct groups with good accuracy (66.1%). “Subjective Well‐being” contrasted the groups WTD and WTL and “Social Support” discriminated between the groups WTD and AMB. “Social Support” was highest in the AMB group.

Conclusions

Our results suggest a simultaneous presence of a WTL and a WTD in older inpatients, and also that the balance between them is determined by “Subjective Well‐being” and “Social Support”. Unexpectedly, the AMB group showed the highest scores on “Social Support”. We hypothesize that higher social support might function as an important determinant of a remaining WTL when a WTD is present because of a lower sense of well‐being. The study suggests that the groups WTL–AMB–WTD can not situated on a one‐dimensional continuum. Copyright © 2016 John Wiley & Sons, Ltd.
Exposure to psychotropics in the French older population living with dementia: a nationwide population‐based study
Authors: Breining Alice , Bonnet‐Zamponi Dominique , Zerah Lorène , Micheneau Carole , Riolacci‐Dhoyen Nathalie , Chan‐Chee Christine , Deligne Jean , Harlin Jean‐Marc , Boddaert Jacques , Verny Marc , Leperre‐Desplanques Armelle
Published: May 2016

Background

Little is known about the level of psychotropic chronic exposure in all patients living with dementia. The aim of the study was to quantify chronic psychotropic exposure in older adults with dementia compared with the general population of the same age.

Methods

This prospective cohort study was conducted in France between 2009 and 2011. Aged at least 65 years, 10,781,812 individuals (440,215 of them with dementia) either community based or nursing home residents were included. The numbers of single or combined prescriptions, per year for antipsychotics, antidepressants, anxiolytics, or hypnotics were measured.

Results

Of patients with dementia, 15.5% are exposed to antipsychotics compared with 2.2% of the age‐matched population (relative risk [RR] = 6.44, 95% confidence interval [CI] [6.39−6.48]), 39.5% to antidepressants compared with 12.6% (RR = 4.10, 95% CI [.4.07–4.12]), and 39.6% to anxiolytics or hypnotics compared with 26.9% (RR = 1.74, 95% CI [1.72–1.75]). Among older adults with dementia, 13.8% simultaneously consumed at least three psychotropics. All class age of older patients with dementia is more exposed to all psychotropics except for long‐acting benzodiazepines. During the study period, chronic anxiolytic/hypnotic and antipsychotic exposure slightly decreased in population with dementia while chronic exposure to antidepressant drugs tended to increase.

Conclusion

This nationwide, population‐based, drug‐used study showed for the first time that older patients with dementia are chronically overexposed not only to antipsychotics but also to psychotropics.
Pathway to neural resilience: Self‐esteem buffers against deleterious effects of poverty on the hippocampus
Authors: Wang Yinan , Zhang Lin , Kong Xiangzhen , Hong Yingyi , Cheon Bobby , Liu Jia
Published: May 2016

Human neuroimaging studies have shown that people living in poverty tend to suffer hippocampal atrophy, which leads to impaired memory and learning throughout life. However, behavioral studies demonstrate that poor people with high self‐esteem are often exempt from the deleterious effect of poverty and instead possess a happy and successful life. Here we investigated whether high self‐esteem can buffer against the deleterious effects of poverty, as indicated by low subjective socioeconomic status (SSS), on the hippocampal gray matter volume (GMV) in a large cohort of young participants (N = 280). As expected, findings revealed that although low (vs. high) SSS was linked with a smaller hippocampal GMV, the deleterious effect of low SSS on hippocampal GMV was alleviated when the participants have high self‐esteem. Commonality analyses further confirmed this observation. The current study suggests that positive psychological resources such as self‐esteem may provide protection for the hippocampal atrophy in adversity. Hum Brain Mapp 37:3757–3766, 2016. © 2016 Wiley Periodicals, Inc.
Connectivity between mPFC and PCC predicts post‐choice attitude change: The self‐referential processing hypothesis of choice justification
Authors: Tompson Steven , Chua Hannah Faye , Kitayama Shinobu
Published: May 2016

Prior research shows that after making a choice, decision makers shift their attitudes in a choice‐congruous direction. Although this post‐choice attitude change effect is robust, the neural mechanisms underlying it are poorly understood. Here, we tested the hypothesis that decision makers elaborate on their choice in reference to self‐knowledge to justify the choice they have made. This self‐referential processing of the choice is thought to play a pivotal role in the post‐choice attitude change. Twenty‐four young American adults made a series of choices. They also rated their attitudes toward the choice options before and after the choices. In support of the current hypothesis, we found that changes in functional connectivity between two putative self‐regions (medial prefrontal cortex and posterior cingulate cortex/precuneus]) during the post‐choice (vs. pre‐choice) rating of the chosen options predicted the post‐choice shift of the attitudes toward the chosen options. This finding is the first to suggest that cognitive integration of various self‐relevant cognitions is instrumental in fostering post‐choice attitude change. Hum Brain Mapp 37:3810–3820, 2016. © 2016 Wiley Periodicals, Inc.
Acute white matter changes following sport‐related concussion: A serial diffusion tensor and diffusion kurtosis tensor imaging study
Authors: Lancaster Melissa A. , Olson Daniel V. , McCrea Michael A. , Nelson Lindsay D. , LaRoche Ashley A. , Muftuler L. Tugan
Published: May 2016

Recent neuroimaging studies have suggested that following sport‐related concussion (SRC) physiological brain alterations may persist after an athlete has shown full symptom recovery. Diffusion MRI is a versatile technique to study white matter injury following SRC, yet serial follow‐up studies in the very acute stages following SRC utilizing a comprehensive set of diffusion metrics are lacking. The aim of the current study was to characterize white matter changes within 24 hours of concussion in a group of high school and collegiate athletes, using Diffusion Tensor and Diffusion Kurtosis Tensor metrics. Participants were reassessed a week later. At 24 hours post‐injury, the concussed group reported significantly more concussion symptoms than a well‐matched control group and demonstrated poorer performance on a cognitive screening measure, yet these differences were nonsignificant at the 8‐day follow‐up. Similarly, within 24‐hours after injury, the concussed group exhibited a widespread decrease in mean diffusivity, increased axial kurtosis and, to a lesser extent, decreased axial and radial diffusivities compared with control subjects. At 8 days post injury, the differences in these diffusion metrics were even more widespread in the injured athletes, despite improvement of symptoms and cognitive performance. These MRI findings suggest that the athletes might not have reached full physiological recovery a week after the injury. These findings have significant implications for the management of SRC because allowing an athlete to return to play before the brain has fully recovered from injury may have negative consequences. Hum Brain Mapp 37:3821–3834, 2016. © 2016 Wiley Periodicals, Inc.
Risk Selection under Public Health Insurance with Opt‐Out
Authors: Panthöfer Sebastian
Published: May 2016

This paper studies risk selection between public and private health insurance when some, but not all, individuals can opt out of otherwise mandatory public insurance. Using a theoretical model, I show that public insurance is adversely selected when insurers and insureds are symmetrically informed about health‐related risks, and that there can be adverse or advantageous selection when insureds are privately informed. Using data from the German Socio‐Economic Panel, I find that (i) public insurance is, on balance, adversely selected under the German public health insurance with opt out scheme, (ii) individuals advantageously select public insurance based on risk aversion and residential location, and (iii) there is suggestive evidence of asymmetric information in the market for private health insurance. Copyright © 2016 John Wiley & Sons, Ltd.
Incidence and epidemiology of non‐Hodgkin lymphoma and risk of second malignancy among 22 466 survivors in Israel with 30 years of follow‐up
Authors: Tadmor Tamar , Liphshitz Irena , Silverman Barbara , Polliack Aaron
Published: May 2016

Previous studies have shown an increase risk of second malignancies after non‐Hodgkin's lymphoma (NHL), which is probably related to a combination of factors including genetic predisposition, molecular background, host immunological status and therapy administered. Here, we determined the incidence of NHL and risk of second solid tumours and haematological malignancies among survivors of NHL diagnosed in Israel during 1980–2011. Data were collected from the records of the Israeli National Cancer Registry. The total cohort of 24 666 NHL‐patients included 22 601 Jews and 2065 Arabs. Median age of diagnosis for Jews was 61.3 years and 48.2 for Arab patients. Of the Jews with NHL, 11 265 (50%) were of European–American origin, 5005 (22%) Asian or African and 6114 (27%) were born in Israel. Second cancers were recorded in 2010 NHL survivors, 1918 Jews and 92 Arabs, representing a rate of 8.5%, and 4.5% o, respectively. Second malignancies in all recorded sites were more frequent than in the general population, with a standardized incidence ratio (SIR) of 1.28 for Jewish men, 1.25 for Jewish women, 1.73 for Arab men and 1.98 for Arab women. This higher risk was even more pronounced for the 309 cases with secondary haematological malignancies (secondary haematological malignancies of 1.97, 1.81, 4.48 and 4.15, respectively). Our findings show that there is an increased risk of second malignancies occurring after diagnosis of NHL in Israel, particularly for haematological malignancies such as leukaemia and NHL. The differences we report in the incidence of NHL and the types of second malignancies occurring among Jews and Arabs suggest that ethnicity and genetic susceptibility may be important relevant risk factors. Copyright © 2016 John Wiley & Sons, Ltd.
Beta‐2 microglobulin as a significant prognostic factor and a new risk model for patients with diffuse large B‐cell lymphoma
Authors: Kanemasa Yusuke , Shimoyama Tatsu , Sasaki Yuki , Tamura Miho , Sawada Takeshi , Omuro Yasushi , Hishima Tsunekazu , Maeda Yoshiharu
Published: May 2016

Previous reports have evaluated the prognostic value of serum beta‐2 microglobulin (B2MG) level in patients with non‐Hodgkin lymphoma. However, its role in predicting clinical outcome of patients with diffuse large B‐cell lymphoma (DLBCL) in the rituximab era has not been extensively investigated. Here, we evaluated the prognostic value of B2MG and proposed a new prognostic model including B2MG for patients with DLBCL. A total of 274 patients with newly diagnosed de novo DLBCL were retrospectively analyzed. We defined the best cutoff value as 3.2 mg/L by using a receiver operating characteristic curve. Patients with a B2MG level ≥3.2 mg/L had significantly lower overall survival (OS) and progression‐free survival than those with a B2MG level <3.2 mg/L (3‐year OS, 50.9% vs. 89.4%, p < 0.001; 3‐year progression‐free survival, 45.3% vs. 79.7%, p < 0.001). Multivariate analysis showed that B2MG, age, performance status, and Ann Arbor stage were independent prognostic factors for OS. We developed a new prognostic model consisting of these four significant factors. We stratified patients into four‐risk groups: low (L, 0 factor), low‐intermediate (LI, 1–2 factors), high‐intermediate (HI, 3 factors), high (H, 4 factors). This new prognostic model showed better risk discrimination compared with the National Comprehensive Cancer Network‐International Prognostic Index (5‐year OS: 100% and 23.4% vs. 100% and 27.1%, in L and H risk groups, respectively). Our study suggested that B2MG level is a significant prognostic factor in patients with DLBCL. A new prognostic index composed of age, performance status, stage, and B2MG could stratify the outcomes of patients with DLBCL effectively and appears to be a valuable risk model for these patients. Copyright © 2016 John Wiley & Sons, Ltd.
Targeting of Mesenchymal Stromal Cells by Cre-Recombinase Transgenes Commonly Used to Target Osteoblast Lineage Cells
Authors: Zhang Jingzhu , Link Daniel C
Published: May 2016

The targeting specificity of tissue-specific Cre-recombinase transgenes is a key to interpreting phenotypes associated with their use. The Ocn-Cre and Dmp1-Cre transgenes are widely used to target osteoblasts and osteocytes, respectively. Here, we used high-resolution microscopy of bone sections and flow cytometry to carefully define the targeting specificity of these transgenes. These transgenes were crossed with Cxcl12gfp mice to identify Cxcl12-abundant reticular (CAR) cells, which are a perivascular mesenchymal stromal population implicated in hematopoietic stem/progenitor cell maintenance. We show that in addition to osteoblasts, Ocn-Cre targets a majority of CAR cells and arteriolar pericytes. Surprisingly, Dmp1-Cre also targets a subset of CAR cells, in which expression of osteoblast-lineage genes is enriched. Finally, we introduce a new tissue-specific Cre-recombinase, Tagln-Cre, which efficiently targets osteoblasts, a majority of CAR cells, and both venous sinusoidal and arteriolar pericytes. These data show that Ocn-Cre and Dmp1-Cre target broader stromal cell populations than previously appreciated and may aid in the design of future studies. Moreover, these data highlight the heterogeneity of mesenchymal stromal cells in the bone marrow and provide tools to interrogate this heterogeneity. © 2016 American Society for Bone and Mineral Research.