bluuebunny/crossref_metadata_2025 huggingface dataset:
K2Mn4O8/Reduced Graphene Oxide Nanocomposites for Excellent Lithium Storage and Adsorption of Lead Ions
Authors: Hao Shu‐Meng , Qu Jin , Yang Jing , Gui Chen‐Xi , Wang Qian‐Qian , Li Qian‐Jie , Li Xiaofeng , Yu Zhong‐Zhen
Published: February 2016

Ion diffusion efficiency at the solid–liquid interface is an important factor for energy storage and adsorption from aqueous solution. Although K2Mn4O8 (KMO) exhibits efficient ion diffusion and ion‐exchange capacities, due to its high interlayer space of 0.70 nm, how to enhance its mass transfer performance is still an issue. Herein, novel layered KMO/reduced graphene oxide (RGO) nanocomposites are fabricated through the anchoring of KMO nanoplates on RGO with a mild solution process. The face‐to‐face structure facilitates fast transfer of lithium and lead ions; thus leading to excellent lithium storage and lead ion adsorption. The anchoring of KMO on RGO not only increases electrical conductivity of the layered nanocomposites, but also effectively prevents aggregation of KMO nanoplates. The KMO/RGO nanocomposite with an optimal RGO content exhibits a first cycle charge capacity of 739 mA h g−1, which is much higher than that of KMO (326 mA h g−1). After 100 charge–discharge cycles, it still retains a charge capacity of 664 mA h g−1. For the adsorption of lead ions, the KMO/RGO nanocomposite exhibits a capacity of 341 mg g−1, which is higher than those of KMO (305 mg g−1) and RGO (63 mg g−1) alone.
Unravelling Mechanistic Aspects of the Gas‐Phase Ethanol Conversion: An Experimental and Computational Study on the Thermal Reactions of MO2+ (M=Mo, W) with Ethanol
Authors: González‐Navarrete Patricio , Schlangen Maria , Wu Xiao‐Nan , Schwarz Helmut
Published: February 2016

The ion/molecule reactions of molybdenum and tungsten dioxide cations with ethanol have been studied by Fourier transform ion‐cyclotron resonance mass spectrometry (FT‐ICR MS) and density functional theory (DFT) calculations. Dehydration of ethanol has been found as the dominant reaction channel, while generation of the ethyl cation corresponds to a minor product. Cleary, the reactions are mainly governed by the Lewis acidity of the metal center. Computational results, together with isotopic labeling experiments, show that the dehydration of ethanol can proceed either through a conventional concerted [1,2]‐elimination mechanism or a step‐wise process; the latter occurs via a hydroxyethoxy intermediate. Formation of C2H5+ takes place by transfer of OH− from ethanol to the metal center of MO2+. The molybdenum and tungsten dioxide cations exhibit comparable reactivities toward ethanol, and this is reflected in similar reaction rate constants and branching ratios.
Discovery, Characterization, and Analogue Synthesis of Bohemamine Dimers Generated by Non‐enzymatic Biosynthesis
Authors: Fu Peng , Legako Aaron , La Scott , MacMillan John B.
Published: February 2016

Dibohemamines A–C (5–7), three new dimeric bohemamine analogues dimerized through a methylene group, were isolated from a marine‐derived Streptomyces spinoverrucosus. The structures determined by spectroscopic analysis were confirmed through the semi‐synthetic derivatization of monomeric bohemamines and formaldehyde. These reactions, which could occur under mild conditions, together with the detection of formaldehyde in the culture, revealed that this dimerization is a non‐enzymatic process. In addition to the unique dimerization of the dibohemamines, dibohemamines B and C were found to have nm cytotoxicity against the non‐small cell‐lung cancer cell line A549. In view of the potent cytotoxicity of compounds 6 and 7, a small library of bohemamine analogues was generated for biological evaluation by utilizing a series of aryl and alkyl aldehydes.
Direct Catalytic Asymmetric Mannich‐type Reaction of α,β‐Unsaturated γ‐Butyrolactam with Ketimines
Authors: Lin Shaoquan , Kumagai Naoya , Shibasaki Masakatsu
Published: February 2016

We report a direct catalytic asymmetric Mannich‐type addition of α,β‐unsaturated γ‐butyrolactam to α‐ethoxycarbonyl ketimines promoted by a soft Lewis acid/Brønsted base cooperative catalyst. A thiophosphinoyl group on the nitrogen of ketimines was crucial for both electrophilic activation and α‐addition of γ‐butyrolactams. The obtained aza‐Morita–Baylis–Hillman‐type products bear an α‐amino acid architecture with a tetra‐substituted stereogenic center.
N‐Heterocyclic Carbene Ligand‐Enabled C(sp3)−H Arylation of Piperidine and Tetrahydropyran Derivatives
Authors: Ye Shengqing , Yang Weibo , Coon Timothy , Fanning Dewey , Neubert Tim , Stamos Dean , Yu Jin‐Quan
Published: February 2016

PdII‐catalyzed C(sp3)−H arylation of saturated heterocycles with a wide range of aryl iodides is enabled by an N‐heterocyclic carbene (NHC) ligand. A C(sp3)−H insertion step by the PdII/NHC complex in the absence of ArI is demonstrated experimentally for the first time. Experimental data suggests that the previously established NHC‐mediated Pd0/PdII catalytic manifold does not operate in this reaction. This transformation provides a new approach for diversifying pharmaceutically relevant piperidine and tetrahydropyran ring systems.
Entwicklung eines Messgeräts zur Kopplung von kalorimetrischen und volumetrischen Sorptionsmessungen
Authors: Bläker Christian , Luckas Michael , Pasel Christoph , Dreisbach Frieder , Bathen Dieter
Published: February 2016

Zur simultanen Messung von Adsorptionsenthalpie und Beladung wurde eine neue Messmethodik entwickelt. Ein volumetrisches Adsorptionsmessgerät wird durch eine kalorimetrische Messanordnung erweitert, in der die Druckdifferenz zwischen zwei identischen Sensorgasvolumina gemessen wird, die eine Messzelle und eine Referenzzelle umschließen. Bei der Adsorption tritt infolge der Sorptionswärme ein Druckanstieg im Gasvolumen um die Messzelle auf. Aus dem zeitlichen Verlauf lässt sich nach einer Kalibrierung die Sorptionswärme berechnen. Erste Ergebnisse der Adsorptionsenthalpie von CO2 an einem 13X‐Zeolithen werden gezeigt.
Professor Dr. Lothar Jaenicke
Authors: Offermanns Heribert
Published: February 2016

Am 29. 12. 2015 verstarb in gesegnetem Alter der emeritierte Professor der Biochemie der Universität Köln, Lothar Jaenicke, ein herausragender akademischer Lehrer und Forscher, ein bemerkenswerter Biograph, ein bedeutender Übersetzer und Rezensent, ein geschätzter Autor der ChiuZ, dem es auch immer ein Anliegen war, dass in der Wissenschaft “Unverständlichkeit nicht zu Unverständnis führt!”. Noch im Jahr seines Todes schrieb er Beiträge für die ChiuZ (Ligninver”wert”ung und Die Ammoniak‐Brennstoffzelle wird Reaktor).
Grünes Rot: chlorfreie Pyrotechnik
Authors: Nowack Ricardo
Published: February 2016

Rote Pyrotechnik ist jedem Fan von Feuerwerkskunst bekannt: Wenn es knallt und Farbblitze den Himmel erhellen, sind Explosivstoffe im Spiel [1]. Doch auch in der Schifffahrt als Notsignal oder im Militär als Signalleuchte kommen rote Leuchtsätze zum Einsatz. Allerdings ist ihre Verwendung unabhängig vom Einsatzgebiet problematisch, weil sie unter Verdacht stehen, dass sie gesundheitsgefährdend sind. Eine Gruppe von Explosivstoffforschern schlägt daher alternative Chemikalienmischungen vor, die ebenso brillant und lichtintensiv sind, aber gesundheitlich unbedenklich.
Multiferroicity Broken by Commensurate Magnetic Ordering in Terbium Orthomanganite
Authors: Zhang Hao , Flacau Roxana , Du Xin , Manuel Pascal , Cong Junzhuang , Sun Young , Sun Junliang , Yang Sihai , Li Guobao , Liao Fuhui , Lin Jianhua
Published: February 2016

TbMnO3 is an important multiferroic material with strong coupling between magnetic and ferroelectric orderings. Incommensurate magnetic ordering is suggested to be vital for this coupling in TbMnO3, which can be modified by doping at the site of Tb and/or Mn. Our study shows that a self‐doped solid solution Tb1−xMnyMnO3 (y≤x) can be formed with Mn doped into the site of Tb of TbMnO3. When y is small Tb1−xMnyMnO3 shows both ferroelectric and incommensurate magnetic orders at low temperature, which is similar to TbMnO3. However, if y is large enough, a commensurate antiferromagnetic ordering appears along with the incommensurate magnetic ordering to prevent the appearance of multiferroicity in Tb1−xMnyMnO3. That is to say, the magnetoeletric coupling can be broken by the co‐existence of a commensurate antiferromagnetic ordering. This finding may be useful to the study of TbMnO3.
Coupling Electrochemistry with Probe Electrospray Ionization Mass Spectrometry
Authors: Cai Yi , Liu Pengyuan , Held Michael A. , Dewald Howard D. , Chen Hao
Published: February 2016

A new coupling of electrochemistry with mass spectrometry (MS) using probe electrospray ionization (PESI) is presented. Due to the high salt tolerance of PESI, the detection of electrochemical reaction products in room‐temperature ionic liquids (RTILs) is realized for the first time. Furthermore, PESI‐MS allows the analysis of electrochemical reaction products on different or multiple electrode surfaces. In addition, peptides and proteins fractionated through isoelectric focusing (IEF) in the presence of an external electric field can also be directly analyzed by using PESI‐MS, suggesting a new and rapid characterization means for the IEF technique. This study reveals the versatility of EC/PESI‐MS, which could have an impact in electrochemistry and bioanalysis fields.
Copper‐Based Catalysts Supported on Highly Porous Silica for the Water Gas Shift Reaction
Authors: Marras Claudia , Loche Danilo , Carta Daniela , Casula Maria Francesca , Schirru Manuela , Cutrufello Maria Giorgia , Corrias Anna
Published: February 2016

Copper‐based nanoparticles, supported on either a silica aerogel or cubic mesostructured silicas obtained by using two different synthetic protocols, were used as catalysts for the water gas shift reaction. The obtained nanocomposites were thoroughly characterised before and after catalysis through nitrogen adsorption–desorption measurements at −196 °C, TEM, and wide‐ and low‐angle XRD. The samples before catalysis contained nanoparticles of copper oxides (either CuO or Cu2O), whereas the formation of metallic copper nanoparticles, constituting the active catalytic phase, was observed either by using pre‐treatment in a reducing atmosphere or directly during the catalytic reaction owing to the presence of carbon monoxide. A key role in determining the catalytic performances of the samples is played by the ability of different matrices to promote a high dispersion of copper metal nanoparticles. The best catalytic performances are obtained with the aerogel sample, which also exhibits constant carbon monoxide conversion values at constant temperature and reproducible behaviour after subsequent catalytic runs. On the other hand, in the catalysts based on cubic mesostructured silica, the detrimental effects related to sintering of copper nanoparticles are avoided only on the silica support, which is able to produce a reasonable dispersion of the copper nanophase.
Nitrogen and Phosphorous Co‐Doped Graphene Monolith for Supercapacitors
Authors: Wen Yangyang , Rufford Thomas E. , Hulicova‐Jurcakova Denisa , Wang Lianzhou
Published: February 2016

The co‐doping of heteroatoms has been regarded as a promising approach to improve the energy‐storage performance of graphene‐based materials because of the synergetic effect of the heteroatom dopants. In this work, a single precursor melamine phosphate was used for the first time to synthesise nitrogen/phosphorus co‐doped graphene (N/P‐G) monoliths by a facile hydrothermal method. The nitrogen contents of 4.27–6.58 at % and phosphorus levels of 1.03–3.00 at % could be controlled by tuning the mass ratio of melamine phosphate to graphene oxide in the precursors. The N/P‐G monoliths exhibited excellent electrochemical performances as electrodes for supercapacitors with a high specific capacitance of 183 F g−1 at a current density of 0.05 A g−1, good rate performance and excellent cycling performance. Additionally, the N/P‐G electrode was stable at 1.6 V in 1 m H2SO4 aqueous electrolyte and delivered a high energy density of 11.33 Wh kg−1 at 1.6 V.
Catalytic Hydrotreatment of Humins in Mixtures of Formic Acid/2‐Propanol with Supported Ruthenium Catalysts
Authors: Wang Yuehu , Agarwal Shilpa , Kloekhorst Arjan , Heeres Hero Jan
Published: February 2016

The catalytic hydrotreatment of humins, which are the solid byproducts from the conversion of C6 sugars (glucose, fructose) into 5‐hydroxymethylfurfural (HMF) and levulinic acid (LA), by using supported ruthenium catalysts has been investigated. Reactions were carried out in a batch setup at elevated temperatures (400 °C) by using a hydrogen donor (formic acid (FA) in isopropanol (IPA) or hydrogen gas), with humins obtained from d‐glucose. Humin conversions of up to 69 % were achieved with Ru/C and FA, whereas the performance for Ru on alumina was slightly poorer (59 % humin conversion). Humin oils were characterized by using a range of analytical techniques (GC, GC–MS, GCxGC, gel permeation chromatography) and were shown to consist of monomers, mainly alkyl phenolics (>45 % based on compounds detectable by GC) and higher oligomers. A reaction network for the reaction is proposed based on structural proposals for humins and the main reaction products.
Hierarchical Zeolites with Amine‐Functionalized Mesoporous Domains for Carbon Dioxide Capture
Authors: Nguyen Tien Hoa , Kim Sungjune , Yoon Minyoung , Bae Tae‐Hyun
Published: February 2016

To prepare materials with high CO2 adsorption, a series of hierarchical LTA zeolites possessing various mesopore spaces that are decorated with alkylamines was designed and synthesized. The highest CO2 uptake capacity was achieved when (3‐aminopropyl)trimethoxysilane (APTMS) was grafted onto the hierarchical LTA zeolite having the largest mesopores. Owing to the contributions of both alkylamine groups grafted onto the mesopore surfaces and active sites in the LTA zeolites, the amount of CO2 that can be taken up on these materials is much higher than for conventional aminosilicas such SBA‐15 and MCM‐41. Furthermore, the adsorbent shows good CO2 uptake capacity and recyclability in dynamic flow conditions.
Homogenizing effects of cities on North American winter bird diversity
Authors: Murthy Adeline C. , Fristoe Trevor S. , Burger Joseph R.
Published: February 2016

Urbanization is widespread throughout the United States and Canada. Studies at different scales have shown mixed consequences of urban areas for ecological communities and biodiversity. Here, we use geographic data on urban extent and survey data from the Christmas Bird Count to investigate the influence of urbanization on winter bird diversity over a continental scale. We compared the alpha (local richness) and beta diversity (turnover with distance) of 42 urban bird communities to nearby non‐urban communities. We investigated the processes underlying beta diversity between non‐urban and urban sites by comparing the frequency of occurrence in species and variability in relative abundances across sites. Alpha diversity was statistically indistinguishable between urban and non‐urban sites when controlling for latitude. Community similarity decreased less rapidly over distance in urban compared to non‐urban sites, indicating that spatial homogenization from urbanization results in lower beta diversity. Eighteen species of non‐native or native generalists occurred across all urban sites, whereas no species occurred in all non‐urban sites. Mean‐variance scaling of relative abundance shows that species in urban sites maintained similar levels of community dominance across space compared to non‐urban sites. The widespread presence of urban species is likely due to similarity in habitats among cities compared to nearby non‐urban sites. The decreased variability in relative abundance of urban species is possibly due to urban resource subsidies (e.g., bird feeders, garbage, and irrigation) and shelter (e.g., landscaping, buildings, and microclimates). The increased occurrence of widespread species in cities and less variation in relative abundances across urban sites contribute to the homogenizing effect of cities on avian communities.
Mimicry of the 2‐His‐1‐Carboxylate Facial Triad Using Bulky N,N,O‐Ligands: Non‐Heme Iron Complexes Featuring a Single Facial Ligand and Easily Exchangeable Co‐Ligands
Authors: Folkertsma Emma , de Waard Esther F. , Korpershoek Gerda , van Schaik Arnoldus J. , Solozabal Mirón Naiara , Borrmann Mandy , Nijsse Sjoerd , Moelands Marcel A. H. , Lutz Martin , Otte Matthias , Moret Marc‐Etienne , Klein Gebbink Robertus J. M.
Published: February 2016

Mononuclear iron(II) complexes with facially coordinating N,N,O‐ligands were synthesized as accurate structural mimics of the 2‐His‐1‐carboxylate facial triad found in mononuclear non‐heme iron enzymes. Mimicking of the facial triad is achieved by designing sterically demanding ligands providing two histidine‐like benzimidazole moieties and a coordinating carboxylate or ester moiety. The new methyl‐substituted analogue of the bis(benzimidazolyl)propionate ligand, BMBMeIP and its ester analogue, BMBMeIPnPr are designed to prevent the formation of previously reported coordinatively saturated FeL2 type complexes. The crystal structure of [Fe(BMBMeIPnPr)(OTf)2] shows a facial N,N,O‐coordination that is very similar to the structure of the enzyme active sites. Both [Fe(BMBMeIPnPr)(OTf)2] and [Fe(BMBMeIP)(OTf)(MeCN)n] catalyze the epoxidation of olefins using H2O2, reaching turnover numbers up to 5.8 per iron. These results represent the first examples of iron complexes bearing a single facial and rigid N,N,O‐coordinating ligand and three readily available coordination sites showing catalytic activity in oxidation reactions.
Morphology, structure and kinematics of a rainfall controlled slow‐moving Andean landslide, Peru
Authors: Zerathe Swann , Lacroix Pascal , Jongmans Denis , Marino Jersy , Taipe Edu , Wathelet Marc , Pari Walter , Smoll Lionel Fidel , Norabuena Edmundo , Guillier Bertrand , Tatard Lucile
Published: February 2016

The large slow‐moving landslide of Maca is located in the upper Colca valley (southern Peru), a region characterized by a well pronounced rainy period, and intense and recurrent sustained seismicity. The landslide, developed in deep lacustrine deposits, has recently accelerated, threatening the Maca village. This work aims at understanding the rupture mechanism and the causes of the recent landslide reactivation/acceleration. We present a multidisciplinary characterization of the Maca landslide that includes: (i) geological and morphological mapping in the field; (ii) remote sensing analysis using an historical aerial photograph of 1955 and the Pléiades satellite images (2013); (iii) global positioning system (GPS) including time‐series of surveys over 13 years, and continuous measurements over 14 months; (iv) a geophysical campaign with deep electrical resistivity tomography profiles acquired across the landslide mass. Our study shows that this 60 Mm3 landslide, which can be classified as a clay/silt compound landslide, moved by 15 m between 2001 and 2014 with a large inter‐annual velocity variation (up to a factor of 500) depending on the rainfall intensity. We suggest that these dramatic changes in velocity are the result of the combination of a threshold mechanism and the short intense rainy season in Peru. This study reveals three main driving factors acting at different timescales: (i) over several decades, the river course has significantly changed, causing the Maca landslide reactivation in the 1980s due to the erosion of its toe; (ii) at the year scale, a minimum amount of rainfall is required to trigger the motion and this amount controls the landslide velocity; (iii) transient changes in slide velocity may occur anytime due to earthquakes. This study particularly highlights the non‐linear behaviour of the motion with rainfall. Copyright © 2016 John Wiley & Sons, Ltd.
IOFI recommended practice for the use of predicted relative‐response factors for the rapid quantification of volatile flavouring compounds by GC‐FID
Authors: Cachet T. , Brevard H. , Chaintreau A. , Demyttenaere J. , French L. , Gassenmeier K. , Joulain D. , Koenig T. , Leijs H. , Liddle P. , Loesing G. , Marchant M. , Merle Ph. , Saito K. , Schippa C. , Sekiya F. , Smith T.
Published: February 2016

This recommended practice enables the quantification of volatile compounds in flavourings to be made by gas chromatography with flame‐ionization detection, without having authentic compounds available, and also in many cases it can avoid time‐consuming calibration procedures. The relative‐response factors (RRF) can be predicted from the molecular formula of the compound, and this approach can be applied to compounds containing the atoms C, H, O, N, S, F, Cl, Br, I, and Si, providing that the molecular formula and number of benzene rings in the analytes are known. The purity of chemically‐defined flavouring substances or chromatographic standards can also be estimated using these predicted RRF, and this procedure can also be used to quantify (poly)hydroxylated compounds, after their derivatization into trimethylsilyl ethers or esters. Copyright © 2016 John Wiley & Sons, Ltd.
Assembly of juxtaparanodes in myelinating DRG culture: Differential clustering of the Kv1/Caspr2 complex and scaffolding protein 4.1B
Authors: Hivert Bruno , Pinatel Delphine , Labasque Marilyne , Tricaud Nicolas , Goutebroze Laurence , Faivre‐Sarrailh Catherine
Published: February 2016

The precise distribution of ion channels at the nodes of Ranvier is essential for the efficient propagation of action potentials along myelinated axons. The voltage‐gated potassium channels Kv1.1/1.2 are clustered at the juxtaparanodes in association with the cell adhesion molecules, Caspr2 and TAG‐1 and the scaffolding protein 4.1B. In the present study, we set up myelinating cultures of DRG neurons and Schwann cells to look through the formation of juxtaparanodes in vitro. We showed that the Kv1.1/Kv1.2 channels were first enriched at paranodes before being restricted to distal paranodes and juxtaparanodes. In addition, the Kv1 channels displayed an asymmetric expression enriched at the distal juxtaparanodes. Caspr2 was strongly co‐localized with Kv1.2 whereas the scaffolding protein 4.1B was preferentially recruited at paranodes while being present at juxtaparanodes too. Kv1.2/Caspr2 but not 4.1B, also transiently accumulated within the nodal region both in myelinated cultures and developing sciatic nerves. Studying cultures and sciatic nerves from 4.1B KO mice, we further showed that 4.1B is required for the proper targeting of Caspr2 early during myelination. Moreover, using adenoviral‐mediated expression of Caspr‐GFP and photobleaching experiments, we analyzed the stability of paranodal junctions and showed that the lateral stability of paranodal Caspr was not altered in 4.1B KO mice indicating that 4.1B is not required for the assembly and stability of the paranodal junctions. Thus, developing an adapted culture paradigm, we provide new insights into the dynamic and differential distribution of Kv1 channels and associated proteins during myelination. GLIA 2016;64:840–852
The mental health and mortality impact of death of a partner with dementia
Authors: Shah Sunil M. , Carey Iain M. , Harris Tess , DeWilde Stephen , Victor Christina R. , Cook Derek G.
Published: February 2016

Objective

Caring for a partner with dementia and partner bereavement are independently associated with poor health. An understanding of the health effects of living with a partner dying with dementia can help optimise support. We describe health in the year before and after loss of a partner with dementia compared with other bereavements.

Methods

In a UK primary care database, 2624 older individuals whose partner died with dementia during 2005–2012 were matched with 7512 individuals experiencing bereavement where the deceased partner had no dementia recorded.

Results

Prior to bereavement, partners of the deceased with dementia were more likely to be diagnosed with depression (OR 2.31, 1.69–3.14) and receive psychotropic medication (OR 1.34, 1.21–1.49) than partners from bereavements without dementia. In contrast, psychotropic medication initiation two months after dementia bereavement was lower (HR 0.69, 0.56–0.85). Compared with other bereaved individuals, mortality after bereavement was lower in men experiencing a dementia bereavement (HR 0.68, 0.49–0.94) but similar in women (HR 1.02, 0.75–1.38). Prior to bereavement, those who died with dementia were less likely to receive palliative care (OR 0.47, 0.41–0.54).

Conclusion

In the year before bereavement, partners of individuals dying with dementia experience poorer mental health than those facing bereavement from other causes, and their partner is less likely to receive palliative care. In the year after, individuals whose partner died with dementia experience some attenuation of the adverse health effects of bereavement. Services need to address the needs of carers for individuals dying with dementia and improve access to palliative care. Copyright © 2016 John Wiley & Sons, Ltd.
The bicaudate index inversely associates with performance in the Montreal Cognitive Assessment (MoCA) in older adults living in rural Ecuador. The Atahualpa project
Authors: Del Brutto Oscar H. , Mera Robertino M. , Del Brutto Victor J. , Sedler Mark J.
Published: February 2016

Objective

Assessment of cognitive impairment in rural areas of developing countries is complicated by illiteracy and cross‐cultural factors. A better way to estimate the usefulness of cognitive screening instruments is to evaluate their correlation with imaging biomarkers. The bicaudate index (a marker of central atrophy) correlates with cognitive performance. We assessed the relationship of the bicaudate index with the MoCA to estimate the usefulness of this test to detect individuals with cognitive decline in these regions.

Methods

Atahualpa residents aged ≥60 years identified during door‐to‐door surveys were evaluated with the MoCA and invited to undergo brain MRI. Using generalized linear models, we estimated whether the bicaudate index correlates with MoCA scores, after adjusting for demographics and relevant clinical and neuroimaging confounders.

Results

Out of 385 eligible persons, 290 (75%) were enrolled. Mean bicaudate index was 0.14 ± 0.03, and mean total MoCA score was 19 ± 5 points. Locally weighted scatterplot smoothing showed a nearly linear inverse relationship between the bicaudate index and the total MoCA score. In the fully adjusted generalized linear model, the bicaudate index was inversely associated with the total MoCA score (p < 0.001), which dropped by 5.3% (95% C.I.: 1.7%–8.8%) for every standard deviation of the bicaudate index. In addition, most domain‐specific MoCA scores were inversely associated with the bicaudate index.

Conclusions

The inverse relationship between the bicaudate index and the MoCA score provides evidence that the MoCA is reliable to detect structural brain damage and useful to assess cognitive performance in less educated individuals. Copyright © 2016 John Wiley & Sons, Ltd.
Impact of caregiver readiness on outcomes of a nonpharmacological intervention to address behavioral symptoms in persons with dementia
Authors: Gitlin Laura N. , Rose Karen
Published: February 2016

Background

Previous research shows that nonpharmacological strategies may effectively manage behavioral symptoms (agitation, wandering) in persons with dementia and improve caregiver wellbeing. However, strategies depend upon caregivers for their implementation. We examine the impact of caregiver readiness to use nonpharmacological strategies on treatment outcomes.

Methods

Data were from a randomized trial involving 110 family caregivers in the treatment group which received nonpharmacologic strategies for managing behavioral symptoms. Interventionists rated caregiver readiness to use nonpharmacologic strategies as pre‐action (precontemplation, contemplation, preparation) or action at treatment initiation and conclusion. Caregivers in pre‐action and action stages by treatment conclusion (16 weeks) were compared on proximal (frequency of, and caregiver upset and confidence with targeted behaviors) and more distal (caregiver burden and wellbeing) outcomes at 16 and 24‐week follow‐ups.

Results

By treatment conclusion, 28.2% (n = 31) and 71.8% (n = 79) of caregivers were rated at pre‐action and action respectively. Means for proximal outcomes differed between the groups at 16 and 24 weeks; those at action showed greater improvement on all proximal and distal outcomes. Hierarchical regressions showed significant relationships of readiness to targeted outcomes. By 24 weeks, caregiver readiness predicted lower frequency estimates of targeted behaviors (β = −.180, p = .041) and higher confidence (β = .27, p = .009). Readiness was not a significant predictor of caregiver burden and wellbeing at 16 or 24 weeks.

Conclusion

By treatment conclusion, >25% of participants were not activated to use nonpharmacologic strategies. Activated caregivers reported greater decline in distressing behavioral symptoms, and more confidence than non‐activated participants. Activation is needed to impact behavioral management but not other caregiver outcomes. Copyright © 2016 John Wiley & Sons, Ltd.
Quantitative multi‐image analysis for biomedical Raman spectroscopic imaging
Authors: Hedegaard Martin A. B. , Bergholt Mads S. , Stevens Molly M.
Published: February 2016

Imaging by Raman spectroscopy enables unparalleled label‐free insights into cell and tissue composition at the molecular level. With established approaches limited to single image analysis, there are currently no general guidelines or consensus on how to quantify biochemical components across multiple Raman images. Here, we describe a broadly applicable methodology for the combination of multiple Raman images into a single image for analysis. This is achieved by removing image specific background interference, unfolding the series of Raman images into a single dataset, and normalisation of each Raman spectrum to render comparable Raman images. Multivariate image analysis is finally applied to derive the contributing ‘pure’ biochemical spectra for relative quantification. We present our methodology using four independently measured Raman images of control cells and four images of cells treated with strontium ions from substituted bioactive glass. We show that the relative biochemical distribution per area of the cells can be quantified. In addition, using k‐means clustering, we are able to discriminate between the two cell types over multiple Raman images. This study shows a streamlined quantitative multi‐image analysis tool for improving cell/tissue characterisation and opens new avenues in biomedical Raman spectroscopic imaging.

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Evaluation of an injectable thermoresponsive hyaluronan hydrogel in a rabbit osteochondral defect model
Authors: D'Este Matteo , Sprecher Christoph Martin , Milz Stefan , Nehrbass Dirk , Dresing Iska , Zeiter Stephan , Alini Mauro , Eglin David
Published: February 2016

Articular cartilage displays very little self‐healing capabilities, generating a major clinical need. Here, we introduce a thermoresponsive hyaluronan hydrogel for cartilage repair obtained by covalently grafting poly(N‐isopropylacrylamide) to hyaluronan, to give a brush co‐polymer HpN. The gel is fluid at room temperature and becomes gel at body temperature. In this pilot study HpN safety and repair response were evaluated in an osteochondral defect model in rabbit. Follow‐up was of 1 week and 12 weeks and the empty defect served as a control, for a total of four experimental groups. At 12 weeks the defect sites were evaluated macroscopically and histologically. Local lymph nodes, spleen, liver, and kidneys were analyzed for histopathological evaluation. HpN could be easily injected and remained into the defect throughout the study. The macroscopic score was statistically superior for HpN versus empty. Histological score gave opposite trend but not statistically significant. A slight tissue reaction was observed around HpN, however, vascularization and subchondral bone formation were not impeded. An upper proteoglycans rich fibro‐cartilaginous tissue with fairly good continuity and lateral integration into the existing articular cartilage was observed in all cases. No signs of local or systemic acute or subacute toxicity were observed. In conclusion, HpN is easily injectable, remains into an osteochondral defect within a moving synovial joint, is biocompatible and does not interfere with the intrinsic healing response of osteochondral defects in a rabbit model. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 1469–1478, 2016.
Persistence, distribution, and impact of distinctly segmented microparticles on cochlear health following in vivo infusion
Authors: Ross Astin M. , Rahmani Sahar , Prieskorn Diane M. , Dishman Acacia F. , Miller Josef M. , Lahann Joerg , Altschuler Richard A.
Published: February 2016

Delivery of pharmaceuticals to the cochleae of patients with auditory dysfunction could potentially have many benefits from enhancing auditory nerve survival to protecting remaining sensory cells and their neuronal connections. Treatment would require platforms to enable drug delivery directly to the cochlea and increase the potential efficacy of intervention. Cochlear implant recipients are a specific patient subset that could benefit from local drug delivery as more candidates have residual hearing; and since residual hearing directly contributes to post‐implantation hearing outcomes, it requires protection from implant insertion‐induced trauma. This study assessed the feasibility of utilizing microparticles for drug delivery into cochlear fluids, testing persistence, distribution, biocompatibility, and drug release characteristics. To allow for delivery of multiple therapeutics, particles were composed of two distinct compartments; one containing polylactide‐co‐glycolide (PLGA), and one composed of acetal‐modified dextran and PLGA. Following in vivo infusion, image analysis revealed microparticle persistence in the cochlea for at least 7 days post‐infusion, primarily in the first and second turns. The majority of subjects maintained or had only slight elevation in auditory brainstem response thresholds at 7 days post‐infusion compared to pre‐infusion baselines. There was only minor to limited loss of cochlear hair cells and negligible immune response based on CD45+ immunolabling. When Piribedil‐loaded microparticles were infused, Piribedil was detectable within the cochlear fluids at 7 days post‐infusion. These results indicate that segmented microparticles are relatively inert, can persist, release their contents, and be functionally and biologically compatible with cochlear function and therefore are promising vehicles for cochlear drug delivery. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 1510–1522, 2016.
Focused grid‐based resampling for protein docking and mapping
Authors: Mamonov Artem B. , Moghadasi Mohammad , Mirzaei Hanieh , Zarbafian Shahrooz , Grove Laurie E. , Bohnuud Tanggis , Vakili Pirooz , Ch. Paschalidis Ioannis , Vajda Sandor , Kozakov Dima
Published: February 2016

The fast Fourier transform (FFT) sampling algorithm has been used with success in application to protein‐protein docking and for protein mapping, the latter docking a variety of small organic molecules for the identification of binding hot spots on the target protein. Here we explore the local rather than global usage of the FFT sampling approach in docking applications. If the global FFT based search yields a near‐native cluster of docked structures for a protein complex, then focused resampling of the cluster generally leads to a substantial increase in the number of conformations close to the native structure. In protein mapping, focused resampling of the selected hot spot regions generally reveals further hot spots that, while not as strong as the primary hot spots, also contribute to ligand binding. The detection of additional ligand binding regions is shown by the improved overlap between hot spots and bound ligands. © 2016 Wiley Periodicals, Inc.
Improvement of clinical outcomes in the patients with gallbladder cancer: lessons from periodic comparison in a tertiary referral center
Authors: Chang Jihoon , Jang Jin‐Young , Lee Kyoung Bun , Kang Mee Joo , Jung Woohyun , Shin Yong Chan , Kim Sun‐Whe
Published: February 2016

Background

Current guidelines for gallbladder cancer (GBC) contain controversies and some reported no survival improvement in GBC during 20 years. This study was designed to explore the chronologic change of survival outcomes in GBC and prognostic factors.

Methods

Clinicopathologic features and survival outcomes were analyzed in 692 consecutive GBC patients who underwent surgery between 1987 and 2014, including 255 treated in Period (P) 1 (1987–2000) and 437 in P2 (2001–2014).

Results

The mean age was 63.3 years. Curative resection rate was 59.2% and 5‐year survival rate (5‐YSR) after curative resection was 67.1%. Comparisons between P1 and P2 showed that mean age, asymptomatic presentation, extended cholecystectomy, curative resection, adjuvant chemotherapy, and tumor ≤ T2 were significantly higher during P2. The overall 5‐YSR after curative surgery was significantly lower in P1. In patients who underwent curative resection, poor prognostic factors included symptomatic presentation, CA 19‐9 >37 IU/ml, poor differentiation, tumor ≥ T3, and lymph nodal involvement. In patients who received non‐curative surgery, well‐ or moderately differentiated tumor and adjuvant chemotherapy provide survival benefit.

Conclusions

Detection of GBC at an early stage and optimal curative surgery may improve survival outcomes in GBC. Chemotherapy provides survival benefit in palliative setting.
Determining preventability of pediatric readmissions using fault tree analysis
Authors: Jonas Jennifer A. , Devon Erin Pete , Ronan Jeanine C. , Ng Sonia C. , Owusu‐McKenzie Jacqueline Y. , Strausbaugh Janet T. , Fieldston Evan S. , Hart Jessica K.
Published: February 2016

BACKGROUND

Previous studies attempting to distinguish preventable from nonpreventable readmissions reported challenges in completing reviews efficiently and consistently.

OBJECTIVES

(1) Examine the efficiency and reliability of a Web‐based fault tree tool designed to guide physicians through chart reviews to a determination about preventability. (2) Investigate root causes of general pediatrics readmissions and identify the percent that are preventable.

DESIGN/SETTING/PATIENTS

General pediatricians from The Children's Hospital of Philadelphia used a Web‐based fault tree tool to classify root causes of all general pediatrics 15‐day readmissions in 2014.

INTERVENTION/MEASUREMENTS

The tool guided reviewers through a logical progression of questions, which resulted in 1 of 18 root causes of readmission, 8 of which were considered potentially preventable. Twenty percent of cases were cross‐checked to measure inter‐rater reliability.

RESULTS

Of the 7252 discharges, 248 were readmitted, for an all‐cause general pediatrics 15‐day readmission rate of 3.4%. Of those readmissions, 15 (6.0%) were deemed potentially preventable, corresponding to 0.2% of total discharges. The most common cause of potentially preventable readmissions was premature discharge. For the 50 cross‐checked cases, both reviews resulted in the same root cause for 44 (86%) of files (κ = 0.79; 95% confidence interval: 0.60‐0.98). Completing 1 review using the tool took approximately 20 minutes.

CONCLUSION

The Web‐based fault tree tool helped physicians to identify root causes of hospital readmissions and classify them as either preventable or not preventable in an efficient and consistent way. It also confirmed that only a small percentage of general pediatrics 15‐day readmissions are potentially preventable. Journal of Hospital Medicine 2016;11:329–335. © 2016 Society of Hospital Medicine
Climatological characteristics and synoptic patterns of snowfall episodes in the central Spanish Mediterranean area
Authors: Mora José Ángel Nuñez , Martín Jesús Riesco , García Manuel Mora , de Pablo Davila Fernando , Rivas Soriano Luís
Published: February 2016

The long‐term temporal and spatial characteristics of snowfalls over the Comunidad Valenciana (Provinces of Castellón, Valencia and Alicante) (central Mediterranean coast of the Iberian Peninsula) were analysed using a 30‐year period (1981–2010). The average number of snowy days per year was 38.7, and annual variability was pronounced. Annual distribution peaked in January (on average, 8.9 snowy days). By contrast, snow was absent in the summertime. Snow was seen even at sea level in most of the months with snowfall. Orography was seen to be a key factor in the spatial distributions of snowy days (covering the ground surface or not) and in the return periods. Snowfall increased with altitude, but not linearly. Finally, five synoptic patterns were found to be associated with heavy snowfall episodes in the domain studied. In each group, a low (often a cut‐off low) in mid‐levels was identified over Spain or surrounding areas. In most cases (79%), an easterly flow was present at low levels and the arrival of cloud bands from the west was detected in a few cases (21%). The former is more frequent because the air mass becomes unstable during its passage over the sea and can produce heavy snowfalls.
Oil quality parameters and quantitative measurement of major secoiridoid derivatives in Neb Jmel olive oil from various Tunisian origins using qNMR
Authors: Ben Mansour Amir , Gargouri Boutheina , Melliou Eleni , Magiatis Prokopios , Bouaziz Mohamed
Published: February 2016

BACKGROUND

Olive oil contains compounds with interesting biological activities which are influenced by the cultivar, the geographic origin and other factors. The aims of this work were to (1) investigate these factors in Neb Jmel olive oil from various Tunisian origins; (2) determine the influence of geographic conditions on phenolic composition of Neb Jmel olive oil and consequently on the antioxidant compounds; and (3) verify whether oils could be discriminated based on geographical origin.

RESULTS

The characterisation of extra‐virgin Neb Jmel olive oil produced in its original location has been conducted. Owing to the effect of the genotype and environmental, agronomic and technological factors on the chemical composition of olive oil and its quality, all studied olives were collected at the same season, and their oil obtained under the same processing technique. Many analyses were carried out to characterise the different olive oils: free acidity, peroxide value, fatty acid composition, Rancimat assay, pigments content and phenolic compounds by 1H NMR. A recently developed method for the direct measurement of the oleocanthal and oleacein levels in olive oil by quantitative 1H NMR was applied. The method was applied to the study of four Neb Jmel olive oils samples, and a broad variation of concentrations of all four secoiridoids was recorded. The concentration of each ranged from 55 to 529 mg kg−1 and the sum of the four major secoiridoids (known as D3) ranged from 436 to 1063 mg kg−1.

CONCLUSION

The quantification of major phenolic compounds of olive oil by NMR indicated that environmental conditions influence the production of qualitative phenolic fractions. All these compounds can be used as base ‘markers’ to characterise and differentiate these olive oil on geographic origin. © 2016 Society of Chemical Industry
Influence of temperature and fish thickness on the mass transfer kinetics during the cod (Gadus morhua) desalting process
Authors: Oliveira Helena , Gonçalves Amparo , Nunes Maria L , Vaz‐Pires Paulo , Costa Rui
Published: February 2016

BACKGROUND

The aim of this study was to analyse the influence of desalting temperature, fish thickness and desalting time on the mass transfer kinetics during the cod desalting process by physico‐chemical analyses.

RESULTS

Both water uptake and salt loss increased with increasing temperature (15 °C > 10 °C > 5 °C) up to 24 h in ‘thicker’ pieces. The equilibrium achievement was faster in ‘thinner’ pieces and also with increasing temperature. Longer desalting times at 10 °C can be a good practice to be used during cod desalting at an industrial scale in order to obtain commercial products with higher yields. The faster mass transfer during desalting of ‘thinner’ pieces appears to follow three periods as a result of diffusion of the components (water, NaCl, and soluble proteins) because of the concentration differences, and pressure gradients due to expansion/shrinkage of the protein matrix, which is dependent on the NaCl content. The refractive index can be used by industry as an indirect measurement to determine the moment at which the ‘thicker’ samples are near the ZNaCl = YNaCl equilibrium.

CONCLUSION

Optimum combinations between the process variables analysed are essential in order to speed up the mass transfer kinetics during cod desalting at an industrial scale. © 2016 Society of Chemical Industry
ERCP in potentially resectable malignant biliary obstruction is frequently unsuccessful when performed outside of a comprehensive pancreaticobiliary center
Authors: Donnan Erica , Bentrem David J. , Komanduri Srinadh , Mahvi David M. , Keswani Rajesh N.
Published: February 2016

Background and Objectives

ERCP prior to pancreaticoduodenectomy is unnecessary in select patients. When performed, it should be in conjunction with endoscopic ultrasound (EUS) to increase diagnostic sensitivity and allow for metal stent placement. The aim of this study was to determine differences in endoscopic practice patterns at community medical centers (CMC) and a comprehensive pancreaticobiliary referral center (PBRC).

Methods

Retrospective cohort study of all patients seen at a PBRC for endoscopic and/or surgical management of potentially resectable malignant distal biliary obstruction from 1/2011 to 6/2014.

Results

Of 75 patients, 30 underwent endoscopic management at a CMC and 45 were initially managed at our PBRC. ERCP was attempted in 92% of patients. EUS was performed more frequently (100% vs. 13.3 %, P < 0.0001), ERCP was more successful (93% vs. 69%, P = 0.02), and metal stent placement more likely (41% vs. 5%, P = 0.005) at our PBRC compared to a CMC. The majority (81%) of patients undergoing initial endoscopy at a CMC required repeat endoscopy at our PBRC.

Conclusions

Patients who are candidates for pancreaticoduodenectomy frequently undergo ERCP. At a CMC, ERCP is often unsuccessful, is rarely accompanied by EUS, and often requires repeat endoscopy. Our findings support regionalizing the management of suspected pancreatic malignancy into dedicated specialty centers. J. Surg. Oncol. 2016;113:647–651. © 2016 Wiley Periodicals, Inc.
Excitation spectra of Bi/Si(001) interfaces
Authors: Buchenko V. V. , Goloborodko A. A. , Afanasieva T. V.
Published: February 2016

Present article deals with the theoretical and experimental investigation of optical properties of Bi/Si(001) interfaces in a wide spectral range (1–4 eV). Theoretical excitation spectra of vicinal Si(001) surface, Bi/Si(001)–0.5 monolayer and Bi/Si(001)–1 monolayer interfaces are calculated by time‐dependent density functional theory with the hybrid Becke and Lee, Yang and Parr pseudopotential. Calculations and experimental studies of the absorption spectrum of the samples revealed the blue shift of the optical absorption edge with increasing of the bismuth covering degree. Features of the experimentally obtained reflectance anisotropy spectra (RAS) and surface differential reflectance spectra (SDRS) concerned with changing of the silicon surface reconstruction from 2 × 1 to 1 × 1 with the increasing of the bismuth covering degree from 0.5 to 1 monolayer. It is shown that the correlation between the theoretically calculated and experimental data makes it possible to identify the electronic transitions in the surface region.