bluuebunny/crossref_metadata_2025 huggingface dataset:
Orientation of AgI Ions in Coordination Architectures through Ligand Conformation and Anion Binding: from Polymeric Chains to Discrete Squares
Authors: Roxburgh Marina , McMorran David A. , Garden Anna L. , Hanton Lyall R.
Published: September 2018

Five new complexes containing AgI salts and the ligand 3,4‐dipyridyl ketone (L34) were synthesized and characterized, namely {[AgL34]ClO4}∞ (1), {[AgL34]BF4}∞ (2), {AgL34NO3}∞ (3), {AgL34CF3CO2}∞ (4) and [AgL34CF3SO3]4 (5). Both the anion and the ligand conformation were found to affect the structure packing. This set of 1:1 M/L structures demonstrated the role of anion binding and ligand conformation in determining the molecular architecture; the increasing alignment of cations in neighboring M‐L chains in structures 1–4 can be attributed to the anions' ability to coordinate to AgI cations. The conformation of the ligand was shown to determine whether a discrete or polymeric architecture formed. In complexes 1–4 the N3py atom was in a cis orientation, with 1 and 2 forming offset chains held together in 2‐D sheets. The anion in 3 helped link 1‐D chains together to form double chains with the double chains offset in the 2‐D sheet. Complex 4 was present as a 2‐D sheet, with the bifurcating CF3CO2– anion causing the alignment of the AgI cations within the sheet. Complex 5 was the only discrete species, with L34 adopting a trans arrangement and acting as corner pieces of a molecular square. DFT calculations showed that the two conformations of the free ligand had a difference in energy of only 2.1 kJ mol–1.
Synthesis and Characterization of the New Manganese Hydroxide Chloride γ‐Mn(OH)Cl
Authors: Falkowski Viktoria , Zeugner Alexander , Isaeva Anna , Ruck Michael , Huppertz Hubert
Published: September 2018

A new modification of Mn(OH)Cl was obtained under high‐pressure/high‐temperature conditions in a Walker‐type multianvil device. The pale pink, hygroscopic compound crystallizes in the orthorhombic space group Pnma (no. 62) with a = 602.90(4), b = 350.98(2), c = 1077.69(7) pm, and V = 228 × 106 pm3. The layered centrosymmetric structure consists of edge‐sharing Mn(OH)3Cl3 octahedra arranged in sheets parallel to the (001) plane. The comparatively long H···Cl distance of 275 pm suggests only weak hydrogen bonds between neighboring layers. Spin‐polarized scalar‐relativistic DFT+U calculations predict a non‐conducting magnetically ordered ground state with a band gap of at least 3.2 eV and an effective magnetic moment of 4.65 µB/f. u. The experimentally determined magnetic response of Mn(OH)Cl is paramagnetic in the range of 10–300 K. The estimated moment of 5.6 µB/f. u. indicates the high‐spin d5 configuration of manganese(II). We find hints for a long‐range magnetic ordering below 10 K.
Substituent‐Controlled and Rhodium‐Catalyzed Intramolecular [2+2+2] and [2+1+2+1] Cycloadditions of Electron‐Deficient Triynes
Authors: Yamano Ryota , Kinoshita Suzuka , Shibata Yu , Tanaka Ken
Published: September 2018

It has been established that the ratio of [2+2+2] and [2+1+2+1] cycloaddition products in the reactions of electron‐deficient 2‐phenylnaphthalene‐linked triynes, possessing carbonyl groups at the alkyne termini, with a cationic rhodium(I)/bisphosphine complex are dominated by substituents on the carbonyl groups rather than the ligands used. Thus, a triyne, possessing the bulky and electron‐withdrawing isobutanoyl and pivaloyl groups at the alkyne termini, exclusively afforded the [2+1+2+1] cycloaddition products, on the contrary, a triyne, possessing the highly coordinating dimethylcarbamoyl groups at the alkyne termini, exclusively afforded the [2+2+2] cycloaddition product. Additionally, helicity stability of the [2+2+2] cycloaddition product, dibenzo[7]helicenes, possessing two adjacent carbonyl groups, was examined. The dibenzo[7]helicenes showed lower racemization barrier than [7]helicenes presumably due to low aromaticity of the two benzene rings in the middle of the two triphenylene skeletons, which may allow flexible bending of two terminal phenanthrene moieties to form the parallel transition state in the racemization process. Furthermore, steric repulsion between the substituents on the carbonyl groups and the benzene rings outside the helicene core affects the helicity stability, which may also affect the ee values of the reaction products.
Prolinamides of Aminouracils, Organocatalyst Modifiable by Complementary Modules
Authors: Ruíz‐Pérez Karen M. , Quiroz‐García Beatriz , Hernández‐Rodríguez Marcos
Published: September 2018

We report the synthesis and evaluation of prolinamide organocatalysts that incorporate aminouracils. The features of these catalysts are enhanced NH acidity of the amide because of the electron‐withdrawing nature of the heterocycle, an additional hydrogen‐bond donor at the α or β positions of this functional group (using 6‐aminouracil or 5,6‐diaminouracil respectively), and it can be recovered due to its low solubility and used again without decreasing the enantioselectivity. A unique feature of these systems is the self‐assembly capability with complementary modules by Watson–Crick interactions. These supramolecular adducts behave differently from the catalyst alone, some of them have lower performance but others improve the selectivity of the product. Therefore, this approach avoids the synthesis of many catalysts.
Synthesis of a 3′‐Deoxy‐C‐Nucleoside Phosphonate Bearing 9‐Deazaadenine as Base Moiety
Authors: Nie Peng , Groaz Elisabetta , De Jonghe Steven , Andrei Graciela , Herdewijn Piet
Published: September 2018

Herein, the synthesis of the first example of a 3′‐deoxy‐5′‐phosphonate 2′[R] C‐nucleoside and its corresponding prodrug is presented. The developed route involves a reductive debromination at the 2′‐position of a suitably substituted 9‐deazaadenosine intermediate, followed by a stereoselective glycosylation at the 5′‐anomeric position to achieve the installation of the phosphonomethoxy functionality. The target compound with the desired configuration is formed upon base‐promoted epimerization at the 2′[S]‐position of the sugar moiety.
1‐(Methylamino)anthracene – An Accessible Building Block for Photoresponsive Compounds
Authors: Ulatowski Filip , Melaniuk Karolina
Published: September 2018

In this paper we present a convenient and scalable synthesis of 1‐(methylamino)anthracene, which is a potent building block for the construction of photoresponsive materials. With this structural motif we have synthesized an anion receptor bearing two anthracene groups. Interaction of a chloride anion with the anthracene moieties increases the association constant. Photocycloaddition allows to obtain a single macrocyclic receptor, which exhibits higher binding constants due to the macrocyclic effect.
CpTiCl2, an Improved Titanocene(III) Catalyst in Organic Synthesis
Authors: Roldan‐Molina Esther , Padial Natalia M. , Lezama Luis , Oltra J. Enrique
Published: September 2018

Preparation, EPR analysis, and advantages in green organic chemistry of CpTiCl2, an improved single‐electron transfer catalyst, are reported. Under mild conditions, this organometallic complex provides excellent yields of homoallylic and homopropargylic alcohols in Barbier‐type allylation and propargylation reactions. Moreover, in the presence of a bidentate BOX ligand, Barbier‐type cyclization reactions catalyzed by CpTiCl2 can be carried out in an enantioselective manner.
Copper(II)‐Promoted Cascade Synthesis of 2‐Aminobenzothiazoles Starting from 2‐Iodoanilines and Sodium Dithiocarbamates
Authors: Zhu Hui , Zhang Shi‐Bo , Liu Xing , Cheng Yu , Peng Han‐Ying , Dong Zhi‐Bing
Published: September 2018

A facile and efficient formation of 2‐aminobenzothiazoles by a copper(II)‐promoted one‐pot cascade process was developed. The desired 2‐aminobenzothiazoles were synthesized in good to excellent yields (up to 97 %) in the presence of Cu(OAc)2 and K2CO3, a variety of functional groups on 2‐iodoanilines could be tolerated. The method features ligand‐free and mild reaction conditions and good yields, illustrating its practical synthetic value in some potentially biologically active compounds.
Intramolecular Hydrogen Bond Activation of Aza‐Methylene Imines in Hydrogen Bond Bifunctional Catalysis – A Density Functional Theory Study
Authors: Martín‐Sómer Ana , Arpa Enrique M. , Díaz‐Tendero Sergio , Alemán José
Published: September 2018

In this work, we present a density functional theory study of the dipolar cycloaddition of azamethylene imines to nitroalkenes, showing the importance of the intramolecular activation of the hydroxyl group and the role of the intermolecular hydrogen bond with Takemoto's catalyst. The importance of non‐covalent interactions is evaluated by means of simulations using non‐covalent interactions, and natural bonding orbital analysis. The combination of these studies allows us to understand the role played by the intra‐ and intermolecular interactions in the reactivity and enantioselectivity of the process.
Guanidiniocarbonyl Pyrrole Cation (GCP) – A New Guest for Cucurbit[8]uril: Application to the Synthesis of Supramolecular Polymers Based on CB[8]@2GCP Complex Formation
Authors: Samanta Krishnananda , Sicking Wilhelm , Schmuck Carsten
Published: September 2018

Herein we introduce a new guest, the guanidiniocarbonyl pyrrole cation (GCP), for host–guest chemistry with cucurbit[8]uril. Macromodel calculations as well as isothermal titration calorimetry (ITC), showed that CB[8] can entrap two GCP molecules inside its hydrophobic cavity. Using this 1:2‐complex formation, we further show that CB[8] can induce crosslinking of a flexibletetracationic guanidiniocarbonyl pyrrole. An extended supramolecular cross‐linked 3D network was observed at pH 4.1 where all GCP groups in guanidiniocarbonyl pyrrole are protonated. At pH 6.5, the GCP groups are only partially protonated nanostructures with a more globular vesicle‐like shape.
Synthesis of Enantiopure Isosteres of Amino Acids Containing a Quaternary Stereocenter: Experimental and Computational Evaluation of a Novel Class of Atropisomers
Authors: Amabili Paolo , Amici Adolfo , Campisi Giovanni , Guerra Giulia , Monari Magda , Orena Mario , Piccinelli Fabio , Rinaldi Samuele , Tolomelli Alessandra
Published: September 2018

Electrophilic amination of diastereomeric 4‐methoxycarbonyl pyrrolidin‐2‐ones allowed to prepare both diastereomers of an amino acid bearing a quaternary chiral center, a key intermediate to antibiotic 8‐methoxyquinolone carboxylic acid. Within this synthesis, novel atropisomers, exceedingly stable at room temperature, were isolated and characterized, which were subsequently converted into the desired products by a novel reductive N–N bond cleavage reaction.
Chiral Inductive Diastereoconvergent Allylation Reactions of Allyltrimethylsilane and Diastereomixtures of Diarylmethanols Catalyzed by FeCl3
Authors: Fujihara Rina , Nakata Kenya
Published: September 2018

We report the chiral‐auxiliary‐controlled diastereoconvergent allylation reactions of allyltrimethylsilane with diastereomeric mixtures of diarylmethanols in the presence of FeCl3 as a Lewis acid catalyst. This reaction was successfully applied to a variety of substrates; it proceeded irrespective of the substituent on the aromatic ring of the substrate. The present method was used as the key step in synthesizing (R)‐tolterodine.
Modern Developments in the Chemistry of Homoenolates
Authors: Mills L. Reginald , Rousseaux Sophie A. L.
Published: September 2018

Homoenolates are unique synthetic intermediates which display umpolung reactivity. Homoenolates and homoenolate equivalents like cyclopropanols have seen a recent surge in popularity due to their particular utility for accessing β‐functionalized carbonyl derivatives. This popularity has been enabled by the development of protocols for facile access to cyclopropanols and homoenolates from a variety of readily available starting materials. This microreview will highlight common strategies for generating cyclopropanols and metal homoenolates, as well as procedures for homoenolate functionalization, with a particular emphasis on protocols that have appeared after 2003. As an amphoteric molecule, two main reactivity modes have been established: the homoenolate reacts as a carbon nucleophile for β‐functionalization reactions and/or as a carbonyl electrophile, a strategy which has only emerged in the past few years. This microreview will highlight the use of homoenolates as convenient intermediates for accessing especially challenging motifs. The use of homoenolate chemistry in the context of natural product and pharmaceutical synthesis will also be presented.
1,4,5,8‐Tetraethynylanthracene – Synthesis, UV/Vis Absorption Spectroscopy and its Application as Building Block for Tetradentate Acceptor Molecules
Authors: Niermeier Philipp , Teichmann Lisa , Neumann Beate , Stammler Hans‐Georg , Mitzel Norbert W.
Published: September 2018

1,4,5,8‐Tetraethynylanthracene was synthesised starting from 1,4,5,8‐tetrachloroanthracene‐9,10‐dione. Different reducing agents, namely sodium borohydride, sodium dithionite and zinc, were tested to convert the anthraquinone into the corresponding tetrachloroanthracene. The latter was functionalised in a fourfold Kumada cross‐coupling reaction with (trimethylsilyl)‐ethynyl substituents, followed by cleavage of the protecting groups using potassium carbonate in methanol. UV/Vis absorption spectroscopy was performed for the highly conjugated tetraalkynyl‐substituted anthracenes. In order to demonstrate the usability of 1,4,5,8‐tetraethynylanthracene in the field of organometallic chemistry, silicon‐ and tin‐containing (acceptor‐)substituents were introduced through (hydro)metalation reactions. Most of the new compounds were characterised by X‐ray diffraction experiments.
Synthesis of a NewN‐Diaminophosphoryl‐N′‐[(2S)‐2‐pyrrolidinylmethyl]thiourea as a Chiral Organocatalyst for the Stereoselective Michael Addition of Cyclohexanone to Nitrostyrenes and Chalcones – Application in Cascade Processes for the Synthesis of Polycyclic Systems
Authors: Cruz‐Hernández Carlos , Martínez‐Martínez Eduardo , Hernández‐González Perla E. , Juaristi Eusebio
Published: September 2018

A highly diastereoselective and enantioselective Michael addition of enolizable ketones such as cyclohexanone and acetophenone to a variety of substitutedtrans‐β‐nitrostyrenes and chalcones was catalyzed by a novel chiral and unsymmetrical thiourea as organocatalyst in the presence of water or under neat reaction conditions. The anticipated Michael adducts, γ‐nitrocarbonyl adducts and 1,5‐dicarbonyl derivatives, were obtained in up to 98:2 diastereomeric ratio and up to 96 % enantiomeric excess. The application of this new chiral organocatalyst was extended to an asymmetric Michael addition‐proton transfer‐aldol reaction cascade process, a formal [3+3] cyclization reaction of cyclohexanone with arylidenepyruvates, with high stereoselectivity. The organocatalyst reported here is one of the very few able to promote the above cascade process, providing the important bicyclic framework that is found in many natural products.
Effects of a companion dog on associations of danger and threat with oriental‐looking targets
Authors: Aydin Nilüfer , Gula Bartosz , Albrecht Julia , Obermeier Marcel , Lermer Eva , Pfundmair Michaela
Published: September 2018

In the current study we extend previous findings on the shooter bias toward targets with Arab ethnicity. In an adapted shooter task, we presented stereotypically oriental‐looking targets without explicit symbols of Islam (e.g., a turban) and additionally tested if presenting a “harmless” companion dog, together with Arab versus White targets, would affect the shooter bias. Participants responded faster and made fewer errors for armed Arab than for armed White targets. Moreover, compared to the “neutral” no dog condition, the presence of a dog triggered fewer false alarms for White than for Arab targets and slowed down (correct) responses in general. Implications and potential underlying mechanisms are discussed.
Application of capillary electrophoresis combined with conductometric and UV detection to monitor meteorite simulant bioleaching by Acidithiobacillus ferrooxidans
Authors: Gonçalves Silva Gabriel , Yamassaki de Almeida Eiji , Seber Pedro , Henrique Settanni Pedro , Pereira de Oliveira Aline , Ferreira Santos Mauro Sergio , Lucio do Lago Claudimir , Cieslarova Zuzana , Rodrigues Fabio
Published: September 2018

The importance of microorganisms and biotechnology in space exploration and future planets colonization has been discussed in the literature. Meteorites are interesting samples to study microbe–mineral interaction focused on space exploration. The chemolithotropic bacterium Acidithiobacillus ferrooxidans has been used as model to understand the iron and sulfur oxidation. In this work, capillary electrophoresis with capacitively coupled contactless conductivity detection and UV detection was used to monitor bacterial growth in a meteorite simulant by measuring the conversion of Fe2+ into Fe+3. The effect of Co2+ and Ni2+ (metals also found in meteorites) on the bacterial growth was also evaluated. The presented method allowed the analyses of all metals in a single run (less than 8 min). The background electrolyte was composted of 10 mmol/L α‐hydroxyisobutyric acid/Histidine. For comparison purpose, the samples were also analyzed by UV‐Vis spectrophotometry. The Fe2+ conversion into Fe3+ by A. ferrooxidans was observed up to 36 h with the growth rate constant of 0.19/h and 0.21/h in Tuovinen and Kelly (T&K) and in meteorite simulant media, respectively. The developed method presents favorable prospect to monitor the growth of other chemolithotropic microorganisms for biotechnology applications.
Open source capillary electrophoresis
Authors: Kubáň Petr , Foret František , Erny Guillaume
Published: September 2018

Open source paradigm is becoming widely accepted in scientific communities and open source hardware is finding its steady place in chemistry research. In this review article, we provide the reader with the most up‐to‐date information on open source hardware and software resources enabling the construction and utilization of an “open source capillary electrophoresis instrument”. While CE is still underused as a separation technique, it offers unique flexibility, low‐cost, and high efficiency and is particularly suitable for open source instrumental development. We overview the major parts of CE instruments, such as high voltage power supplies, detectors, data acquisition systems, and CE software resources with emphasis on availability of the open source information on the web and in the scientific literature. This review is the first of its kind, revealing accessible blueprints of most parts from which a fully functional open source CE system can be built. By collecting the extensive information on open source capillary electrophoresis in this review article, the authors aim at facilitating the dissemination of knowledge on CE within and outside the scientific community, fosters innovation and inspire other researchers to improve the shared CE blueprints.
Lacosamide at therapeutic concentrations induces histone hyperacetylation in vitro
Authors: Granit Avital , Tetro Nino , Shmuel Miri , Peretz Tamar , Eyal Sara
Published: September 2018

Inhibition of histone deacetylases (HDACs) and subsequent hyperacetylation of histone proteins lead to altered gene expression associated with therapeutic drug effects, but also with teratogenicity. The only US Food and Drug Administration (FDA)–approved antiepileptic drug that has been consistently shown to induce histone hyperacetylation is valproic acid. More recently, lacosamide was reported to interfere with histone modifications, but histone hyperacetylation was not demonstrated. In the current study we evaluated the effects of lacosamide on histone acetylation in vitro. MDA‐MB‐231 (triple‐negative breast cancer) cells and human placental BeWo cells were exposed for 16 hours to 5‐20 μg/ml (20‐80 μm) lacosamide. Histone acetylation was evaluated by western blot analysis. We additionally measured HDAC1 activity in the presence of lacosamide. At 5, 10, and 20 μg/ml, lacosamide enhanced histone acetylation in BeWo cells by 1.7‐fold (p > 0.05), 3.4‐fold (p < 0.05), and 3.0‐fold (p > 0.05), respectively. Histone H3 acetylation and total histones H3 and H4 levels were not significantly modified (p > 0.05). The magnitude of change in histone acetylation in MDA‐MB‐231 cells was smaller (p > 0.05). In contrast to valproic acid, lacosamide did not inhibit HDAC1. Our findings suggest that the effects of lacosamide on gene expression, and the related potential antitumor activity and teratogenicity, may differ from those of valproic acid.
Evolution of grain size distributions and bed mobility during hydrographs in gravel‐bed braided rivers
Authors: Peirce S. , Ashmore P. , Leduc P.
Published: September 2018

Evolution of bed material mobility and bedload grain size distributions under a range of discharges is rarely observed in braiding gravel‐bed rivers. Yet, the changing of bedload grain size distributions with discharge is expected to be different from laterally‐stable, threshold, channels on which most gravel bedload theory and observation are based. Here, simultaneous observations of flow, bedload transport rate, and morphological change were made in a physical model of a gravel‐bed braided river to document the evolution of grain size distributions and bed mobility over three experimental event hydrographs. Bedload transport rate and grain size distributions were measured from bedload samples collected in sediment baskets. Morphological change was mapped with high‐resolution (~1 mm precision) digital elevation models generated from close‐range digital photogrammetry. Bedload transport rates were extremely low below a discharge equivalent to ~50% of the channel‐forming discharge (dimensionless stream power ~70). Fractional transport rates and plots of grain size distributions indicate that the bed experienced partial mobility at low discharge when the coarsest grains on the bed were immobile, weak selective mobility at higher discharge, and occasionally near‐equal mobility at peak channel‐forming discharge. The transition to selective mobility and increased bedload transport rates coincided with the lower threshold for morphological change measured by the morphological active depth and active width. Below this threshold discharge, active depths were of the order of D90 and active widths were narrow (< 3% of wetted width). Above this discharge, both increased so that at channel‐forming discharge, the active depth had a local maximum of 9D90 while active width was up to 20% of wetted width. The modelled rivers approached equal mobility when rates of morphological change were greatest. Therefore, changes in the morphological active layer with discharge are directly connected to the conditions of bed mobility, and strongly correlated with bedload transport rate. © 2018 John Wiley & Sons, Ltd.
Cascades of sub‐decadal, channel‐floodplain changes in low‐gradient, non‐vegetated reaches near a dryland river terminus: Salar de Uyuni, Bolivia
Authors: Li Jiaguang , Tooth Stephen , Yao Guangqing
Published: September 2018

The terminus of the ephemeral Río Colorado is located at the margins of Salar de Uyuni, Bolivia, the world's largest salt lake. The low‐gradient (<0.0006 m m‐1), non‐vegetated reaches approaching the terminus provide an excellent natural laboratory for investigating cascades of channel‐floodplain changes that occur in response to quasi‐regular flows (at least once annually) and fine‐grained sediment supply (dominantly silt and clay). High‐resolution satellite imagery (<0.65 m, various dates from 2004 onwards) and field data reveal widespread, pronounced and rapid morphodynamics on sub‐decadal timescales, including channel erosion and chute cutoff formation, and development of crevasse channels and splays, floodouts (unchannelled surfaces at channel termini), and erosion cells (floodplain scour‐transport‐fill features). In particular, following high annual precipitation (>400 mm) in 2004–2005 and two subsequent high magnitude daily precipitation events (~40 mm), all of which led to widespread flooding, numerous crevasse splays formed between 2004 and 2016, avulsions occurred at nearby floodouts, and erosion cells downstream of the splays and floodouts underwent striking morphological changes. High‐precision GPS data reveal two preferential localities for erosion cell development: partially or fully abandoned channels with crevasse splay remnants, and topographic lows between channels. In this overall low‐gradient setting, comparatively high gradients (up to ~0.0006 m m‐1) at the edge of splay deposits and topography created by crevasses and abandoned channels may initiate knickpoint retreat and thereafter erosion cell development. Abandoned channels with splays tend to give rise to narrow, deep erosion cells, while topographic lows promote relatively shallow, wide erosion cells. In both situations, erosion cells may extend upslope and downslope, and eventually connect to form straight channels. The channel‐floodplain morphodynamics near the Río Colorado terminus extend previous analyses of low‐gradient, dryland river systems, particularly because the lack of vegetation and quasi‐regular floods drive cascades of rapid changes on sub‐decadal timescales. © 2018 John Wiley & Sons, Ltd.
Wind erosion and dust emissions in central Asia: Spatiotemporal simulations in a typical dust year
Authors: Pi Huawei , Sharratt Brenton , Lei Jiaqiang
Published: September 2018

The prediction of wind erosion and dust emissions is important for controlling erosion and identifying dust sources in arid and semiarid regions of the world. This study predicts quantitatively wind erosion and dust emissions in Xinjiang Province, central Asia. The wind erosion prediction system (WEPS) was used to simulate annual soil and PM10 (particulate matter ≤10 μm in aerodynamic diameter) loss at 64 meteorological stations across the province. Soil and PM10 loss were simulated from bare surfaces at all 64 stations and from cotton and wheat fields at 11 stations. Simulated annual bare soil and PM10 loss were lowest in the Junggar (soil and PM10 loss were, respectively, 121.7 and 7.6 kg m‐2) and Tarim basins (soil loss was 78.2 kg ha‐1 and PM10 loss was 6.5 kg m‐2) and highest in the Tu‐ha Basin (soil and PM10 loss were, respectively, 638.2 and 37.7 kg m‐2). Stations with the highest annual soil loss in the Tarim and Tu‐ha basins also had the highest number of days with wind speeds >8 m s‐1. This indicated wind influenced erosion, but other factors such as soil type also affect wind erosion. The maximum monthly bare soil and PM10 loss occurred in May in the three basins, substantiating that dust storms occur most frequently during spring in the region. Simulated soil and PM10 loss were lower for cotton and wheat than bare soil, thus suggesting that maintaining vegetative cover during a portion of the year provided some protection to the soil surface from wind erosion. © 2018 John Wiley & Sons, Ltd.
Source and supply of sediment to a shoreline salient in a fringing reef environment
Authors: Cuttler Michael V.W. , Hansen Jeff E. , Lowe Ryan J. , Trotter Julie A. , McCulloch Malcolm T.
Published: September 2018

Reef‐associated landforms are coupled to the health of the reef ecosystem which produces the sediment that forms and maintains these landforms. However, this connection can make reef‐fronted coastlines sensitive to the impacts of climate change, given that any decline in ecosystem health (e.g. decreasing sediment supply) or changes to physical processes (e.g. sea level rise, increasing wave energy) could drive the sediment budgets of these systems into a net erosive state. Therefore, knowledge of both the sediment sources and transport mechanisms is required to predict the sensitivity of reef‐associated landforms to future climate change. Here, we examine the benthic habitat composition, sediment characteristics (composition, texture, and age), and transport mechanisms and pathways to understand the interconnections between coastal morphology and the reef system at Tantabiddi, Ningaloo Reef, Western Australia. Benthic surveys and sediment composition analysis revealed that although live coral accounts for less than 5% of the benthic cover, coral is the dominant sediment constituent (34% on average). Sediment ages (238U/230Th) were mostly found to be thousands of years old, suggesting that the primary sediment source is relic reef material (e.g. Holocene reef framework). Sediment transport across the lagoon was quantified through measurements of ripple migration rates, which were found to be shoreward migrating and responsible for feeding the large shoreline salient in the lee of the reef. The derived sediment fluxes were comparable with previously measured rates of sediment production by bioerosion. These results suggest that sediment budgets of systems dependent on old (>103 years) source materials may be more resilient to climate change as present‐day reef health and community composition (i.e. sources of ‘new’ carbonate production) have limited influence on sediment supply. Therefore, the vulnerability of reef‐associated landforms in these systems will be dictated by future changes to mechanisms of sediment generation (e.g. bioerosion) and/or physical processes. © 2018 John Wiley & Sons, Ltd.
Per- and polyfluoroalkyl substances in Northern California cats: Temporal comparison and a possible link to cat hyperthyroidism
Authors: Wang Miaomiao , Guo Weihong , Gardner Steve , Petreas Myrto , Park June-Soo
Published: September 2018

The indoor environment and dietary intake are considered to be major human exposure pathways to per- and polyfluoroalkyl substances (PFASs). Cats have similar exposures to humans by sharing their residential environments, although they have different diet, body sizes, and indoor activities. In the present study, we report PFAS levels in the serum of 2 groups of Northern California cats (>10 yr old) collected during 2 time periods: 2008 to 2010 (n = 21) and 2012 to 2013 (n = 22). Levels of ∑PFAS (geometric mean) were lower in the second period (geometric mean = 8.10 ng/mL) than the first time period (geometric mean = 15.8 ng/mL), although PFAS profiles remained similar. We also analyzed PFAS levels in human serum collected in the same time period (2008–2010) and geographic area, and compared the profiles and ∑PFAS levels (15.8 vs 14.3 ng/mL for cat and human, respectively). Long chain perfluorinated carboxylic acids, especially perfluorononanoic acid and perfluoroundecanoic acid, were significantly higher in cat serum than in humans. Furthermore, serum from hyperthyroid cats in the second time period showed higher ∑PFAS level (9.50 ng/mL) compared to nonhyperthyroid cats (7.24 ng/mL), and it is the perfluorooctanoic acid levels that were statistically significantly higher in hyperthyroid cats’ serum (p < 0.05). This result may indicate a possible link between PFAS levels and cat hyperthyroid, warranting a larger study for further investigation. Environ Toxicol Chem 2018;37:2523–2529. © 2018 SETAC
Resilience in family caregiving for people with dementia: A systematic review
Authors: Teahan Áine , Lafferty Attracta , McAuliffe Eilish , Phelan Amanda , O'Sullivan Liam , O'Shea Diarmuid , Fealy Gerard
Published: September 2018

Objective

The objective of this review is to critically examine, evaluate, and synthesize the literature on resilience in family caregiving for people with dementia.

Methods

A systematic literature review was conducted according to PRISMA guidelines to identify articles which examined resilience and related concepts in family caregiving for people with dementia. The review was based on a systematic search of scholarly databases, to yield peer‐reviewed articles and grey literature, published between 2006 and 2016. Two independent reviewers prescreened the search results and conducted formal assessments and quality appraisals of the retrieved articles.

Results

A total of 13 863 articles were identified by the systematic search, and 52 articles were included in the review. Based on a critical narrative synthesis of the literature, the study proposes a model of resilience for family carers of people with dementia, which incorporates the context of caring, social and cultural characteristics, and psychological dimensions of caring.

Conclusions

The results indicate that there is no single approach to enhancing resilience among family carers of people with dementia. Resilience is a multifaceted response to the caregiving role, and is influenced by a multitude of interrelated factors. However, the factors and resources outlined have been addressed, with limited success in some cases, by psychosocial interventions in the field. While the work conducted to date to develop resilience‐enhancing interventions has been marked with some success, the next wave of carer research could usefully examine ecological perspectives on carer outcomes, including carer resilience.
Does abuse in late life worsen sleep quality? A two‐year prospective cohort study among rural older adults
Authors: Yunus Raudah M. , Hairi Noran N. , Yuen ChooWan , Sooryanarayana Rajini , Hairi Farizah , Ismail Norliana , Kandiben Shathanapriya , Peng Tey Nai , Ali Zainudin M. , Ahmad Sharifah N. , Razak Inayah A. , Othman Sajaratulnisah , Peramalah Devi , Mydin Fadzilah H.M. , Bulgiba Awang
Published: September 2018

Background

Elder abuse and neglect (EAN) is a growing public health problem, and numerous adverse health effects of abuse in late life have been documented. Little is known, however, about the impact of elder abuse on sleep quality. This study examines the longitudinal relationship between EAN and sleep quality.

Methods

This was a 2‐year prospective cohort study involving 1927 older adults in a rural Malaysian district, Kuala Pilah. A multi‐stage cluster sampling strategy was employed. After 2 years, 1189 respondents were re‐assessed. EAN was determined using the modified Conflict Tactic Scale, while sleep quality was measured using the Pittsburgh Sleep Quality Index (PSQI).

Results

The prevalence of elder abuse was 8.1% (95% CI:6.9,9.3). Longitudinal analysis using generalized estimating equations showed that elder abuse contributed to higher PSQI scores (B:0.49, 95% CI:0.17,0.58). Sub‐analyses demonstrated that psychological abuse and neglect had significant longitudinal relationships with increase of PSQI scores, while other subtypes did not.

Conclusion

Abuse in late life, particularly psychological abuse and neglect, result in greater PSQI scores. Even though this may imply decline in sleep quality, our findings were not considered clinically significant as they did not exceed the clinical cut‐off score of five. Nevertheless, sleep quality is an important determinant of health and a predictor of mortality among older adults; thus, understanding its relationship with abuse is useful to health care providers and policy‐makers in improving health services and upgrading preventive measures.
Resilience attenuates the association between neurocognitive functioning and everyday functioning in individuals aging with HIV in the Deep South
Authors: Fazeli Pariya L. , Moore Raeanne C. , Vance David E.
Published: September 2018

Objectives

Adults aging with HIV are at risk for poorer neurocognitive and daily functioning. Identifying factors to protect such outcomes is a significant research priority. The aim of this study was to explore the role of resilience in cognitive and everyday functioning in a largely African American and low socioeconomic status sample of adults and older adults with HIV in the Deep South.

Methods/Design

In this cross‐sectional study 100 HIV+ middle‐aged and older adults (range 40‐73; 61% aged 50+) completed a comprehensive neurocognitive battery along with self‐reported measures of resilience and everyday functioning.

Results

Higher resilience was associated with better global neurocognitive functioning (rho = 0.31, P < 0.01), as well as better functioning in all domains (verbal fluency, executive functioning, speed of information processing, learning, working memory) except recall and motor skills. Resilience was also significantly associated with instrumental activities of daily living (IADL) dependence, with lower resilience observed in those with IADL dependence compared with those who were IADL independent (P < 0.01). In a multiple regression adjusting for data‐driven covariates (verbal IQ, income, depression), and global neurocognitive impairment, resilience was the only significant (P = 0.02) correlate of IADL dependence. A follow‐up mediation showed that the direct relationship between neurocognitive functioning and IADL declines was fully attenuated after accounting for shared variance with resilience.

Conclusions

Resilience is associated with better cognitive and functional outcomes in people aging with HIV. While further work is needed to understand these associations over time, results suggest interventions to build resilience may promote successful aging in this vulnerable population.
Green synthesis and cytotoxic activity of dibenzyl α‐hydroxyphosphonates and α‐hydroxyphosphonic acids
Authors: Rádai Zita , Szeles Petra , Kiss Nóra Zsuzsa , Hegedűs László , Windt Tímea , Nagy Veronika , Keglevich György
Published: September 2018

A series of dibenzyl α‐hydroxyphosphonates and the corresponding α‐hydroxyphosphonic acids, mostly new compounds, have been synthesized. The dibenzyl α‐hydroxyphosphonates have been obtained in the Pudovik reaction of substituted benzaldehydes and dibenzyl phosphite in the presence of triethylamine as the catalyst. The amount of the solvent was minimized during the reaction, and the workup involved crystallization from the reaction mixture. A new protocol was developed to transform the dibenzyl 1‐hydroxyphosphonates to the corresponding phosphonic acids by catalytic hydrogenation. The derivatives prepared were screened as potential cytotoxic agents against Mes‐Sa human uterine sarcoma cell line.
The effects of import competition on health in the local economy
Authors: Lang Matthew , McManus T. Clay , Schaur Georg
Published: September 2018

We provide evidence that average mental, physical, and general health worsens for employed workers in local U.S. labor markets exposed to greater import competition from China. The effects are greatest for mental health. Moving a region from the 25th to 75th percentiles of import exposure corresponds to a 7.8% increase in the morbidity of poor mental health, adding about 3 days of poor mental health per year for the average adult. Concurrently, the ability to afford health care decreases. Our results complement documented consequences of import competition on labor markets and temporary business cycle shocks on health outcomes.
Is It Time to Reconsider the Milan Criteria for Selecting Patients With Hepatocellular Carcinoma for Deceased‐Donor Liver Transplantation?
Authors: Costentin Charlotte E. , Bababekov Yanik J. , Zhu Andrew X. , Yeh Heidi
Published: September 2018

Liver transplantation (LT) is considered the optimal treatment for hepatocellular carcinoma (HCC) because it removes tumor as well as the underlying cirrhotic liver. Because of a global organ shortage, LT for patients with HCC is limited to patients with expected survival comparable to that of nonmalignant indications. Therefore, identifying patients with lower rates of HCC recurrence and higher rates of survival is critical. International guidelines have considered the Milan Criteria (MC) the standard for selecting patients with HCC for deceased‐donor LT (DDLT). However, several alternative criteria have been reported in the Western world. Interestingly, the two most recent models combining α‐fetoprotein level, number of nodules, and size of the largest nodule have been shown to outperform MC in identifying patients with low risk of HCC recurrence or those who will survive for 5 years after liver transplantation. In addition, new models overcome limitations of MC in improving classification of high‐ versus low‐risk patients with HCC for DDLT. These recent scoring systems also provide clinicians with user‐friendly tools to better identify patients at lower risk of recurrence. Conclusion: Although most Western countries still select patients based on MC, there is a mounting change in recent practice patterns regarding the selection of patients with HCC for DDLT. Herein, we describe how alternative criteria should lead to reconsideration of MC as it applies to selecting patients with HCC for DDLT in international guidelines.
Economic burden, impoverishment, and coping mechanisms associated with out‐of‐pocket health expenditure in India: A disaggregated analysis at the state level
Authors: Sangar Shivendra , Dutt Varun , Thakur Ramna
Published: September 2018

Introduction

The high share of out‐of‐pocket (OOP) health expenditure imposes an extreme financial burden on households, and they have to incur a substantial amount of expenditure to avail health care services. This study analyses the inter‐state differentials in the economic burden of OOP health expenditure, resultant impoverishment impact, and sources of finance used as coping mechanisms.

Materials and methods

The study is based on health expenditure survey, namely the 71st Round on “Key Indicators of Social Consumption in India: Health,” (2014) conducted in India by the National Sample Survey Organisation. The study uses headcount, payment gap, and concentration index to measure the economic burden, impoverishment impact of OOP health expenditure, and the level of inequality.

Results

On the basis of results, the states can be divided into four distinct categories: (1) States with low economic burden and low poverty impact of OOP health expenditure, (2) low economic burden and high poverty impact of OOP health expenditure, (3) high economic burden and low poverty impact of OOP health expenditure, and (4) high economic burden and high poverty impact of OOP health expenditure.

Conclusions

Inter‐state differentials in OOP health expenditure and impoverishment need proper attention of the government especially the policy makers.
Direct RIG‐I activation in human NK cells induces TRAIL‐dependent cytotoxicity toward autologous melanoma cells
Authors: Daßler‐Plenker Juliane , Paschen Annette , Putschli Bastian , Rattay Stephanie , Schmitz Saskia , Goldeck Marion , Bartok Eva , Hartmann Gunther , Coch Christoph
Published: September 2018

Activation of the innate immune receptor retinoic acid‐inducible gene I (RIG‐I) by its specific ligand 5′‐triphosphate RNA (3pRNA) triggers anti‐tumor immunity, which is dependent on natural killer (NK) cell activation and cytokine induction. However, to date, RIG‐I expression and the functional consequences of RIG‐I activation in NK cells have not been examined. Here, we show for the first time the expression of RIG‐I in human NK cells and their activation upon RIG‐I ligand (3pRNA) transfection. 3pRNA‐activated NK cells killed melanoma cells more efficiently than NK cells activated by type I interferon. Stimulation of RIG‐I in NK cells specifically increased the surface expression of membrane‐bound TNF‐related apoptosis‐inducing ligand (TRAIL) on NK cells, while activated NK cell receptors were not affected. RIG‐I‐induced membrane‐bound TRAIL initiated death‐receptor‐pathway‐mediated apoptosis not only in allogeneic but also in autologous human leukocyte antigen (HLA) class I‐positive and HLA class I‐negative melanoma cells. These results identify the direct activation of RIG‐I in NK cells as a novel mechanism for how RIG‐I can trigger enhanced NK cell killing of tumor cells, underscoring the potential of RIG‐I activation for tumor immunotherapy.
Determination of optimized cropping patterns according to crop yield response under baseline condition and climate‐change condition
Authors: Abdi‐Dehkordi Mehri , Bozorg‐Haddad Omid , Chu Xuefeng
Published: September 2018

Due to water shortage, climate change, and increased water demands, the optimal allocation of agricultural water is crucial, especially during a drought period. The objective of this study is to optimize the cropping patterns in the Aidoghmush River Basin in Iran for both the baseline condition and climate‐change condition. For this purpose, the genetic algorithm was applied and an optimization model was developed with the goal of maximizing the agricultural benefits for a 14‐year planning horizon. The baseline condition and climate‐change condition 14‐year periods employed in this study are 1987–2000 and 2026–2039, respectively. The results showed that the scenarios of cropping pattern changes with consideration of the crop yield response achieved higher benefits than those for the present condition and other optimal conditions without considering the crop yield response. With considering the optimum cropping patterns based on the crop yield response, the benefits in the planning horizon increased by 46.7 and 37.8% for the baseline condition and climate‐change condition, respectively, compared to the present condition. © 2018 John Wiley & Sons, Ltd.
Adapting or Chasing Water? Crop Choice and Farmers' Responses to Water Stress in Peri‐Urban Bangalore, India
Authors: Patil Vikram S. , Thomas Bejoy K. , Lele Sharachchandra , Eswar Meghana , Srinivasan Veena
Published: September 2018

Unregulated groundwater extraction has led to declining groundwater tables and increasing water scarcity in the Indian subcontinent. Understanding how farmers respond to this scarcity is important from multiple perspectives—equity in access, livelihood security and resource sustainability. We present a case from the rapidly urbanizing Arkavathy sub‐basin near Bangalore city in southern India where irrigation is fully groundwater dependent. Using cross‐sectional data from a stratified random sample of 333 farmers from 15 villages, we investigated the factors that determine their choice of crops under conditions of water scarcity and urbanization. Binary logit analysis showed that farmers with a large landholding respond by tapping deep groundwater using borewells. Multinomial logit analysis revealed that access to groundwater, variation in the proximity to the product market (city) and labour availability influence crop choice decisions. We observe that current responses indicate what has been characterized in the literature as chasing strategies. These largely favour well‐off farmers and hence are inequitable. While the choice of water‐intensive crops and unregulated pumping have aggravated water stress, the uptake of water‐saving technologies among irrigated farmers has been low, showing that resource sustainability may not be a concern where non‐farm diversification opportunities exist. © 2018 John Wiley & Sons, Ltd.
The Living Dead: Mitochondria and Metabolic Arrest
Authors: Hadj‐Moussa Hanane , Green Stuart R. , Storey Kenneth B.
Published: September 2018

Mitochondria are not just the powerhouses of the cell; these ‘end of function’ organelles are crucial components of cellular physiology and influence many central metabolic and signaling pathways that support complex multicellular life. Not surprisingly, these organelles play vital roles in adaptations for extreme survival strategies including hibernation and freeze tolerance, both of which are united by requirements for a strong reduction and reprioritization of metabolic processes. To facilitate metabolic rate depression, adaptations of all aspects of mitochondrial function are required, including; energetics, physiology, abundance, gene regulation, and enzymatic controls. This review discusses these factors with a focus on the stress‐specific nature of mitochondrial genes and transcriptional regulators, and processes including apoptosis and chaperone protein responses. We also analyze the regulation of glutamate dehydrogenase and pyruvate dehydrogenase, central mitochondrial enzymes involved in coordinating the shifts in metabolic fuel use associated with extreme survival strategies. Finally, an emphasis is given to the novel mitochondrial research areas of microRNAs, peptides, epigenetics, and gaseous mediators and their potential roles in facilitating hypometabolism. © 2018 IUBMB Life, 70(12):1260–1266, 2018