bluuebunny/crossref_metadata_2025 huggingface dataset:
Effect of Support on Metathesis of n‐Decane: Drastic Improvement in Alkane Metathesis with WMe5 Linked to Silica–Alumina
Authors: Samantaray Manoja K. , Dey Raju , Abou‐Hamad Edy , Hamieh Ali , Basset Jean‐Marie
Published: March 2015

[WMe6] (1) supported on the surface of SiO2–Al2O3(500) (2) has been extensively characterized by solid‐state NMR spectroscopy, elemental analysis, and gas quantification, which clearly reveal the formation of a mixture of monopodal and bipodal species with the migration of methyl from W to Al. The supported species SiO2–Al2O3(500) (2) transformed at 120 °C into two types of carbynic centers, one of which is cationic and the other neutral. These species are very efficient for the metathesis of n‐decane. Comparison with already‐synthesized neutral bipodal tungsten indicates that the high increase in activity is due to the cationic character of the grafted tungsten.
Platinum Oxoboryl Complexes as Substrates for the Formation of 1:1, 1:2, and 2:1 Lewis Acid–Base Adducts and 1,2‐Dipolar Additions
Authors: Bertsch Stefanie , Brand Johannes , Braunschweig Holger , Hupp Florian , Radacki Krzysztof
Published: March 2015

The oxoboryl complex trans‐[(Cy3P)2BrPt(BO)] (2) reacts with the Group 13 Lewis acids EBr3 (E=Al, Ga, In) to form the 1:1 Lewis acid–base adducts trans‐[(Cy3P)2BrPt(BOEBr3)] (6–8). This reactivity can be extended by using two equivalents of the respective Lewis acid EBr3 (E=Al, Ga) to form the 2:1 Lewis acid–base adducts trans‐[(Cy3P)2(Br3Al‐Br)Pt(BOAlBr3)] (18) and trans‐[(Cy3P)2(Br3Ga‐Br)Pt(BOGaBr3)] (15). Another reactivity pattern was demonstrated by coordinating two oxoboryl complexes 2 to InBr3, forming the 1:2 Lewis acid–base adduct trans‐[{(Cy3P)2BrPt(BO)}2InBr3] (20). It was also possible to functionalize the BO triple bond itself. Trimethylsilylisothiocyanate reacts with 2 in a 1,2‐dipolar addition to form the boryl complex trans‐[(Cy3P)2BrPt{B(NCS)(OSiMe3)}] (27).
Discrete Stimuli‐Responsive Multirotaxanes with Supramolecular Cores Constructed through a Modular Approach
Authors: Wang Wei , Sun Bin , Wang Xu‐Qing , Ren Yuan‐Yuan , Chen Li‐Jun , Ma Jianqiu , Zhang Yanyan , Li Xiaopeng , Yu Yihua , Tan Hongwei , Yang Hai‐Bo
Published: March 2015

The synthesis of discrete multirotaxanes with well‐defined structures remains a great challenge. Herein, we present the successful construction of diverse discrete multirotaxanes with well‐defined supramolecular metallacycles as cores by a modular approach. Moreover, these novel multirotaxanes featured a stimuli‐responsive property that enabled the introduction and removal of the bromide anion by taking advantage of dynamic nature of the supramolecular metallacycle scaffold. Through the combination of rotaxane‐containing prefunctionalized building blocks with the corresponding different organoplatinum(II) acceptor building blocks (60, 120, or 180°), diverse discrete multirotaxanes with well‐defined metallacycles (rhomboid or hexagon) as cores as well as certain numbers of rotaxane units were successfully obtained quantitatively by means of coordination‐driven self‐assembly. Furthermore, owing to the existence of a dynamic metallacycle as the supramolecular cores, the resultant multirotaxanes showed anion‐induced disassembly and reassembly properties, which allowed for the reversible transformation between multirotaxanes and the corresponding individual rotaxane‐containing building blocks. Therefore, this research not only enriches the family of discrete multirotaxanes, but also provides a novel strategy for the construction of “smart” stimuli‐responsive multirotaxane systems.
Nazarov Cyclization of Divinyl and Arylvinyl Epoxides: Application in the Synthesis of Resveratrol‐Based Natural Products
Authors: Sudhakar Gangarajula , Satish Kovela
Published: March 2015

New variation in the Nazarov cyclization has been developed by preparing divinyl and arylvinyl epoxides as pentadienyl cation precursors for the first time. Highly substituted cyclopentadienes, hydrindienes, and indenes were synthesized to demonstrate the compatibility of this reaction with substrates bearing a variety of substitutions and having different types of epoxides. Application of this method in the synthesis of resveratrol‐based natural products was also demonstrated.
Unraveling Ultrafast Photoinduced Proton Transfer Dynamics in a Fluorescent Protein Biosensor for Ca2+ Imaging
Authors: Tang Longteng , Liu Weimin , Wang Yanli , Zhao Yongxin , Oscar Breland G. , Campbell Robert E. , Fang Chong
Published: March 2015

Imaging Ca2+ dynamics in living systems holds great potential to advance neuroscience and cellular biology. G‐GECO1.1 is an intensiometric fluorescent protein Ca2+ biosensor with a Thr‐Tyr‐Gly chromophore. The protonated chromophore emits green upon photoexcitation via excited‐state proton transfer (ESPT). Upon Ca2+ binding, a significant population of the chromophores becomes deprotonated. It remains elusive how the chromophore structurally evolves prior to and during ESPT, and how it is affected by Ca2+. We use femtosecond stimulated Raman spectroscopy to dissect ESPT in both the Ca2+‐free and bound states. The protein chromophores exhibit a sub‐200 fs vibrational frequency shift due to coherent small‐scale proton motions. After wavepackets move out of the Franck–Condon region, ESPT gets faster in the Ca2+‐bound protein, indicative of the formation of a more hydrophilic environment. These results reveal the governing structure–function relationship of Ca2+‐sensing protein biosensors.
Straightforward Synthesis of 5‐Bromopenta‐2,4‐diynenitrile and Its Reactivity Towards Terminal Alkynes: A Direct Access to Diene and Benzofulvene Scaffolds
Authors: Kerisit Nicolas , Toupet Loïc , Larini Paolo , Perrin Lionel , Guillemin Jean‐Claude , Trolez Yann
Published: March 2015

The high‐yielding synthesis of 5‐bromopenta‐2,4‐diynenitrile (BrC5N) was achieved for the first time. Its reactivity with triisopropylsilylacetylene and triisopropylsilylbutadiyne in the presence of copper and palladium as co‐catalysts and diisopropylamine was evaluated. It revealed an unprecedented cascade reaction leading to a diene in one case and to a benzofulvene in the other case, with a unique structure. Both of them were characterized by X‐ray crystallography, among other techniques. The mechanism of the reaction leading to the diene was investigated experimentally. Theoretical calculations at the DFT level suggest that the mechanism leading to the benzofulvene relies on a hexa‐dehydro Diels–Alder (HDDA)‐type of mechanism. This work constitutes an example of an unanticipated reactivity leading to an important increase of chemical complexity.
Chemical and Spectroscopic Properties of Soil Hydrophilic Fulvic Acid Purified by Tangential Flow Ultrafiltration
Authors: Navarrete Ian A. , Tsutsuki Kiyoshi
Published: March 2015

There is a growing recognition that unless soil hydrophilic fulvic acid (HiFA) is studied together with soil hydrophobic FA (HoFA), we will not fully understand the characteristics of the FA fraction in soils. The aim of this study was to characterize soil HiFA, which were extracted from soil and purified by tangential flow ultrafiltration (TFU), by means of elemental (C, H, O, N, S) and isotope (13C, 15N) analyses, Fourier transform IR (FT‐IR) and fluorescence spectroscopy and neutral sugars analysis. Results revealed marked differences between HiFA and HoFA in terms of chemical (elemental, isotopic and neutral sugar compositions) and spectroscopic properties (FT‐IR, fluorescence spectra). The HiFA carbon accounted for 46 to 80% of the total FA carbon and thus, an important constituent of the FA fraction. On average, neutral sugars contents in HiFA is twofold larger than in HoFA and are mostly dominated by rhamnose, galactose, and fucose, while in HoFA, mannose was the most abundant neutral sugars, indicating that not only quantity, but also quality of neutral sugars varies between HiFA and HoFA. To further enhance the understanding of the characteristics and composition of soil HiFA including its turnover rate, fate and chemical transformation in soils, it is indispensable to isolate and purify HiFA. As such, purification of soil HiFA by TFU is satisfactory for such purpose.
Tungstate Supported on Periodic Mesoporous Organosilica with Imidazolium Framework as an Efficient and Recyclable Catalyst for the Selective Oxidation of Sulfides
Authors: Karimi Babak , Khorasani Mojtaba , Bakhshandeh Rostami Fatemeh , Elhamifar Dawood , Vali Hojatollah
Published: March 2015

A catalyst based on immobilization of tungstate ions (WO42−) inside the mesochannels of periodic mesoporous organosilica comprising bridged ionic liquid (1,3‐bis(3‐trimethoxysilylpropyl)imidazolium chloride) has been synthesized and characterized. This catalyst was then employed for the selective oxidation of organic sulfides to the corresponding sulfoxides or sulfones. The final synthesized catalyst was characterized by various techniques such as nitrogen sorption analysis, transmission electron microscopy, and thermogravimetric analysis. The catalyst was also applied to the selective oxidation of sulfides containing readily oxidizable functional groups such as hydroxyl, allylic, and even challenging aliphatic sulfides. Interestingly, it was found that on changing the reaction medium from aqueous methanol to aqueous acetonitrile, the product selectivity was changed successfully from sulfoxide to sulfone with good to excellent yields. Moreover, the catalyst can also be recovered and reused efficiently in nine subsequent reaction cycles without any remarkable decrease in the catalyst activity and selectivity.
Soil depth and soil production
Authors: Hunt Allen G.
Published: March 2015

Soil column depth is predicted over time scales up to a million years based on dynamics at the pore scale. The power law result integrates result for solute transport from percolation theory with typical flow velocities. Verification was based on studied soils from 14 regions worldwide over time scales from decades to a million years. The time derivative of the soil depth generates the soil production function as a function of depth. Comparison with soil production data from five locations, over similar time scales, verifies the accuracy of the predicted power to within 2%. The prediction thus unites within one framework time scales of seconds with a million years. The results allow calculation of the effects of physical soil removal on the rates of silicate weathering at the base of the column, important inputs to the global carbon cycle, neotectonics, and drainage basin evolution. © 2015 Wiley Periodicals, Inc. Complexity 21: 42–49, 2016
Medical cannabis vs. synthetic cannabinoids: What does the future hold?
Authors: Bolognini D , Ross RA
Published: March 2015

The medical use of cannabis has an intricate therapeutic history that finds its roots in ancient China (∼2700 BC). The main psychoactive component of cannabis, Δ9‐tetrahydrocannabinol (Δ9‐THC), was discovered in 1964. This was a significant breakthrough, as it allowed the generation of synthetic analogs of Δ9‐THC, the discovery of cannabinoid receptors, and the generation of synthetic small molecules. Despite this, today there is still a paucity of drugs that target the cannabinoid system.
Real‐time cytometric assay of nitric oxide and superoxide interaction in peripheral blood monocytes: A no‐wash, no‐lyse kinetic method
Authors: Balaguer Susana , Diaz Laura , Gomes Angela , Herrera Guadalupe , O'Connor José‐Enrique , Urios Amparo , Felipo Vicente , Montoliu Carmina
Published: March 2015

Background

Nitric oxide (NO) and its related reactive nitrogen species (RNS) and reactive oxygen species (ROS) are crucial in monocyte responses against pathogens and also in inflammatory conditions. Central to both processes is the generation of the strong oxidant peroxynitrite (ONOO) by a fast reaction between NO and superoxide anion. ONOO is a biochemical junction for ROS‐ and RNS cytotoxicity and causes protein nitrosylation. Circulating by‐products of protein nitrosylation are early biomarkers of inflammation‐based conditions, including minimal hepatic encephalopathy in cirrhotic patients (Montoliu et al., Am J Gastroenterol 2011; 106:1629–1637). In this context, we have designed a novel no‐wash, no‐lyse real‐time flow cytometry assay to detect and follow‐up the NO‐ and superoxide‐driven generation of ONOO in peripheral blood monocytes.

Methods

Whole blood samples were stained with CD45 and CD14 antibodies plus one of a series of fluorescent probes sensitive to RNS, ROS, or glutathione, namely 4‐amino‐5‐methylamino‐2',7'‐difluorofluorescein diacetate, dihydrorhodamine 123, MitoSOX Red, dihydroethidium, and 5‐chloromethylfluorescein diacetate. Samples were exposed sequentially to a NO donor and three different superoxide donors, and analyzed in real time by kinetic flow cytometry. Relevant kinetic descriptors, such as the rate of fluorescence change, were calculated from the kinetic plot.

Results

The generation of ONOO, which consumes both NO and superoxide, led to a decrease in the intensity of the cellular fluorescence of the probes sensitive to these molecules.

Conclusion

This is a fast and simple assay that may be used to monitor the intracellular generation of ONOO in physiological, pathological, and pharmacological contexts. © 2015 International Clinical Cytometry Society
Contrasting responses to Pleistocene climate changes: a case study of two sister species Allium cyathophorum and A. spicata (Amaryllidaceae) distributed in the eastern and western Qinghai–Tibet Plateau
Authors: Wang Xinyu , Li Yuanshuo , Liang Qianlong , Zhang Lei , Wang Qian , Hu Huan , Sun Yongshuai
Published: March 2015

It has been hypothesized that species occurring in the eastern and the western Qinghai–Tibet Plateau (QTP) responded differently to climate changes during the Pleistocene. Here, we test this hypothesis by phylogeographic analysis of two sister species, Allium cyathophorum and A. spicata. We sequenced two chloroplast DNA (cpDNA) fragments (accD‐psaI and the rpl16 intron) of 150 individuals, and the nuclear (ITS) region of 114 individuals, from 19 populations throughout the distributional ranges of these species. The divergence between the two species was dated at 779 ‐ 714 thousand years before the present and was likely initiated by the most major glaciation in the QTP. Analysis of chlorotype diversity showed that A. spicata, the species occurring in the western QTP, contains much lower genetic diversity (0.25) than A. cyathophorum (0.93), which is distributed in the eastern QTP. Moreover, multiple independent tests suggested that the A. spicata population had expanded recently, while no such expansion was detected in A. cyathophorum, indicating a contrasting pattern of responses to Pleistocene climate changes. These findings highlight the importance of geographical topography in determining how species responded to the climate changes that took place in the QTP during the Pleistocene.
On the Reactivity of RSnCl and RSiMe3 {R = 4‐tBu‐2,6‐[P(O)(OiPr)2]2C6H2} towards BF3·OEt2: Competing Lewis Acidities
Authors: Wagner Michael , Lutter Michael , Dietz Christina , Prosenc Marc H. , Jurkschat Klaus
Published: March 2015

The reactions of boron trifluoride with the organostannylene RSnCl {R = 4‐tBu‐2,6‐[P(O)(OiPr)2]2C6H2} and the organosilane RSiMe3 provided the corresponding 1:1 and 1:2 complexes, respectively, through the formation of P=O→B interactions. In the former reaction, even with excess BF3·OEt2, no Sn→B complexation involving the lone electron pair at the tin(II) center was observed. The experimental results are supported by DFT calculations.
In situ synchrotron‐based X‐ray powder diffraction and micro‐Raman study of biomass and residue model compounds at hydrothermal conditions
Authors: Thomas Morgan L. , Butler Ian S. , Kozinski Janusz A.
Published: March 2015

The applications of synchrotron X‐ray powder diffraction (XRPD) and laser micro‐Raman techniques in an examination of the dissolution, transformation, and gasification of pure cellulose and models for biomass residue under hydrothermal conditions in a diamond‐anvil cell are reported. The results contribute to the measurement of in situ time‐resolved profiles of biomass reactions, catalyst stability, and residue formation that occur in aqueous fluids at near‐ and supercritical conditions.
Improving reptile ecological risk assessment: Oral and dermal toxicity of pesticides to a common lizard species (Sceloporus occidentalis)
Authors: Weir Scott M. , Yu Shuangying , Talent Larry G. , Maul Jonathan D. , Anderson Todd A. , Salice Christopher J.
Published: March 2015

Reptiles have been understudied in ecotoxicology, which limits consideration in ecological risk assessments. The goals of the present study were 3-fold: to improve oral and dermal dosing methodologies for reptiles, to generate reptile toxicity data for pesticides, and to correlate reptile and avian toxicity. The authors first assessed the toxicity of different dosing vehicles: 100 μL of water, propylene glycol, and acetone were not toxic. The authors then assessed the oral and dermal toxicity of 4 pesticides following the up-and-down procedure. Neither brodifacoum nor chlorothalonil caused mortality at doses ≤ 1750 μg/g. Under the “neat pesticide” oral exposure, endosulfan (median lethal dose [LD50] = 9.8 μg/g) was more toxic than λ-cyhalothrin (LD50 = 916.5 μg/g). Neither chemical was toxic via dermal exposure. An acetone dosing vehicle increased λ-cyhalothrin toxicity (oral LD50 = 9.8 μg/g; dermal LD50 = 17.5 μg/g), but not endosulfan. Finally, changes in dosing method and husbandry significantly increased dermal λ-cyhalothrin LD50s, which highlights the importance of standardized methods. The authors combined data from the present study with other reptile LD50s to correlate with available avian data. When only definitive LD50s were used in the analysis, a strong correlation was found between avian and reptile toxicity. The results suggest it is possible to build predictive relationships between avian and reptile LD50s. More research is needed, however, to understand trends associated with chemical classes and modes of action. Environ Toxicol Chem 2015;34:1778–1786. © 2015 SETAC
Copper and nickel partitioning with nanoscale goethite under variable aquatic conditions
Authors: Danner Kelsey M. , Hammerschmidt Chad R. , Costello David M. , Burton G. Allen
Published: March 2015

Metal contaminated sediments can be toxic to aquatic organisms and are common in human-dominated ecosystems, which results in metals being a leading cause of ecosystem impairment. Bioavailability of metals is influenced by their affinity for dissolved and solid-phase ligands, including iron (Fe) oxyhydroxides, which have been hypothesized to reduce metal toxicity in sediments. The authors examined the adsorption kinetics of copper (Cu) and nickel (Ni) with goethite (α-FeOOH) and characterized the influences of solute metal concentration, pH, ionic strength, and humate concentration on steady-state partitioning of the metals with goethite under conditions representative of natural aquatic environments. Copper and Ni readily adsorbed to goethite, and steady-state partitioning was achieved within 2 h. Although ionic strength had no effect on metal partitioning, adsorption of Cu and Ni to goethite was enhanced by alkaline pH and reduced by competition with humate. Because distribution coefficient (KD) values for Cu and Ni from the present study are comparable to values measured in natural systems, the authors hypothesize that goethite may contribute significantly to the adsorption of both Ni and Cu to particles in the environment. The authors suggest that incorporating binding by Fe oxides in metal bioavailability models should be a priority for improving risk assessment of metal-contaminated oxic sediments. Environ Toxicol Chem 2015;34:1705–1710. © 2015 SETAC
Proteomics analysis of Xenopus laevis gonad tissue following chronic exposure to atrazine
Authors: Chen Xiuping , Wang Jiamei , Zhu Haojun , Ding Jiatong , Peng Yufa
Published: March 2015

Atrazine is the most commonly detected pesticide contaminant in ground and surface water. Previous studies have shown that atrazine is an endocrine disruptor owing to its adverse effects on the male reproductive system in several vertebrates, but very few molecular mechanisms for these effects have been revealed. In the present study, Xenopus laevis were exposed to 100 ppb of atrazine for 120 d, and then the isobaric tags for relative and absolute quantitation (iTRAQ) technique was used to detect global changes in protein profiles of the testes and ovaries. The results showed that 100 ppb of atrazine exposure adversely affected the growth of X. laevis and did not induce hermaphroditism but delayed or prevented the development of male seminiferous tubules. Proteomic analysis showed that atrazine altered expression of 143 and 121 proteins in the testes and ovaries, respectively, and most of them are involved in cellular and metabolic processes and biological regulation based on their biological processes. In addition, apoptosis, tight junctions, and metabolic pathways were significantly altered in the atrazine-treated gonads. Based on the above results, it is postulated that the reproductive toxicity of atrazine may be the result of disruption of tight junctions and metabolic signaling pathways and/or induction of apoptosis in germ cells. Environ Toxicol Chem 2015;34:1770–1777. © 2015 SETAC
Implicit LES of free and wall‐bounded turbulent flows based on the discontinuous Galerkin/symmetric interior penalty method
Authors: de Wiart C. Carton , Hillewaert K. , Bricteux L. , Winckelmans G.
Published: March 2015

This paper presents the second validation step of a compressible discontinuous Galerkin solver with symmetric interior penalty (DGM/SIP) for the direct numerical simulation (DNS) and the large eddy simulation (LES) of complex flows. The method has already been successfully validated for DNS of an academic flow and has been applied to flows around complex geometries (e.g. airfoils and turbomachinery blades). During these studies, the advantages of the dissipation properties of the method have been highlighted, showing a natural tendency to dissipate only the under‐resolved scales (i.e the smallest scales present on the mesh), leaving the larger scales unaffected. This phenomenon is further enhanced as the polynomial order is increased. Indeed, the order increases the dissipation at the largest wave numbers, while its range of impact is reduced. These properties are spectrally compatible with a subgrid‐scale model, and hence DGM may be well suited to be used for an implicit LES (ILES) approach. A validation of this DGM/ILES approach is here investigated on canonical flows, allowing to study the impact of the discretisation on the turbulence for under‐resolved computations. The first test case is the LES of decaying homogeneous isotropic turbulence (HIT) at very high Reynolds number. This benchmark allows to assess the spectral behaviour of the method for implicit LES. The results are in agreement with theory and are even slightly more accurate than other numerical results from literature, obtained using a pseudo‐spectral (PS) method with a state‐of‐the‐art subgrid‐scale model. The second benchmark is the LES of the channel flow. Three Reynolds numbers are considered: Reτ=395, 590 and 950. The results are compared with DNS of Moser et al. and Hoyas et al., also using PS methods. Both averaged velocity and fluctuations are globally in good agreement with the reference, showing the ability of the method to predict equilibrium wall‐bounded flow turbulence. To show that the method is able to perform accurate DNS, a DNS of HIT at Reλ=64 and a DNS of the channel flow at Reτ=180 are also performed. The effects of the grid refinement are investigated on the channel flow at Reτ=395, highlighting the improvement of the results when refining the mesh in the spanwise direction. Finally, the modification of the ILES parameters, that is the Riemann solver and of the SIP coefficient, is studied on both cases, showing a significant influence on the choice of the Riemann solver. Copyright © 2015 John Wiley & Sons, Ltd.
Family Structure and Long‐Term Care Insurance Purchase
Authors: Van Houtven Courtney Harold , Coe Norma B. , Konetzka R. Tamara
Published: March 2015

While it has long been assumed that family structure and potential sources of informal care play a large role in the purchase decisions for long‐term care insurance (LTCI), current empirical evidence is inconclusive. Our study examines the relationship between family structure and LTCI purchase and addresses several major limitations of the prior literature by using a long panel of data and considering modern family relationships, such as the presence of stepchildren. We find that family structure characteristics from one's own generation, particularly about one's spouse, are associated with purchase, but that few family structure attributes from the younger generation have an influence. Family factors that may indicate future caregiver supply are negatively associated with purchase: having a coresidential child, signaling close proximity, and having a currently working spouse, signaling a healthy and able spouse, that long‐term care planning has not occurred yet or that there is less need for asset protection afforded by LTCI. Dynamic factors, such as increasing wealth or turning 65, are associated with higher likelihood of LTCI purchase. Copyright © 2015 John Wiley & Sons, Ltd.
The Effect of Free Personal Care for the Elderly on Informal Caregiving
Authors: Karlsberg Schaffer Sarah
Published: March 2015

Population forecasters have predicted that the proportion of people in the UK aged 65 years and older will rise significantly in coming decades. This shift in demographics will put increasing pressure on the National Health Service and providers of social care. However, older people do not rely only on care provided by the state; informal care of the elderly is often supplied by family and friends. Therefore, the relationship between formal and informal care and the reaction of informal carers to institutional changes is an important policy issue. This study uses individual level data from the British Household Panel Survey to estimate the effects of the introduction of free personal care for the elderly in Scotland on informal care behaviour. As the change in policy applied only to Scotland, a natural experiment is formed allowing a difference‐in‐differences approach to be used. This paper finds that the introduction of the policy increased the probability of women supplying informal care by around six percentage points. In addition, for both sexes, it reports evidence of a shift away from the upper and lower tails towards the middle of the hours of care distribution as a result of the change in policy. Copyright © 2015 John Wiley & Sons, Ltd.
Crowding Out of Long‐Term Care Insurance: Evidence from European Expectations Data
Authors: Costa‐Font Joan , Courbage Christophe
Published: March 2015

Long‐term care (LTC) is the largest insurable risk that old‐age individuals face in most western societies. However, the demand for LTC insurance is still ostensibly small in comparison with the financial risk. One explanation that has received limited support is that expectations of either ‘public sector funding’ and ‘family support’ crowd out individual incentives to seek insurance. This paper aims to investigate further the aforementioned motivational crowding‐out hypothesis by developing a theoretical model and by drawing on an innovative empirical analysis of representative European survey data containing records on individual expectations of LTC funding sources (including private insurance, social insurance, and the family). The theoretical model predicts that, when informal care is treated as exogenously determined, expectations of both state support and informal care can potentially crowd out LTC insurance expectations, while this is not necessarily the case when informal care is endogenous to insurance, as happens when intra‐family moral hazard is integrated in the insurance decision. We find evidence consistent with the presence of family crowding out but no robust evidence of public sector crowding out. Copyright © 2015 John Wiley & Sons, Ltd.
The Causal Effects of Home Care Use on Institutional Long‐Term Care Utilization and Expenditures
Authors: Guo Jing , Konetzka R. Tamara , Manning Willard G.
Published: March 2015

Limited evidence exists on whether expanding home care saves money overall or how much institutional long‐term care can be reduced. This paper estimates the causal effect of Medicaid‐financed home care services on the costs and utilization of institutional long‐term care using Medicaid claims data. A unique instrumental variable was applied to address the potential bias caused by omitted variables or reverse effect of institutional care use. We find that the use of Medicaid‐financed home care services significantly reduced but only partially offset utilization and Medicaid expenditures on nursing facility services. A $1000 increase in Medicaid home care expenditures avoided 2.75 days in nursing facilities and reduced annual Medicaid nursing facility costs by $351 among people over age 65 when selection bias is addressed. Failure to address selection biases would misestimate the substitution and offset effects. Copyright © 2015 John Wiley & Sons, Ltd.
Novel role for carbohydrate responsive element binding protein in the control of ethanol metabolism and susceptibility to binge drinking
Authors: Marmier Solenne , Dentin Renaud , Daujat‐Chavanieu Martine , Guillou Hervé , Bertrand‐Michel Justine , Gerbal‐Chaloin Sabine , Girard Jean , Lotersztajn Sophie , Postic Catherine
Published: March 2015

Carbohydrate responsive element binding protein (ChREBP) is central for de novo fatty acid synthesis under physiological conditions and in the context of nonalcoholic fatty liver disease. We explored its contribution to alcohol‐induced steatosis in a mouse model of binge drinking as acute ethanol (EtOH) intoxication has become an alarming health problem. Within 6 hours, ChREBP acetylation and its recruitment onto target gene promoters were increased in liver of EtOH‐fed mice. Acetylation of ChREBP was dependent on alcohol metabolism because inhibition of alcohol dehydrogenase (ADH) activity blunted ChREBP EtOH‐induced acetylation in mouse hepatocytes. Transfection of an acetylation‐defective mutant of ChREBP (ChREBPK672A) in HepG2 cells impaired the stimulatory effect of EtOH on ChREBP activity. Importantly, ChREBP silencing in the liver of EtOH‐fed mice prevented alcohol‐induced triglyceride accumulation through an inhibition of the lipogenic pathway but also led, unexpectedly, to hypothermia, increased blood acetaldehyde concentrations, and enhanced lethality. This phenotype was associated with impaired hepatic EtOH metabolism as a consequence of reduced ADH activity. While the expression and activity of the NAD+ dependent deacetylase sirtuin 1, a ChREBP‐negative target, were down‐regulated in the liver of alcohol‐fed mice, they were restored to control levels upon ChREBP silencing. In turn, ADH acetylation was reduced, suggesting that ChREBP regulates EtOH metabolism and ADH activity through its direct control of sirtuin 1 expression. Indeed, when sirtuin 1 activity was rescued by resveratrol pretreatment in EtOH‐treated hepatocytes, a significant decrease in ADH protein content and/or acetylation was observed. Conclusion: our study describes a novel role for ChREBP in EtOH metabolism and unravels its protective effect against severe intoxication in response to binge drinking. (Hepatology 2015;62:1086‐1100)
Systemic inflammatory response and serum lipopolysaccharide levels predict multiple organ failure and death in alcoholic hepatitis
Authors: Michelena Javier , Altamirano José , Abraldes Juan G. , Affò Silvia , Morales‐Ibanez Oriol , Sancho‐Bru Pau , Dominguez Marlene , García‐Pagán Juan Carlos , Fernández Javier , Arroyo Vicente , Ginès Pere , Louvet Alexandre , Mathurin Philippe , Mehal Wajahat Z. , Caballería Juan , Bataller Ramón
Published: March 2015

Alcoholic hepatitis (AH) frequently progresses to multiple organ failure (MOF) and death. However, the driving factors are largely unknown. At admission, patients with AH often show criteria of systemic inflammatory response syndrome (SIRS) even in the absence of an infection. We hypothesize that the presence of SIRS may predispose to MOF and death. To test this hypothesis, we studied a cohort including 162 patients with biopsy‐proven AH. The presence of SIRS and infections was assessed in all patients, and multivariate analyses identified variables independently associated with MOF and 90‐day mortality. At admission, 32 (19.8%) patients were diagnosed with a bacterial infection, while 75 (46.3%) fulfilled SIRS criteria; 58 patients (35.8%) developed MOF during hospitalization. Short‐term mortality was significantly higher among patients who developed MOF (62.1% versus 3.8%, P < 0.001). The presence of SIRS was a major predictor of MOF (odds ratio = 2.69, P = 0.025) and strongly correlated with mortality. Importantly, the course of patients with SIRS with and without infection was similar in terms of MOF development and short‐term mortality. Finally, we sought to identify serum markers that differentiate SIRS with and without infection. We studied serum levels of high‐sensitivity C‐reactive protein, procalcitonin, and lipopolysaccharide at admission. All of them predicted mortality. Procalcitonin, but not high‐sensitivity C‐reactive protein, serum levels identified those patients with SIRS and infection. Lipopolysaccharide serum levels predicted MOF and the response to prednisolone. Conclusion: In the presence or absence of infections, SIRS is a major determinant of MOF and mortality in AH, and the mechanisms involved in the development of SIRS should be investigated; procalcitonin serum levels can help to identify patients with infection, and lipopolysaccharide levels may help to predict mortality and the response to steroids. (Hepatology 2015;62:762–772)
Active and Passive Problem Solving: Moderating Role in the Relation Between Depressive Symptoms and Future Suicidal Ideation Varies by Suicide Attempt History
Authors: Quiñones Victoria , Jurska Justyna , Fener Eileen , Miranda Regina
Published: March 2015

Objective

Research suggests that being unable to generate solutions to problems in times of distress may contribute to suicidal thoughts and behavior, and that depression is associated with problem‐solving deficits. This study examined active and passive problem solving as moderators of the association between depressive symptoms and future suicidal ideation among suicide attempters and nonattempters.

Method

Young adults (n = 324, 73% female, mean age = 19, standard deviation = 2.22) with (n = 78) and without (n = 246) a suicide attempt history completed a problem‐solving task, self‐report measures of hopelessness, depression, and suicidal ideation at baseline, and a self‐report measure of suicidal ideation at 6‐month follow‐up.

Results

Passive problem solving was higher among suicide attempters but did not moderate the association between depressive symptoms and future suicidal ideation. Among attempters, active problem solving buffered against depressive symptoms in predicting future suicidal ideation.

Conclusions

Suicide prevention should foster active problem solving, especially among suicide attempters.
EVALUATION OF ALL BABIES CRY, A SECOND GENERATION UNIVERSAL ABUSIVE HEAD TRAUMA PREVENTION PROGRAM
Authors: Morrill Allison C. , McElaney Lisa , Peixotto Betsy , VanVleet Marcia , Sege Robert
Published: March 2015

Child maltreatment results in significant individual, family, and societal costs. This study assessed the efficacy of All Babies Cry (ABC), a media‐based infant maltreatment prevention program, using a mixed‐method, quasi‐experimental staged evaluation design. ABC's messaging, designed and tested through a series of focus groups, provides strategies for reducing parental stress and soothing infants. Participants (n = 423) were first‐time parents, 70% fathers, recruited at two hospitals. The first 211 were controls; the next 212 received ABC. Participants were interviewed 3 times: at baseline in hospital, and by telephone 5 weeks (n = 359; 85%) and 17 weeks (n = 326; 77%) later. Researchers measured parents’ perceptions, intentions, and use of strategies to calm crying and manage caregiver stress. Outcomes were based on the Strengthening Families Model and the Theory of Planned Behavior. The intervention was well received, appears effective in improving mediators of behavior, and may change parental behavior.
THE MARCH GOES ON: COMMUNITY ACCESS FOR PEOPLE WITH DISABILITIES
Authors: McDonald Katherine E. , Williamson Pamela , Weiss Sally , Adya Meera , Blanck Peter ,   DBTAC: Southeast ADA Center PAR Research Consortium
Published: March 2015

Although civil rights legislation designed to remove barriers to and promote full and equal participation in communities has led to some improvements, barriers remain. These barriers create participation disparities among people with disabilities, which in turn contribute to feelings of isolation and poorer health. We used participatory action research to understand present‐day accessibility of important and understudied community settings, namely, state and local government facilities, programs, and services. Using an innovative approach to examining accessibility, we were able to compare the experiences of researchers with and without disabilities, thereby allowing us to identify disparities between the two groups. We found that some progress in providing access has been achieved but that other barriers persist; access for individuals with vision‐related disabilities may be most problematic. Findings indicate that more needs to be done to achieve full accessibility and inclusion.
Upregulation of miR‐155 in CD4+ T Cells Promoted Th1 Bias in Patients With Unstable Angina
Authors: Chen Yanmei , Li Lang , Lu Yongguang , Su Qiang , Sun Yuhan , Liu Yang , Yang Dong
Published: March 2015

An imbalance between T helper 1 (Th1) and T helper 2 (Th2) cells has been reported to increase plaque instability in patients with unstable angina (UA). MicroRNAs play a vital role in the differentiation of CD4+ T cells. However, the role of microRNAs in regulation of Th1/Th2 balance in UA remains unclear. In this study, we aimed to elucidate microRNA expression profiles of circulating CD4+ T cells in UA and to explore the function of microRNAs in the Th1/Th2 balance. A total of 53 patients with UA and 31 control subjects without coronary artery disease were enrolled. Microarray analysis of the microRNA expression profiles of CD4+ T cells revealed that miR‐155 was the most significantly upregulated microRNA of the 451 differentially expressed microRNAs. The upregulation of miR‐155 expression was positively correlated with the percentage of Th1 cells and interferon‐gamma (IFN‐γ) levels in patients with UA. In addition, overexpression of miR‐155 in human circulating CD4+ T cells promoted Th1 differentiation. Further studies identified IFN‐γ receptor alpha chain (IFN‐γ Rα) mRNA as a direct and functional target of miR‐155. A luciferase reporter assay verified that miR‐155 directly targeted IFN‐γ Rα mRNA. Small‐interfering RNA‐mediated knockdown of IFN‐γ Rα mRNA showed effects similar to those of ectopic miR‐155 expression. Thus, our study indicated that upregulation of miR‐155 in circulating CD4+ T cells in patients with UA promoted a shift in the Th1/Th2 balance toward Th1 dominance by repressing IFN‐γ Rα, which may subsequently enhance plaque instability. J. Cell. Physiol. 230: 2498–2509, 2015. © 2015 Wiley Periodicals, Inc.
The dependence of efficiency of transmembrane molecular transfer using electroporation on medium viscosity
Authors: Sungailaitė Sandra , Ruzgys Paulius , Šatkauskienė Ingrida , Čepurnienė Karolina , Šatkauskas Saulius
Published: March 2015

Background

In the present study, we aimed to evaluate the efficiency of drug and gene electrotransfer into cells in vitro depending on medium viscosity.

Methods

Experiments were performed using Chinese hamster ovary cells. Efficiency of molecular electrotransfer depending of medium viscosity was evaluated using two different electroporation conditions: a high‐voltage (HV) pulse and a combination of a high‐voltage pulse and a low‐voltage pulse (HV + LV). To evaluate the efficiency of molecular electrotransfer, anticancer drug bleomycin and two different plasmids coding for green fluorescent protein and luciferase were used.

Results

We found that a slight increase in medium viscosity from 1.3–1.4 mPa·s significantly decreased the transfection efficiency, both in terms of transfected cells and total protein production, which was abolished completely with an increase in medium viscosity to 6.1 mPa·s. Notably, at this medium viscosity, electrotransfer of the small anticancer drug was still efficient. Using HV and HV + LV pulse combinations, we showed that a decrease of DNA electrotransfer, especially at lower medium viscosities, can be compensated for by the LV pulse to some extent. On the other hand, the addition of the LV pulse after the HV pulse did not have any positive effect on the efficiency of bleomycin electrotransfer.

Conclusions

These findings demonstrate that transfection is very susceptible to medium viscosity and highlights the importance of the electrophoretic component in experiments when a considerable transfection level is needed. Copyright © 2015 John Wiley & Sons, Ltd.
Glycosaminoglycan chemical exchange saturation transfer of lumbar intervertebral discs in patients with spondyloarthritis
Authors: Schleich Christoph , Müller‐Lutz Anja , Matuschke Felix , Sewerin Philipp , Sengewein Ruben , Schmitt Benjamin , Ostendorf Benedikt , Wittsack Hans‐Jörg , Stanke Karolin , Antoch Gerald , Miese Falk
Published: March 2015

Purpose

To assess glycosaminoglycan (GAG) content of lumbar intervertebral discs (IVD) in patients with spondyloarthritis (SpA) using glycosaminoglycan chemical exchange saturation transfer (gagCEST).

Materials and Methods

Ninety lumbar intervertebral discs of nine patients with SpA and nine age‐matched healthy controls (eight patients with ankylosing spondylitis; one patient with spondylitis related to inflammatory bowel disease; mean age: 44.1 ± 14.0 years; range: 27–72 years) were examined with a 3T magnetic resonance imaging (MRI) scanner in this prospective study. The MRI protocol included standard morphological, sagittal T2‐weighted (T2w) images to assess Pfirrmann score of the five lumbar IVDs (L1 to S1) and biochemical imaging with gagCEST to calculate a region of interest analysis of nucleus pulposus (NP) and annulus fibrosus (AF). Prior to statistical testing of gagCEST effects (MTRasym values in percent) in patients and controls, IVDs were classified according to the Pfirrmann score.

Results

Significantly lower gagCEST values of NP and AF were found in SpA patients compared with healthy volunteers (NP: 1.41% ± 0.41%, P = 0.001; 95% confidence interval, CI [0.600%–2.226%]; AF: 1.19% ± 0.32%, P < 0.001; CI [0.560%–1.822%]) by comparing the differences of the means. Pooled nondegenerative IVDs (Pfirrmann 1 and 2) had significantly lower gagCEST effects in patients suffering from SpA compared with healthy controls in NP (P < 0.001; CI [1.176%–2.337%]) and AF (P < 0.001; CI [0.858%–1.779%]). No significant difference of MTRasym values was found in degenerative IVDs between patients and controls in NP (P = 0.204; CI [–0.504%–2.170%]).

Conclusion

GagCEST analysis of morphologically nondegenerative IVDs (Pfirrmann score 1 and 2) in T2w images demonstrated significantly lower GAG values in patients with spondyloarthritis in NP and AF, possibly representing a depletion of GAG in spondyloarthritis in the absence of morphologic degeneration.J. Magn. Reson. Imaging 2015. J. Magn. Reson. Imaging 2015;42:1057–1063.
Simulating activities of daily living with finite element analysis improves fracture prediction for patients with metastatic femoral lesions
Authors: Goodheart Jacklyn R. , Cleary Richard J. , Damron Timothy A. , Mann Kenneth A.
Published: March 2015

Predicting fracture risk for patients with metastatic femoral lesions remains an important clinical problem. Mirels' criterion remains the most formalized radiographic scoring system with good sensitivity (correctly identifying clinical fractures) but relatively poor specificity (correctly identify cases that do not fracture). A series of patients with metastatic femoral lesions had Computed Tomography (CT) scans, were followed prospectively for 4 months, and categorized into fracture (n = 5), non‐fracture (n = 28), or stabilized (n = 11) groups. CT based‐Finite Element (FE) modeling was used to predict fracture for these cases using axial compression (AC), level walking (LW), and aggressive stair ascent (ASA) loading conditions. The FE predicted fracture force was greater for the non‐fracture compared to the fracture group for all loading cases. The ability of the FE models to predict fracture cases (sensitivity) was similar for the groups (Mirels, AC, LW: 80%, ASA: 100%). The ability of the models to correctly predict the non‐fracture cases (specificity) was improved for AC (71%) and LW (86%) loading conditions, when compared to Mirels specificity (43%), but poorer for the ASA (21%) conditions. The results suggest that FE models that assess fracture risk using LW conditions can improve fracture prediction over Mirels scoring in a clinical population. © 2015 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 33:1226–1234, 2015.
Biomechanical study of ACL reconstruction grafts
Authors: Pailhé Régis , Cavaignac Etienne , Murgier Jérôme , Laffosse Jean‐Michel , Swider Pascal
Published: March 2015

There are no published studies describing the strength quadrupled gracilis tendon alone and quadrupled semitendinosus tendon alone in the configuration used for anterior cruciate ligament (ACL) reconstruction. The primary objective was to compare the mechanical properties of grafts used for ACL reconstruction during a tensile failure test. The secondary objective was to evaluate the effect of uniform suturing on graft strength. Fifteen pairs of knees were used. The mechanical properties of five types of ACL grafts were evaluated: patellar tendon (PT), sutured patellar tendon (sPT), both hamstring tendons (GST4), quadrupled semitendinosus (ST4), and quadrupled gracilis (G4). Validated methods were used to perform the tensile tests to failure and to record the results. Student's t‐test was used to compare the various samples. The maximum load to failure was 630.8N (± 239.1) for the ST4, 473.5N (± 176.9) for the GST4, 413.3N (± 120.4) for the sPT, and 416.4N (± 187.7) for the G4 construct. Only the ST4 had a significantly higher failure load than the other grafts. The sPT had a higher failure load than the PT. The ST4 construct had the highest maximum load to failure of all the ACL graft types in the testing performed here. Uniform suturing of the grafts improved their ability to withstand tensile loading. © 2015 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 33:1188–1196, 2015.