bluuebunny/crossref_metadata_2025 huggingface dataset:
Analysis of the Role of Peripheral Ligands Coordinated to ZnII in Enhancing the Energy Barrier in Luminescent Linear Trinuclear Zn‐Dy‐Zn Single‐Molecule Magnets
Authors: Costes Jean Pierre , Titos‐Padilla Silvia , Oyarzabal Itziar , Gupta Tulika , Duhayon Carine , Rajaraman Gopalan , Colacio Enrique
Published: September 2015

Three new Dy complexes have been prepared according to a complex‐as‐ligand strategy. Structural determinations indicate that the central Dy ion is surrounded by two LZn units (L2− is the di‐deprotonated form of the N2O2 compartmental N,N′‐2,2‐dimethylpropylenedi(3‐methoxysalicylideneiminato) Schiff base. The Dy ions are nonacoordinate to eight oxygen atoms from the two L ligands and to a water molecule. The Zn ions are pentacoordinate in all cases, linked to the N2O2 atoms from L, and the apical position of the Zn coordination sphere is occupied by a water molecule or bromide or chloride ions. These resulting complexes, formulated (LZnX)‐Dy‐(LZnX), are tricationic with X=H2O and monocationic with X=Br or Cl. They behave as field‐free single‐molecule magnets (SMMs) with effective energy barriers (Ueff) for the reversal of the magnetization of 96.9(6) K with τ0=2.4×10−7 s, 146.8(5) K with τ0=9.2×10−8 s, and 146.1(10) K with τ0=9.9×10−8 s for compounds with ZnOH2, ZnBr, and ZnCl motifs, respectively. The Cole–Cole plots exhibit semicircular shapes with α parameters in the range of 0.19 to 0.29, which suggests multiple relaxation processes. Under a dc applied magnetic field of 1000 Oe, the quantum tunneling of magnetization (QTM) is partly or fully suppressed and the energy barriers increase to Ueff=128.6(5) K and τ0=1.8×10−8 s for 1, Ueff=214.7 K and τ0=9.8×10−9 s for 2, and Ueff=202.4 K and τ0=1.5×10−8 s for 3. The two pairs of largely negatively charged phenoxido oxygen atoms with short DyO bonds are positioned at opposite sides of the Dy3+ ion, which thus creates a strong crystal field that stabilizes the axial MJ=±15/2 doublet as the ground Kramers doublet. Although the compound with the ZnOH2 motifs possesses the larger negative charges on the phenolate oxygen atoms, as confirmed by using DFT calculations, it exhibits the larger distortions of the DyO9 coordination polyhedron from ideal geometries and a smaller Ueff value. Ab initio calculations support the easy‐axis anisotropy of the ground Kramers doublet and predict zero‐field SMM behavior through Orbach and TA‐QTM relaxations via the first excited Kramers doublet, which leads to large energy barriers. In accordance with the experimental results, ab initio calculations have also shown that, compared with water, the peripheral halide ligands coordinated to the Zn2+ ions increase the barrier height when the distortions of the DyO9 have a negative effect. All the complexes exhibit metal‐centered luminescence after excitation into the UV π–π* absorption band of ligand L2− at λ=335 nm, which results in the appearance of the characteristic DyIII (4F9/2→6HJ/2; J=15/2, 13/2) emission bands in the visible region.
Selective and Scalable Chemical Removal of Thin Single‐Walled Carbon Nanotubes from their Mixtures with Double‐Walled Carbon Nanotubes
Authors: Komínková Zuzana , Valeš Václav , Kalbáč Martin
Published: September 2015

Double‐walled carbon nanotubes (DWCNTs) are materials in high demand due to their superior properties. However, it is very challenging to prepare DWCNTs samples of high purity. In particular, the removal of single‐walled carbon nanotubes (SWCNTs) contaminants is a major problem. Here, a procedure for a selective removal of thin‐diameter SWCNTs from their mixtures with DWCNTs by lithium vapor treatment is investigated. The results are evaluated by Raman spectroscopy and in situ Raman spectroelectrochemistry. It is shown that the amount of SWCNTs was reduced by about 35 % after lithium vapor treatment of the studied SWCNTs–DWCNTs mixture.
One‐Pot Synthesis of Carbon‐Coated Nanostructured Iron Oxide on Few‐Layer Graphene for Lithium‐Ion Batteries
Authors: Sun Zhenyu , Madej Edyta , Wiktor Christian , Sinev Ilya , Fischer Roland A. , van Tendeloo Gustaaf , Muhler Martin , Schuhmann Wolfgang , Ventosa Edgar
Published: September 2015

Nanostructure engineering has been demonstrated to improve the electrochemical performance of iron oxide based electrodes in Li‐ion batteries (LIBs). However, the synthesis of advanced functional materials often requires multiple steps. Herein, we present a facile one‐pot synthesis of carbon‐coated nanostructured iron oxide on few‐layer graphene through high‐pressure pyrolysis of ferrocene in the presence of pristine graphene. The ferrocene precursor supplies both iron and carbon to form the carbon‐coated iron oxide, while the graphene acts as a high‐surface‐area anchor to achieve small metal oxide nanoparticles. When evaluated as a negative‐electrode material for LIBs, our composite showed improved electrochemical performance compared to commercial iron oxide nanopowders, especially at fast charge/discharge rates.
Real‐Time Detection of Traces of Benzaldehyde in Benzyl Alcohol as a Solvent by a Flexible Lanthanide Microporous Metal–Organic Framework
Authors: Zhang Huan , Chen Diming , Ma Huili , Cheng Peng
Published: September 2015

Luminescent 3D lanthanide metal–organic framework (Ln‐MOF) {[Tb2(TATAB)2]⋅4 H2O⋅6 DMF}n (1) was synthesized under solvothermal conditions by using flexible ligand 4,4′,4′′‐s‐triazine‐1,3,5‐triyltri‐p‐aminobenzoate (TATAB). A phase transition was observed between low temperature and room temperature. The luminescence of 1 could be enhanced by formaldehyde and quenched efficiently by trace amounts of benzaldehyde in solvents such as benzyl alcohol (0.01–2.0 vol %) and ethanol (0.01–2.5 vol %). This is the first use of a Ln‐MOF as chemical sensor for both formaldehyde and benzaldehyde. The high sensitivity and selectivity of the luminescence response of 1 to benzaldehyde allows it to be used as an excellent sensor for identifying benzaldehyde and provides a simple and convenient method for detecting traces of benzaldehyde in benzyl alcohol based injections. This work establishes a new strategy for detection of benzaldehyde in benzyl alcohol by luminescent MOFs.
Caspase 3 Targeted Cargo Delivery in Apoptotic Cells Using Capped Mesoporous Silica Nanoparticles
Authors: de la Torre Cristina , Mondragón Laura , Coll Carmen , García‐Fernández Alba , Sancenón Félix , Martínez‐Máñez Ramón , Amorós Pedro , Pérez‐Payá Enrique , Orzáez Mar
Published: September 2015

Excessive apoptotic cell death is at the origin of several pathologies, such as degenerative disorders, stroke or ischemia‐reperfusion damage. In this context, strategies to improve inhibition of apoptosis and other types of cell death are of interest and may represent a pharmacological opportunity for the treatment of cell‐death‐related disorders. In this scenario new peptide‐containing delivery systems (solids S1‐P1 and S1‐P2) are described based on mesoporous silica nanoparticles (MSNs) loaded with a dye and capped with the KKGDEVDKKARDEVDK (P1) peptide that contains two repeats of the DEVD target sequence that are selectively hydrolyzed by caspase 3 (C3). This enzyme plays a central role in the execution‐phase of apoptosis. HeLa cells electroporated with S1–P1 are able to deliver the cargo in the presence of staurosporin (STS), which induces apoptosis with the consequent activation of the cytoplasmic C3 enzyme. Moreover, the nanoparticles S1‐P2, containing both a cell‐penetrating TAT peptide and P1 also entered in HeLa cells and delivered the cargo preferentially in cells treated with the apoptosis inducer cisplatin.
Unveiling the Importance of π‐Stacking in Borrowing‐Hydrogen Processes Catalysed by Iridium Complexes with Pyrene Tags
Authors: Ruiz‐Botella Sheila , Peris Eduardo
Published: September 2015

This work describes the preparation of a series of pyrene‐tagged N‐heterocyclic carbene complexes of iridium, and their use in two benchmark borrowing hydrogen reactions: the reduction of ketones by transfer hydrogenation and the β‐alkylation of secondary alcohols with primary alcohols. The detailed study of these homogeneously catalysed reactions reveals several important implications regarding the strong influence of the pyrene tags in the catalysts. First, the catalytic activity is partially inhibited by addition of an external amount of pyrene, but only when pyrene‐tagged catalysts and aromatic substrates are used. Second, the rate order of the reaction is highly dependent on the nature of the substrates and the ligand. When pyrene‐tagged catalysts and aromatic substrates are used, the reaction follows a zero‐order dependence on the concentration of the substrate. All other combinations afford a second‐order rate in the substrates. And third, the presence or absence of the pyrene functionality in the catalyst also influences the reaction order with respect to the concentration of the catalyst. Pyrene‐containing catalysts display a fractional rate order of below 1. Finally, two pyrene‐tagged catalysts were supported onto reduced‐graphene oxide (rGO), and used as heterogeneous catalysts. While the dimetallic catalyst was effectively recycled 12 times, the monometallic catalyst maintained its activity for only three runs.
Iodine‐Catalyzed Decarboxylative Amidation of β,γ‐Unsaturated Carboxylic Acids with Chloramine Salts Leading to Allylic Amides
Authors: Kiyokawa Kensuke , Kojima Takumi , Hishikawa Yusuke , Minakata Satoshi
Published: September 2015

The iodine‐catalyzed decarboxylative amidation of β,γ‐unsaturated carboxylic acids with chloramine salts is described. This method enables the regioselective synthesis of allylic amides from various types of β,γ‐unsaturated carboxylic acids containing substituents at the α‐ and β‐positions. In the reaction, N‐iodo‐N‐chloroamides, generated by the reaction of a chloramine salt with I2, function as a key active species. The reaction provides an attractive alternative to existing methods for the synthesis of useful secondary allylic amine derivatives.
A Theoretical Study of Ene Reactions in Solution: A Solution‐Phase Translational Entropy Model
Authors: Zhao Liu , Li Shi‐Jun , Fang De‐Cai
Published: September 2015

Several density functional theory (DFT) methods, such as CAM‐B3LYP, M06, ωB97x, and ωB97xD, are used to characterize a range of ene reactions. The Gibbs free energy, activation enthalpy, and entropy are calculated with both the gas‐ and solution‐phase translational entropy; the results obtained from the solution‐phase translational entropies are quite close to the experimental measurements, whereas the gas‐phase translational entropies do not perform well. For ene reactions between the enophile propanedioic acid (2‐oxo‐1,3‐dimethyl ester) and π donors, the two‐solvent‐involved explicit+implicit model can be employed to obtain accurate activation entropies and free‐energy barriers, because the interaction between the carbonyl oxygen atom and the solvent in the transition state is strengthened with the formation of C−C and O−H bonds. In contrast, an implicit solvent model is adequate to calculate activation entropies and free‐energy barriers for the corresponding reactions of the enophile 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione.
Design Guidelines for High‐Performance Particle‐Based Photoanodes for Water Splitting: Lanthanum Titanium Oxynitride as a Model
Authors: Landsmann Steve , Maegli Alexandra E. , Trottmann Matthias , Battaglia Corsin , Weidenkaff Anke , Pokrant Simone
Published: September 2015

Semiconductor powders are perfectly suited for the scalable fabrication of particle‐based photoelectrodes, which can be used to split water using the sun as a renewable energy source. This systematic study is focused on variation of the electrode design using LaTiO2N as a model system. We present the influence of particle morphology on charge separation and transport properties combined with post‐treatment procedures, such as necking and size‐dependent co‐catalyst loading. Five rules are proposed to guide the design of high‐performance particle‐based photoanodes by adding or varying several process steps. We also specify how much efficiency improvement can be achieved using each of the steps. For example, implementation of a connectivity network and surface area enhancement leads to thirty times improvement in efficiency and co‐catalyst loading achieves an improvement in efficiency by a factor of seven. Some of these guidelines can be adapted to non‐particle‐based photoelectrodes.
Circulating tumor cells are correlated with disease progression and treatment response in an orthotopic hepatocellular carcinoma model
Authors: Yan Jun , Fan Zhichao , Wu Xiufeng , Xu Min , Jiang Jiahao , Tan Changjun , Wu Weizhong , Wei Xunbin , Zhou Jian
Published: September 2015

Hepatocellular carcinoma (HCC) is a highly malignant tumor characterized by rapid progression, poor prognosis, and frequent hematogenous metastasis. A minimally invasive diagnostic biomarker that can predict disease progression and treatment response would be of extraordinary benefit. Therefore, we have investigated whether the number of circulating tumor cells (CTCs) is correlated with disease progression and treatment response in HCC. Here we report that the number of CTCs, monitored by in vivo flow cytometry (IVFC), is strongly correlated with disease progression and treatment response in a highly metastatic orthotopic nude mouse model of green fluorescent protein (GFP)‐labeled HCC. Sorafenib treatment reduces the number of CTCs significantly. The decreased number of CTCs is consistent with low lung metastasis. This study has demonstrated a considerable clinical value of CTCs as a biomarker in predicting disease progression and monitoring therapeutic efficacy in patients with HCC. © 2015 International Society for Advancement of Cytometry
A New Role for an Old Drug: Metformin Targets MicroRNAs in Treating Diabetes and Cancer
Authors: Zhou Joseph Yi , Xu Biao , Li Lixin
Published: September 2015

Preclinical Research

MicroRNAs (miRNAs) are a family of short, noncoding, 19–23 base pair RNA molecules. Due to their unique role in gene regulation in various tissues, miRNAs play important roles in regulating insulin secretion, metabolic disease, and cancer biology. Emerging evidence demonstrates that miRNAs could also be novel diagnostic markers for a variety of disease states. Additionally, miRNAs have been found to function either as oncogenes, or tumor suppressor genes in cerian cancers. An increasing number of studies have been conducted investigating new drugs targeting miRNAs as a potential anticancer therapy. Metformin is the most widely prescribed medication for treating Type 2 diabetes (T2D). Recent clinical data suggests that metformin impacts the miRNA profile in T2D subjects. Most excitingly, studies have found that metformin is protective against cancer. The anticancer activity of metformin is mediated through a direct regulation of miRNAs, which further modulates several downstream genes in metabolic or preoncogenic pathways. These miRNAs are, therefore, prospective therapeutic targets for treating diabetes and cancer which is the topic of this review. Further study on the regulation of miRNAs by metformin could result in novel therapeutic strategies for recurrent or drug‐esistant cancer, and as part of combinatorial approaches with conventional anticancer therapies. Drug Dev Res 76 : 263–269, 2015. © 2015 Wiley Periodicals, Inc.
Fuels from oils and fats: Recent developments and perspectives
Authors: Mittelbach Martin
Published: September 2015

Fats and oils continue to be the main feedstock for alternative transport fuels, especially for FAME (biodiesel) production. Nevertheless, hydrotreated vegetable oils (HVO), which are mixtures of alkanes, are also established as a commercial fuel. This review describes recent developments in FAME and HVO production and utilization, including microbial oil use. However, the use of unmodified plant oil as fuel or their corresponding engine and emission tests are not discussed. Recent developed catalysts are described for FAME production, including heterogeneous catalysts, such as super acids, ion‐exchange resins, and other green catalysts produced from biomass. Bio‐catalytic approaches using soluble or immobilized enzymes are at the early commercialization stage. Since HVO production technology is based mainly on current mineral oil industry processing methods, the scientific literature is not as extensive as that of FAME production. The main reaction routes of HVO are a combination of hydrogenation, decarboxylation, decarbonylation, hydroisomerization, and cracking under high pressure and temperatures, using supported and unsupported heterogeneous metal catalysts. Recent reports have highlighted the potential use of non‐food oils, such as microalgae lipids, but industrial significant progress has not occurred, leading to some disillusionment with this approach. Therefore, a clear strategy should be developed for upstream and downstream processes with parallel evaluation of life cycle assessment (LCA). In addition, energy intensive steps of biomass drying and solvent extraction should be avoided by using intelligent technologies, such as in situ processing of wet biomass.

Biodiesel and hydrotreated vegetable oils today are the most important alternative diesel fuels in the transport sector. They are produced from the same feedstock, namely oil and fat containing biomass. There has been a shift from food sources to waste material like used cooking oil and animal fat residues as well microbial oils. The latest developments in new feedstock sources, process technologies as well as life cycle assessment and future perspectives are discussed.
Loose excitation–secretion coupling in astrocytes
Authors: Vardjan Nina , Parpura Vladimir , Zorec Robert
Published: September 2015

Astrocytes play an important housekeeping role in the central nervous system. Additionally, as secretory cells, they actively participate in cell‐to‐cell communication, which can be mediated by membrane‐bound vesicles. The gliosignaling molecules stored in these vesicles are discharged into the extracellular space after the vesicle membrane fuses with the plasma membrane. This process is termed exocytosis, regulated by SNARE proteins, and triggered by elevations in cytosolic calcium levels, which are necessary and sufficient for exocytosis in astrocytes. For astrocytic exocytosis, calcium is sourced from the intracellular endoplasmic reticulum store, although its entry from the extracellular space contributes to cytosolic calcium dynamics in astrocytes. Here, we discuss calcium management in astrocytic exocytosis and the properties of the membrane‐bound vesicles that store gliosignaling molecules, including the vesicle fusion machinery and kinetics of vesicle content discharge. In astrocytes, the delay between the increase in cytosolic calcium activity and the discharge of secretions from the vesicular lumen is orders of magnitude longer than that in neurons. This relatively loose excitation‐secretion coupling is likely tailored to the participation of astrocytes in modulating neural network processing. GLIA 2016;64:655–667
Long term motor function after neonatal stroke: Lesion localization above all
Authors: Dinomais Mickael , Hertz‐Pannier Lucie , Groeschel Samuel , Chabrier Stéphane , Delion Matthieu , Husson Béatrice , Kossorotoff Manoelle , Renaud Cyrille , Nguyen The Tich Sylvie ,   for the AVCnn Study Group
Published: September 2015

Motor outcome is variable following neonatal arterial ischemic stroke (NAIS). We analyzed the relationship between lesion characteristics on brain MRI and motor function in children who had suffered from NAIS. Thirty eight full term born children with unilateral NAIS were investigated at the age of seven. 3D T1‐ and 3D FLAIR‐weighted MR images were acquired on a 3T MRI scanner. Lesion characteristics were compared between patients with and without cerebral palsy (CP) using the following approaches: lesion localization either using a category‐based analysis, lesion mapping as well as voxel‐based lesion‐symptom mapping (VLSM). Using diffusion‐weighted imaging the microstructure of the cortico‐spinal tract (CST) was related to the status of CP by measuring DTI parameters. Whereas children with lesions sparing the primary motor system did not develop CP, CP was always present when extensive lesions damaged at least two brain structures involving the motor system. The VLSM approach provided a statistical map that confirmed the cortical lesions in the primary motor system and revealed that CP was highly correlated with lesions in close proximity to the CST. In children with CP, diffusion parameters indicated microstructural changes in the CST at the level of internal capsule and the centrum semiovale. White matter damage of the CST in centrum semiovale was a highly reproducible marker of CP. This is the first description of the implication of this latter region in motor impairment after NAIS. In conclusion, CP in childhood was closely linked to the location of the infarct in the motor system.Hum Brain Mapp 36:4793–4807, 2015.. © 2015 Wiley Periodicals, Inc.
Altered expression of histone deacetylases, inflammatory cytokines and contractile‐associated factors in uterine myometrium of Long Evans rats gestationally exposed to benzo[a]pyrene
Authors: Laknaur Archana , Foster Terri‐Lee , Bobb Lesley E. , Ramesh Aramandla , Ladson Gwinnett M. , Hood Darryl B. , Al‐Hendy Ayman , Thota Chandrasekhar
Published: September 2015

Etiology of preterm birth (PTB) is multifactorial; therefore, decreasing the incidence of PTB is a major challenge in the field of obstetrics. Epidemiological studies have reported an association between toxicants and PTB. However, there are no studies on the role of benzo[a]pyrene (BaP), an environmental toxicant, in the incidence of PTB. We first assessed the effects of BaP (150 and 300 µg kg–1 body weight) dosed via gavage from day 14 to 17 of pregnancy on gestation length in Long Evans rats. We further assessed the histopathology of the uterus, expression of inflammatory cytokines, contractile‐associated factors, histone deacetylases (HDACs) and NFқB‐p65 in myometrium collected on day 22 postpartum versus vehicle‐treated controls. In our study, rats exposed to BaP delivered prematurely (P < 0.05) compared to control. Hematoxylin and eosin staining of uterus showed squamous metaplasia, glandular and stromal hyperplasia in BaP‐exposed rats versus control. The concentrations of BaP metabolites measured by high‐pressure liquid chromatography were higher in uterine myometrium of BaP‐exposed rats while they were undetectable in controls. Quantitative real‐time polymerase chain reaction showed significant increases in mRNA expression of interleukin‐1β and ‐8, tumor necrosis factor‐α, connexin 43, cyclo‐oxygenase‐2 and prostaglandin F2α receptor as compared to controls (P < 0.05). Western blot analysis revealed that BaP exposure caused decreases in class I HDACs 1 and 3 and increases in class II HDAC 5, cyclo‐oxygenase‐2 and nuclear translocation of NFκB‐p65 relative to controls. Our results suggest that gestational exposure to BaP increases incidence of PTB through epigenetic changes that causes increases in the expression of contractile‐associated factors through the NFκB pathway. Copyright © 2015 John Wiley & Sons, Ltd.
Effect of renal impairment on the pharmacokinetics, pharmacodynamics, and safety of apixaban
Authors: Chang Ming , Yu Zhigang , Shenker Andrew , Wang Jessie , Pursley Janice , Byon Wonkyung , Boyd Rebecca A. , LaCreta Frank , Frost Charles E.
Published: September 2015

This open‐label study evaluated apixaban pharmacokinetics, pharmacodynamics, and safety in subjects with mild, moderate, or severe renal impairment and in healthy subjects following a single 10‐mg oral dose. The primary analysis determined the relationship between apixaban AUC∞ and 24‐hour creatinine clearance (CLcr) as a measure of renal function. The relationships between 24‐hour CLcr and iohexol clearance, estimated CLcr (Cockcroft‐Gault equation), and estimated glomerular filtration rate (modification of diet in renal disease [MDRD] equation) were also assessed. Secondary objectives included assessment of safety and tolerability as well as international normalized ratio (INR) and anti–factor Xa activity as pharmacodynamic endpoints. The regression analysis showed that decreasing renal function resulted in modestly increased apixaban exposure (AUC∞ increased by 44% in severe impairment with a 24‐hour CLcr of 15 mL/min, compared with subjects with normal renal function), but it did not affect Cmax or the direct relationship between apixaban plasma concentration and anti–factor Xa activity or INR. The assessment of renal function measured by iohexol clearance, Cockcroft‐Gault, and MDRD was consistent with that determined by 24‐hour CLcr. Apixaban was well tolerated in this study. These results suggest that dose adjustment of apixaban is not required on the basis of renal function alone.
Ocular pharmacology
Authors: Novack Gary D. , Robin Alan L.
Published: September 2015

Ophthalmic diseases include both those analogous to systemic diseases (eg, inflammation, infection, neuronal degeneration) and not analogous (eg, cataract, myopia). Many anterior segment diseases are treated pharmacologically through eye drops, which have an implied therapeutic index of local therapy. Unlike oral dosage forms administered for systemic diseases, eyedrops require patients not only to adhere to treatment, but to be able to accurately perform—ie, instill drops correctly.

Anatomical and physiological barriers make topical delivery to the anterior chamber challenging—in some cases more challenging than absorption through the skin, nasal passages, or gut. Treatment of the posterior segment (eg, vitreous, retina, choroid, and optic nerve) is more challenging due to additional barriers. Recently, intravitreal injections have become a standard of care with biologics for the treatment of macular degeneration and other diseases. Although the eye has esterases, hydroxylases, and transporters, it has relatively little CYP450 enzymes. Because it is challenging to obtain drug concentrations at the target site, ocular clinical pharmacokinetics, and thus pharmacokinetic‐pharmacodynamic interactions, are rarely available. Ophthalmic pharmaceuticals require consideration of solubility, physiological pH, and osmolarity, as well as sterility and stability, which in turn requires optimal pharmaceutics. Although applied locally, ocular medications may be absorbed systemically, which results in morbidity and mortality (eg, systemic hypotension, bronchospasm, and bradycardia).
Excellent outcomes of liver transplantation using severely steatotic grafts from brain‐dead donors
Authors: Wong Tiffany C. L. , Fung James Y. Y. , Chok Kenneth S. H. , Cheung Tan To , Chan Albert C. Y. , Sharr William W. , Dai Wing Chiu , Chan See Ching , Lo Chung Mau
Published: September 2015

Liver grafts with macrovesicular steatosis of >60% are considered unsuitable for deceased donor liver transplantation (DDLT) because of the unacceptably high risk of primary nonfunction (PNF) and graft loss. This study reports our experience in using such grafts from brain‐dead donors. Prospectively collected data of DDLT recipient outcomes from 1991 to 2013 were retrospectively analyzed. Macrovesicular steatosis >60% at postperfusion graft biopsy was defined as severe steatosis. In total, 373 patients underwent DDLT. Nineteen patients received severely steatotic grafts (ie, macrovesicular steatosis >60%), and 354 patients had grafts with ≤60% steatosis (control group). Baseline demographics were comparable except that recipient age was older in the severe steatosis group (51 versus 55 years; P = 0.03). Median Model for End‐Stage Liver Disease (MELD) score was 20 in the severe steatosis group and 22 in the control group. Cold ischemia time (CIT) was 384 minutes in the severe steatosis group and 397.5 minutes in the control group (P = 0.66). The 2 groups were similar in duration of stay in the hospital and in the intensive care unit. Risk of early allograft dysfunction (0/19 [0%] versus 1/354 [0.3%]; P>0.99) and 30‐day mortality (0/19 [0%] versus 11/354 [3.1%]; P = 0.93) were also similar between groups. No patient developed PNF. The 1‐year and 3‐year overall survival rates in the severe steatosis group were both 94.7%. The corresponding rates in the control group were 91.8% and 85.8% (P = 0.55). The use of severely steatotic liver grafts from low‐risk donors was safe, and excellent outcomes were achieved; however, these grafts should be used with caution, especially in patients with high MELD score. Keeping a short CIT was crucial for the successful use of such grafts in liver transplantation. Liver Transpl 22:226‐236, 2016. © 2015 AASLD.
Global stability properties of age‐dependent epidemic models with varying rates of recurrence
Authors: Vargas‐De‐León Cruz
Published: September 2015

The purpose of this paper is to study the global stability properties of equilibria for age‐dependent epidemiological models in presence of recurrence phenomenon. In these systems, the recurrence rate depends on asymptomatic–infection–age. The models are appropriate for human herpes virus (HSV‐1 and HSV‐2) and varicella‐zoster virus. We derived explicit formulas for the basic reproductive number, which completely characterizes the global behaviour of solutions to the models: if the basic reproductive number is less than or equal to unity, the disease will die out; if the basic reproductive number is greater than unity, the disease will be persistent. Volterra‐type Lyapunov functions are constructed to establish the global asymptotic stability of the infection‐free and endemic steady states. Copyright © 2015 John Wiley & Sons, Ltd.
An augmented Cartesian grid method for Stokes–Darcy fluid–structure interactions
Authors: Li Zhilin
Published: September 2015

A new finite difference method based on Cartesian meshes is proposed for solving the fluid–structure interaction between a fluid flow modeled by the Stokes equations and a porous media modeled by the Darcy's law. The idea is to introduce several augmented variables along the interface between the fluid flow and the porous media so that the problem can be decoupled as several Poisson equations. The augmented variables should be chosen so that the Beavers–Joseph–Saffman and other interface conditions are satisfied. In the discretization, the augmented variables have co‐dimension one compared with that of the primitive variables and are solved through the Schur complement system. A non‐trivial analytic solution with a circular interface is constructed to check second‐order convergency of the proposed method. Numerical examples with various interfaces and parameters are also presented. Some simulations show interesting behaviors of the fluid–structure interaction between the fluid flow and the porous media. The computational framework can be applied to other multi‐phase and multi‐physics problems. Copyright © 2015 John Wiley & Sons, Ltd.
Mechanism of the Transmetalation of Organosilanes to Gold
Authors: Falivene Laura , Nelson David J. , Dupuy Stéphanie , Nolan Steven P. , Poater Albert , Cavallo Luigi
Published: September 2015

Density functional theory (DFT) calculations were carried out to study the reaction mechanism of the first transmetalation of organosilanes to gold as a cheap fluoride‐free process. The versatile gold(I) complex [Au(OH)(IPr)] permits very straightforward access to a series of aryl‐, vinyl‐, and alkylgold silanolates by reaction with the appropriate silane reagent. These silanolate compounds are key intermediates in a fluoride‐free process that results in the net transmetalation of organosilanes to gold, rather than the classic activation of silanes as silicates using external fluoride sources. However, here we propose that the gold silanolate is not the active species (as proposed during experimental studies) but is, in fact, a resting state during the transmetalation process, as a concerted step is preferred.
Three‐dimensional Scan Registration using Curvelet Features in Planetary Environments
Authors: Ahuja Siddhant , Iles Peter , Waslander Steven L.
Published: September 2015

Topographic mapping in planetary environments relies on accurate three‐dimensional (3D) scan registration methods. However, most global registration algorithms relying on features such as fast point feature histograms and Harris‐3D show poor alignment accuracy in these settings due to the poor structure of the Mars‐like terrain, and the variable‐resolution, occluded, sparse range data that are difficult to register without some a priori knowledge of the environment. In this paper, we propose an alternative approach to 3D scan registration using the curvelet transform that performs multiresolution geometric analysis to obtain a set of coefficients indexed by scale (coarsest to finest), angle, and spatial position. Features are detected in the curvelet domain to take advantage of the directional selectivity of the transform. A descriptor is computed for each feature by calculating the 3D spatial histogram of the image gradients, and nearest‐neighbor‐based matching is used to calculate the feature correspondences. Correspondence rejection using random sample consensus identifies inliers, and a locally optimal singular value decomposition‐based estimation of the rigid‐body transformation aligns the laser scans given the reprojected correspondences in the metric space. Experimental results on a publicly available dataset of a planetary analogue indoor facility, as well as simulated and real‐world scans from Neptec Design Group's IVIGMS 3D laser rangefinder at the outdoor CSA Mars yard, demonstrate improved performance over existing methods in the challenging sparse Mars‐like terrain.
Image forgery detection in contourlet transform domain based on new chaotic cellular automata
Authors: Barani Milad Jafari , Ayubi Peyman , Jalili Fooad , Valandar Milad Yousefi , Azariyun Ehsan
Published: September 2015

Image authentication includes techniques that detect unauthorized changes in digital pictures. Image authentication is generally categorized into two primary categories, active and passive methods. In this paper, a new active image authentication method is proposed for tamper detection based on contourlet transform. Cellular automata and ‘Game of Life’ are also used to improve the detection of tampered area. A pseudo‐random number generator based on cellular automata has been used to improve security of proposed technique. We evaluates security and randomness of proposed pseudo‐random number generator using by NIST statistical test suite. Experimental results show that the proposed method is sensitive to any tampers, and it can detect forged areas of the images. Visual quality of image after embedding process is desirable due to Peak Signal‐to‐Noise Ratio (PSNR) measure. Copyright © 2015 John Wiley & Sons, Ltd.
Toward An Integration of the Behavioral and Cognitive Influences on the Entrepreneurship Process
Authors: Pryor Christopher , Webb Justin W. , Ireland R. Duane , Ketchen, Jr. David J.
Published: September 2015

Research summary

Entrepreneurs develop innovations, fulfill customer needs, and spur economic growth by recognizing, evaluating, and exploiting opportunities. Despite progress, scholarly understanding of how entrepreneurs achieve these objectives may be incomplete. For instance, little explanation exists for why entrepreneurs may pursue activities seemingly at random, nor is there a clear endpoint to the entrepreneurship process. To address these concerns, we present a framework that integrates sensemaking and structuration perspectives to specify the cognitive and behavioral influences on the entrepreneurship process. Within this framework, entrepreneurs ultimately pursue opportunities through developing and deploying capabilities to create value for customers.

Managerial summary

While entrepreneurs' initial insights regarding innovations and customer needs are important, these insights are only the beginning of an interactive, iterative path that ends with the formation of an organization that can reliably produce value for customers. One of entrepreneurs' most important tools along this path is their set of scripts. Scripts help define how entrepreneurs act and interact so they can fully understand market needs and develop the means for solving these needs. In this paper, our objective is to describe how these scripts help entrepreneurs do the hard work of thinking and acting to effectively create new venture capabilities and to explain how entrepreneurs, who may possess similar sets of scripts, may nevertheless conceptualize different opportunities and solutions.
A survival tree method for the analysis of discrete event times in clinical and epidemiological studies
Authors: Schmid Matthias , Küchenhoff Helmut , Hoerauf Achim , Tutz Gerhard
Published: September 2015

Survival trees are a popular alternative to parametric survival modeling when there are interactions between the predictor variables or when the aim is to stratify patients into prognostic subgroups. A limitation of classical survival tree methodology is that most algorithms for tree construction are designed for continuous outcome variables. Hence, classical methods might not be appropriate if failure time data are measured on a discrete time scale (as is often the case in longitudinal studies where data are collected, e.g., quarterly or yearly). To address this issue, we develop a method for discrete survival tree construction. The proposed technique is based on the result that the likelihood of a discrete survival model is equivalent to the likelihood of a regression model for binary outcome data. Hence, we modify tree construction methods for binary outcomes such that they result in optimized partitions for the estimation of discrete hazard functions. By applying the proposed method to data from a randomized trial in patients with filarial lymphedema, we demonstrate how discrete survival trees can be used to identify clinically relevant patient groups with similar survival behavior. Copyright © 2015 John Wiley & Sons, Ltd.
Optimization of Slag Chemistry Toward Inclusion Control for 28CrMo47 Drill Pipe Steel Based on Viscosity and Equilibration Studies
Authors: Sui Yafei , Yue Changsheng , Peng Ben , Wang Canguo , Guo Min , Zhang Mei , Seetharaman Seshadri
Published: September 2015

During the refining of 28CrMo47 drill pipe steel, it is found that the product often has internal defects and cracks. The present work is initiated with a view to examine if these problems could be solved by optimizing the slag chemistry of the refining slag. Three series of slags, namely, slag A (57.09%CaO–15.74%SiO2–16.35%Al2O3–5.35%MgO, original slag in the steel plant), slag B (55%CaO–21%SiO2–12%Al2O3–7%MgO–5%CaF2), and slag C (51%CaO–17%SiO2–25%Al2O3–7%MgO) are designed and their viscosities are measured. The effect of Al2O3 content on viscosity of the slag C is also investigated as part of the slag optimization. Slag–steel equilibrium experiments are subsequently carried out in order to understand the effect of the slag chemistry, especially the variation in the Al2O3 content in the same on the inclusions in drill pipe steel. It is concluded that both increasing Al2O3 content of the slag used in the refining unit in the plant and addition of CaF2 could decrease effectively the slag viscosity. Inclusions in steel equilibrated with slag C1, corresponding to 51%CaO–7%MgO–25%Al2O3–17SiO2, consisted mainly of low melting point CaO–Al2O3 complex, which did not have any negative effect on the steel quality.
A Note on Unrestricted Composition
Authors: McCarthy Timothy ,   Philosophy Documentation Center
Published: September 2015

I discuss a general limitative consequence of the unrestricted mereological composition thesis. The unrestricted composition thesis, which is roughly the assertion that every plurality of objects possesses a fusion or sum, is shown to be in conflict with general existence-conditions for certain categories of mereologically non-composite objects. The conclusion is that the unrestricted composition thesis,which is a maximizing principle about what aggregates exist, places sharp limits on what unaggregated items can exist.
Revisiting the importance of accounting for seasonal and diel rhythms in fecal stress hormone studies
Authors: Jachowski David S. , Washburn Brian E. , Millspaugh Joshua J.
Published: September 2015

Measurement of fecal glucocorticoid metabolites (FGMs) has been used to quantify stress responses by a wide variety of species; yet, few studies attempt to conduct baseline research prior to investigating effects of disturbances on FGM levels. We evaluated the potential confounding effect of seasonal and diel rhythms on the interpretation of FGM values, by studying long‐term patterns of FGMs in white‐tailed deer (Odocoileus virginianus) and mourning doves (Zenaida macroura) between 2001 and 2002 in a controlled environment at facilities located at the Charles W. Green Conservation Area, near Ashland, Missouri, USA. For 1 year, we collected fresh fecal samples (<1 hr old) on a weekly basis from 17 captive deer and 8 captive doves. We also conducted hourly sampling over discrete 48‐hour periods to evaluate diel rhythms. In deer, we observed that FGMs were nearly 2 times higher during spring months of April and May compared with late winter (i.e., Jan and Feb) and late summer (i.e., Jul and Aug). Dove FGMs were 50% higher during the late spring (i.e., May and Jun) compared with early spring and winter months (Jan–Apr), and twice as high as during late summer, autumn, and early winter months of August through December. In both species, we observed considerable variation in diel rhythms that was inconsistent across individuals. Collectively, our findings emphasize the need for researchers to design sampling schemes that account for high levels of individual and temporal variability in baseline FGMs—and consistently ask: What are “normal” FGM values in the context of the animal's environment and prevailing stressors. © 2015 The Wildlife Society.
On the motion of lumped‐mass and distributed‐mass self‐propelling systems in a linear resistive environment
Authors: Bolotnik N. , Pivovarov M. , Zeidis I. , Zimmermann K.
Published: September 2015

The motion of self‐propelling limbless locomotion systems in a linear viscous environment is considered. The resistance (friction) force acting on an element of the systems is assumed to be proportional to the velocity of this element relative to the environment, the coefficient of proportionality (coefficient of friction) being constant. Two models of interaction of the locomotor with the environment are distinguished. In the first model, the coefficient of friction is constant for a mass element, whereas in the second model, this coefficient is constant for a length element. It is shown that progressive locomotion is impossible for the first model and is possible for the second model. This is explained by the fact that in the second model, the coefficient of friction for a mass element is in fact controlled by changing the length of this element due to deformation of the locomotor's body. The first model applies for lumped mass systems, while the second model is adequate for distributed mass limbless locomotors, like worms. For both models, the equations of motion of the system's center of mass are derived and analyzed.
Bayesian Probabilistic Projection of International Migration
Authors: Azose Jonathan J. , Raftery Adrian E.
Published: September 2015

We propose a method for obtaining joint probabilistic projections of migration for all countries, broken down by age and sex. Joint trajectories for all countries are constrained to satisfy the requirement of zero global net migration. We evaluate our model using out-of-sample validation and compare point projections to the projected migration rates from a persistence model similar to the method used in the United Nations’ World Population Prospects, and also to a state-of-the-art gravity model.
‘The writings of querulous women’: contraception, conscience and clerical authority in 1960s Britain
Authors: Harris Alana
Published: September 2015

On 31 May 1964, Dr Anne Bieżanek travelled from Wallasey to Westminster Cathedral to attend Mass and receive Holy Communion. She was flanked by hoards of reporters, who over the previous six months had fueled extensive media coverage of her establishment of one of the firstCatholicbirth control clinics in the world, alongside her intertwined personal story of the physical and emotional strain caused by ten pregnancies. Repeatedly refused the sacraments by her local parish priest in consequence of these activities, and unable to gain satisfaction from the Bishop of Shrewsbury, Dr Bieżanek wrote to the Archbishop of Westminster to announce her intention to ‘resolve the issue’ through an ethical adjudication at the Communion rails.

As the first sustained exploration of this exceptional woman and her sensational life story, this article examines Dr Bieżanek’s private correspondence and public persona to illustrate the ways in which her idiosyncratic re-negotiation of spiritual and sexual politics was path breaking in articulating a ‘modern’ Catholic approach to love and sex and in anticipating the cacophony of such voices elicited by theHumanae Vitaeencyclical in 1968. As such, it illustrates the form and force of contrasting and modulating Catholic discourses about love, marriage, and contraception in the post-war period and demonstrates the continuing and critical interplay of religion, infused with the insights of sexology and psychology, when negotiating the sexual and spiritual revolutions of the sixties.
Research on the Muzzle Blast Flow with Gas-Particle Mixtures Based on Eulerian-Eulerian Approach
Authors: Zhuo C.-F. , Yao W.-J. , Wu X.-S. , Feng F. , Xu P.
Published: September 2015

The issue on the muzzle blast flow with gas-particle mixtures was numerically investigated in this paper. The propellant gas in the cannon was assumed to be gas-particle mixtures consisting of a variety of gaseous species and particles. The model made use of the Eulerian-Eulerican approach, where the particle were modeled as a second fluid with parameters like bulk density, velocity and temperature, interacting with the gas flow. A high-resolution upwind scheme(AUSMPW+) and detailed reaction kinetics model were employed to solve the chemical non-equilibrium Euler equations for gas phase. The Euler equations for particle phase were solved by MacCormack scheme. The particle diameter and the mass fraction of particle were tested to show their effects on the development process of muzzle blast flow with gas-particle mixtures. The distribution of the main flow parameters of both gas and particle were obtained at different time intervals. The results show the evolution of the muzzle blast flow with gas-particle mixtures and demonstrate the effects of key parameter on the flow field of the gas-particle flow. This paper is a significant investigation for understanding the muzzle blast flow with gas-particle mixtures, which can provide valuable reference for the research on the muzzle blast flow.