bluuebunny/crossref_metadata_2025 huggingface dataset:
Mechanism of Back Electron Transfer in an Intermolecular Photoinduced Electron Transfer Reaction: Solvent as a Charge Mediator
Authors: Narra Sudhakar , Nishimura Yoshifumi , Witek Henryk A. , Shigeto Shinsuke
Published: July 2014

Back electron transfer (BET) is one of the important processes that govern the decay of generated ion pairs in intermolecular photoinduced electron transfer reactions. Unfortunately, a detailed mechanism of BET reactions remains largely unknown in spite of their importance for the development of molecular photovoltaic structures. Here, we examine the BET reaction of pyrene (Py) and 1,4‐dicyanobenzene (DCB) in acetonitrile (ACN) by using time‐resolved near‐ and mid‐IR spectroscopy. The Py dimer radical cation (Py2.+) and DCB radical anion (DCB.−) generated after photoexcitation of Py show asynchronous decay kinetics. To account for this observation, we propose a reaction mechanism that involves electron transfer from DCB.− to the solvent and charge recombination between the resulting ACN dimer anion and Py2.+. The unique role of ACN as a charge mediator revealed herein could have implications for strategies that retard charge recombination in dye‐sensitized solar cells.
Metal Coordination and Isomerization of a Hydrazone Switch
Authors: Croteau Molly L. , Su Xin , Wilcox Dean E. , Aprahamian Ivan
Published: July 2014

Metal coordination and isomerization of a hydrazone‐based molecular switch (1) was investigated with isothermal titration calorimetry (ITC) and UV/Vis spectroscopy. Three equilibria—initial binding, ligand redistribution, and isomerization (1→1′)—are required to characterize the interaction of metal ions with the molecular switch. The stoichiometry of the initial complex and the relative magnitudes of the three equilibria constants depend on the size and Lewis acidity of the metal ion and competition from the counterion. Strongly coordinating anions (e.g., Cl−) suppress the formation of the initial metal–switch complex and isomerization. The thermodynamics for the equilibrium M2++2 1⇌M(1′)22+ have been determined for Zn2+, Cd2+, and Hg2+ from the ITC data.
Quantifying cobalt in doping control urine samples – a pilot study
Authors: Krug Oliver , Kutscher Daniel , Piper Thomas , Geyer Hans , Schänzer Wilhelm , Thevis Mario
Published: July 2014

Since first reports on the impact of metals such as manganese and cobalt on erythropoiesis were published in the late 1920s, cobaltous chloride became a viable though not widespread means for the treatment of anaemic conditions. Today, its use is de facto eliminated from clinical practice; however, its (mis)use in human as well as animal sport as an erythropoiesis‐stimulating agent has been discussed frequently. In order to assess possible analytical options and to provide relevant information on the prevalence of cobalt use/misuse among athletes, urinary cobalt concentrations were determined by inductively coupled plasma‐mass spectrometry (ICP‐MS) from four groups of subjects. The cohorts consisted of (1) a reference population with specimens of 100 non‐elite athletes (not being part of the doping control system), (2) a total of 96 doping control samples from endurance sport athletes, (3) elimination study urine samples collected from six individuals having ingested cobaltous chloride (500 µg/day) through dietary supplements, and (4) samples from people supplementing vitamin B12 (cobalamin) at 500 µg/day, accounting for approximately 22 µg of cobalt. The obtained results demonstrated that urinary cobalt concentrations of the reference population as well as the group of elite athletes were within normal ranges (0.1–2.2 ng/mL). A modest but significant difference between these two groups was observed (Wilcoxon rank sum test, p < 0.01) with the athletes' samples presenting slightly higher urinary cobalt levels. The elimination study urine specimens yielded cobalt concentrations between 40 and 318 ng/mL during the first 6 h post‐administration, and levels remained elevated (>22 ng/mL) up to 33 h. Oral supplementation of 500 µg of cobalamin did not result in urinary cobalt concentrations > 2 ng/mL. Based on these pilot study data it is concluded that measuring the urinary concentration of cobalt can provide information indicating the use of cobaltous chloride by athletes. Additional studies are however required to elucidate further factors potentially influencing urinary cobalt levels. Copyright © 2014 John Wiley & Sons, Ltd.
The Chemistry of Ni–Sb Carbonyl Clusters – Synthesis and Characterization of the [Ni19Sb4(CO)26]4– Tetraanion and the Viologen Salts of [Ni13Sb2(CO)24]n– Carbonyl Clusters
Authors: Femoni Cristina , Iapalucci Maria Carmela , Longoni Giuliano , Zacchini Stefano , Ciabatti Iacopo , Della Valle Raffaele Guido , Mazzani Marcello , Riccò Mauro
Published: July 2014

Within the reinvestigation of Ni–Sb carbonyl cluster chemistry, we report here the synthesis and characterization of the new [Ni19Sb4(CO)26]4– cluster and the synthesis, structure, magnetic characterization and electrical resistivity of the viologen salts of the previously known [Ni13Sb2(CO)24]n– (n = 2, 3) anionic species. The crystal structures of [NEt4]4[Ni19Sb4(CO)26], [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 and [EtV]3[Ni13Sb2(CO)24]·1.5THF (EtV = 1,1′‐diethyl‐4,4′‐bipyridilium cation, DMF = N,N‐dimethylformamide, THF = tetrahydrofuran) are described. Notably, the unit cell of [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 involves a mixture of two [Ni13Sb2(CO)24]3– trianions and one [Ni13Sb2(CO)24]2– dianion, as it also contains eight [EtV]+· radical monocations, which are assembled in infinite stacks. In contrast, the unit cell of the [EtV]3[Ni13Sb2(CO)24]·1.5THF salt contains four [Ni13Sb2(CO)24]3– trianions along with twelve [EtV]+· radical monocations, four of which are arranged into two pairs of isolated dimers, whereas the other two sets of four form two infinite stacks that extend over the whole crystal. The charges of the miscellaneous ions have been assigned on the basis of electroneutrality and spectroscopic evidence. More specifically, the infrared spectra of [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14, both in the solid state and in solution, clearly indicate the presence of a 2:1 mixture of [Ni13Sb2(CO)24]3– and [Ni13Sb2(CO)24]2– anions. Resistivity measurements performed on pellets of powdered samples indicate that the [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 salt substantially behaves as an insulator. A study of the magnetic behaviour of [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 evidences pairing among the electrons of the EtV+· molecules, in agreement with DFT calculations, and the odd‐electron clusters behave as paramagnetic centres of spin S = 1.
Aromaticity and Magnetic Properties of 1‐ and 2‐Indenones and Their Aza Derivatives
Authors: Poater Jordi , Solà Miquel , Alkorta Ibon , Elguero José
Published: July 2014

The almost unknown series of 1‐ and 2‐indenones and their aza‐derivatives have been analyzed with the aim of understanding the higher stability and aromaticity of the 1‐one compared to the 2‐one series. The effect of tetrafluorination of the six‐membered ring on their relative stability and aromaticity and the corresponding 19F–19F spin–spin coupling constants (SSCC) have been analyzed for the compounds of these two series. Magnetic NICS and electronic PDI, FLU, and MCI aromaticity criteria, complemented by an energy decomposition analysis, allow the higher stability and aromaticity of 1‐indenones compared with 2‐indenones to be attributed to the π‐component of the orbital interaction term. The reduced aromatic character of the 2‐one series also provides an explanation for the 19F–19F SSCC observed in the tetrafluorinated 2‐one compounds, which differ significantly from those of 1,2,3,4‐tetrafluorobenzene.
Unsymmetrical vic‐Tricarbonyl Compounds for the Total Syntheses of Cladoniamide G and Cladoniamide F
Authors: Schütte Julia , Kilgenstein Frank , Fischer Michel , Koert Ulrich
Published: July 2014

A 2‐unsubstituted indole adds under Cu‐box‐catalysis to mesoxalic ester amides with high enantioselectivity, whereas low enantiomeric excess is obtained for 2‐substituted indoles. A mesoxalic ester amide is used as key component in the total syntheses of alkaloids cladoniamide G and cladoniamide F. The natural product syntheses involve Suzuki cross‐coupling to a 2,2′‐biindole, arylation of the vic‐tricarbonyl compound, and intramolecular lactam formation.
Gold Nanobone/Carbon Nanotube Hybrids for the Efficient Nonenzymatic Detection of H2O2 and Glucose
Authors: Jou Amily Fang‐ju , Tai Nyan‐Hwa , Ho Ja‐an Annie
Published: July 2014

We report a facile strategy for the synthesis of gold nanobone/carbon nanotube (CNT@GNB) nanoassemblies, which were prepared through hybridization of CNTs and GNBs mediated by a thiolated pyrene derivative. The SEM images confirmed the successful construction of the CNT@GNB nanoassemblies. Screen printed electrodes modified with the CNT@GNB nanoassemblies exhibited decent electrocatalytic activity, large surface‐to‐volume ratios, high electrochemical reversibility, and efficient electron transport properties, thereby enabling stable and sensitive nonenzymatic detection of H2O2 and glucose, with detection limits of 0.8 µM and 0.07 mM, respectively. Moreover, no interference was observed at a potential of +0.38 V for the interfering species, such as ascorbic acid and urea, indicating high selectivity toward the glucose detection.
Application of temperature‐correlated mobility theory for optimizing the MEKC separation of the main lignans from Schisandra Chinensis Fructus and its prescription Yuye Decoction
Authors: Liu Jingyi , Petersen Nickolaj Jacob , Lee Kai‐Fai , Hansen Steen Honoré , Lao Lixing , Sze Chowing , Zhang Yanbo
Published: July 2014

The present work shows the application of the temperature‐correlated mobility theory for the optimization of the separation and peak alignment of the main lignans from water extracts of traditional Chinese medicine Schisandra Chinensis Fructus as well as its prescription Yuye Decoction (Jade Fluid Decoction; YYD). This is the first application of this theory for MEKC separations, and the data presentation allows a much easier peak tracking and thereby identification of the analytes. Most interestingly, the data obtained and presented in the mobility scale at 298 K, show that Schisantherin A, which is easily mistaken as one of the analytes using traditional time scale, was actually not detected in Schisandra Chinensis Fructus and Yuye Decoction (Jade Fluid Decoction) water extracts. This proves the value of the temperature‐correlated mobility scale for method optimization of complex samples. Thus, in the temperature‐correlated mobility scale, the optimization of the system conditions for the MEKC separations can easily be achieved by correcting for viscosity changes. Also, the influence of the operating temperature can be monitored in a more distinct way.
Detection of S‐adenosylhomocysteine and methylation index in blood by capillary electrophoresis
Authors: Ivanov Alexander V. , Luzyanin Boris P. , Virus Edward D. , Rotkina Anna S. , Kubatiev Aslan A.
Published: July 2014

This work proposes an approach to the direct analysis of S‐adenosylhomocysteine (SAH) and the methylation index in blood using CE with UV detection (CE‐UV). After application of meglumine postinjection, we achieved SAH in‐capillary preconcentration in the HClO4 extracts of erythrocytes, which improved the detection limit (S/N = 3) of SAH up to 3 fmol or 180 nmol/L at the injection volume of 50 nL, taking into account the sample dilution rate. CE‐UV was carried out in 30 mM glycine and 45 mmol/L HCl (pH ∼1.8) at 17 kV in a capillary 48 cm in length and 50 μm id. Accuracy of the technique was 101% and reproducibility was about 12%.
Recent advances in capillary electrochromatography using molecularly imprinted polymers
Authors: Iacob Bogdan‐Cezar , Bodoki Ede , Oprean Radu
Published: July 2014

There is an increased and continuous need for developing new methods for the separation and quantification of an increasing number of analytes in the environmental, pharmaceutical, pharmacological, and toxicological sciences. CEC is still withholding its popularity, representing a viable alternative to the more conventional techniques (HPLC, GC) due to the numerous advantages, such as, low sample/reagent volumes, high separation efficiencies, hybrid separation principle, etc. One particular promising direction in CEC is the use of molecularly imprinted polymers (MIPs) as stationary phases. They are usually immobilized in the capillary column as a continuous polymeric monolith or as a thin polymer coating attached to the capillary's inner wall. Another emerging trend is the use of MIPs in the form of nanoparticles as a pseudostationary phase. This review discusses the recent developments (2011–2013) in finding the optimal polymerization mixture and the suitable MIP format that should be employed in CEC separations. The most important applications of MIPs in CEC technique are also highlighted.
Integration in microalgal bioprocess development: Design of efficient, sustainable, and economic processes
Authors: Fresewinkel Mark , Rosello Rosa , Wilhelm Christian , Kruse Olaf , Hankamer Ben , Posten Clemens
Published: July 2014

The use of microalgae as a production system has gained huge interest in recent years. Recent research has concentrated on single aspects, such as the microalgal cells or the photobioreactors. The design of sustainable, effective, and economic processes for microalgal products requires the integration of microalgal biology including strain selection and genetic engineering, process, and reactor design and integration into environmental mass and energy fluxes. This involves tools of biotechnology and process engineering. Several attempts of such integrated processes have been developed. This review groups the integration aspects into several degrees of integration with respect to the classical upstream, bioreaction, and downstream steps. The integration levels consider metabolic, process, environmental, and social integration. At the end, the following question remains: How far can microalgal biotechnology help to solve the problems of feed, food, and fuel supply and contribute to a better society? Overall, this review gives an overview of the different stages of integration in microalgal processes. It is a guide towards conceptual positioning and planning of microalgal plants. Furthermore, it is a decision guide to support microalgal technologies.
A simulation study of a bioethanol‐solar‐reforming system for proton‐exchange membrane fuel cell home cogeneration system
Authors: Obara Shin'ya
Published: July 2014

The energy supply characteristic of a proton‐exchange membrane fuel cell for houses is strongly influenced in a hydrogen supply unit. Therefore, a bioethanol reforming system (FBSR) with a sunlight heat source is developed as a potential fuel supply system for distributed fuel cells. However, the temperature distribution of a catalyst layer in the reactor is not stable under conditions of unstable solar radiation and unstable outside air temperature; as a result, it is thought that the inversion ratio (the percentage of hydrogen obtained from ethanol) of a reforming reaction will decrease. In this paper, heat transmission analysis was used in the catalyst layer of the reformer of FBSR, and the fundamental performance of FBSR was investigated. Fluctuations of the solar insolation over a short period of time affect the hydrogen‐generating rate of FBSR. Moreover, the amount of hydrogen production of FBSR was simulated using meteorological data from a day in March and a day in August in a cold region (Sapporo in Japan). In this research, the relation between the collected area of a solar collector and the energy supply to an individual house was obtained.
Deregulated FOX genes in Hodgkin lymphoma
Authors: Nagel Stefan , Meyer Corinna , Kaufmann Maren , Drexler Hans G. , MacLeod Roderick A. F.
Published: July 2014

FOX genes encode transcription factors which regulate basic developmental processes during embryogenesis and in the adult. Several FOX genes show deregulated expression in particular malignancies, representing oncogenes or tumor suppressors. Here, we screened six Hodgkin lymphoma (HL) cell lines for FOX gene activity by comparative microarray profiling, revealing overexpression of FOXC1 and FOXD1, and reduced transcription of FOXN3, FOXO1, and FOXP1. In silico expression analyses of these FOX gene candidates in HL patient samples supported the cell line data. Chromosomal analyses demonstrated an amplification of the FOXC1 locus at 6p25 and a gain of the FOXR2 locus at Xp11, indicting genomic aberrations for their upregulation. Comparative expression profiling and ensuing stimulation experiments revealed implementation of the TGFβ‐ and WNT‐signaling pathways in deregulation of FOXD1 and FOXN3. Functional analysis of FOXP1 implicated miR9 and miR34a as upstream regulators and PAX5, TCF3, and RAG2 as downstream targets. A similar exercise for FOXC1 revealed repression of MSX1 and activation of IPO7, both mediating inhibition of the B‐cell specific homeobox gene ZHX2. Taken together, our data show that aberrantly expressed FOX genes and their downstream targets are involved in the pathogenesis of HL via deregulation of B‐cell differentiation and may represent useful diagnostic markers and/or therapeutic targets. © 2014 Wiley Periodicals, Inc.
Applying multi‐parameter runoff elasticity to assess water availability in a changing climate: an example from Texas, USA
Authors: Brikowski T. H.
Published: July 2014

Adaptation and mitigation efforts related to global trends in climate and water scarcity must often be implemented at the local, single‐catchment scale. A key requirement is understanding the impact of local climate and watershed characteristics coupled with these regional trends. For surface water, determination of multi‐parameter runoff elasticities is a promising tool for achieving such understanding, as explored here for two surface‐water dependent basins in Texas. The first basin is the water supply for Dallas‐Ft. Worth (DFW), and exhibits relatively high precipitation elasticity (proportional change in runoff to change in precipitation) εP = 2.64, and temperature elasticity εT = − 0.41. Standard precipitation–temperature elasticity diagrams exhibit unusual concave contours of runoff change, indicating influence of additional parameters, which can be isolated using multi‐parameter approaches. The most influential local parameter in DFW is unexpected reduced runoff fraction in cooler wetter years. Those years exhibit increased summer (JJA) precipitation fraction, but predominant cracking soils in DFW minimize JJA runoff, yielding negative . A comparative basin near Houston shows positive , reflecting the local impact of tropical cyclones and lesser abundance of cracking soils. Both basins exhibit positive elasticity to 1‐year previous precipitation (e.g. DFW εP − 1 = 1.24), reflecting the influence of soil moisture storage. Only DFW exhibits negative elasticity to 2‐year previous precipitation (εP − 2 = − 0.65), reflecting multi‐year influence of vegetation growth and increased evapotranspiration.

Using these elasticities, analysis of historical multi‐decadal climate departures for DFW indicates the 80% decrease in runoff during the 1950–1957 drought of record was primarily caused by reduced precipitation. Runoff 56% above‐normal during an unprecedented 1986–1998 wet period was primarily caused by increased precipitation. Since 2000, despite precipitation slightly above normal, runoff has decreased 20%, primarily in response to ∼ 1∘C warming. Future precipitation droughts superimposed on this new drier normal are likely to be much more severe than historical experience would indicate. Copyright © 2014 John Wiley & Sons, Ltd.
Aquatic risk assessment of pesticides in Latin America
Authors: Carriquiriborde Pedro , Mirabella Paula , Waichman Andrea , Solomon Keith , Van den Brink Paul J , Maund Steve
Published: July 2014

Latin America is anticipated to be a major growth market for agriculture and production is increasing with use of technologies such as pesticides. Reports of contamination of aquatic ecosystems by pesticides in Latin America have raised concerns about potential for adverse ecological effects. In the registration process of pesticides, all countries require significant data packages on aquatic toxicology and environmental fate. However, there are usually no specific requirements to conduct an aquatic risk assessment. To address this issue, the Society of Environmental Toxicology and Chemistry organized a workshop that brought together scientists from academia, government, and industry to review and elaborate on aquatic risk assessment frameworks that can be implemented into regulation of pesticides in Latin America. The workshop concluded that the international framework for risk assessments (protection goals, effects, and exposure assessments, risk characterization, and risk mitigation) is broadly applicable in Latin America but needs further refinement for the use in the region. Some of the challenges associated with these refinements are discussed in the article. It was recognized that there is potential for data sharing both within and outside of the region where conditions are similar. However, there is a need for research to compare local species and environmental conditions to those in other jurisdictions to be able to evaluate the applicability of data used in other countries. Development should also focus on human resources as there is a need to build local capacity and capability, and scientific collaboration and exchange between stakeholders in industry, government, and academia is also important. The meeting also emphasized that, although establishing a regionally relevant risk assessment framework is important, this also needs to be accompanied by enforcement of developed regulations and good management practices to help protect aquatic habitats. Education, training, and communication efforts are needed to achieve this. Integr Environ Assess Manag 2014;10:539–542. © 2014 SETAC

Key Points

Participants at a SETAC workshop concluded that the international framework for risk assessment of pesticides in aquatic systems is applicable but needs further refinement to be made specific for Latin American uses of pesticides. Of the countries in the survey, Brazil and Peru were the only countries with a framework for environmental risk assessment included in their legislation, and only Peru's legislation included specific protection goals Research is needed to compare local species and environmental conditions, to evaluate applicability of data generated in other jurisdictions and to characterize pesticide use in each country. Risk assessment of pesticides is important but there also needs to be a focus on good management practices to protect aquatic habitats.
Comparative Effects of Teriparatide, Denosumab, and Combination Therapy on Peripheral Compartmental Bone Density, Microarchitecture, and Estimated Strength: the DATA-HRpQCT Study
Authors: Tsai Joy N , Uihlein Alexander V , Burnett-Bowie Sherri-Ann M , Neer Robert M , Zhu Yuli , Derrico Nicholas , Lee Hang , Bouxsein Mary L , Leder Benjamin Z
Published: July 2014

Combined teriparatide and denosumab increases spine and hip bone mineral density more than either drug alone. The effect of this combination on skeletal microstructure and microarchitecture, however, is unknown. Because skeletal microstructure and microarchitecture are important components of skeletal integrity, we performed high-resolution peripheral quantitative computed tomography (HR-pQCT) assessments at the distal tibia and radius in postmenopausal osteoporotic women randomized to receive teriparatide 20 µg daily (n = 31), denosumab 60 mg every 6 months (n = 33), or both (n = 30) for 12 months. In the teriparatide group, total volumetric bone mineral density (vBMD) did not change at either anatomic site but increased in both other groups at both sites. The increase in vBMD at the tibia was greater in the combination group (3.1 ± 2.2%) than both the denosumab (2.2 ± 1.9%) and teriparatide groups (–0.3 ± 1.9%) (p < 0.02 for both comparisons). Cortical vBMD decreased by 1.6 ± 1.9% at the tibia and by 0.9 ± 2.8% at the radius in the teriparatide group, whereas it increased in both other groups at both sites. Tibia cortical vBMD increased more in the combination group (1.5 ± 1.5%) than both monotherapy groups (p < 0.04 for both comparisons). Cortical thickness did not change in the teriparatide group but increased in both other groups. The increase in cortical thickness at the tibia was greater in the combination group (5.4 ± 3.9%) than both monotherapy groups (p < 0.01 for both comparisons). In the teriparatide group, radial cortical porosity increased by 20.9 ± 37.6% and by 5.6 ± 9.9% at the tibia but did not change in the other two groups. Bone stiffness and failure load, as estimated by finite element analysis, did not change in the teriparatide group but increased in the other two groups at both sites. Together, these findings suggest that the use of denosumab and teriparatide in combination improves HR-pQCT measures of bone quality more than either drug alone and may be of significant clinical benefit in the treatment of postmenopausal osteoporosis. © 2014 American Society for Bone and Mineral Research.
Combined MEK Inhibition and BMP2 Treatment Promotes Osteoblast Differentiation and Bone Healing in Nf1Osx−/− Mice
Authors: de la Croix Ndong Jean , Stevens David M , Vignaux Guillaume , Uppuganti Sasidhar , Perrien Daniel S , Yang Xiangli , Nyman Jeffry S , Harth Eva , Elefteriou Florent
Published: July 2014

Neurofibromatosis type I (NF1) is an autosomal dominant disease with an incidence of 1/3000, caused by mutations in the NF1 gene, which encodes the RAS/GTPase-activating protein neurofibromin. Non-bone union after fracture (pseudarthrosis) in children with NF1 remains a challenging orthopedic condition to treat. Recent progress in understanding the biology of neurofibromin suggested that NF1 pseudarthrosis stems primarily from defects in the bone mesenchymal lineage and hypersensitivity of hematopoietic cells to TGFβ. However, clinically relevant pharmacological approaches to augment bone union in these patients remain limited. In this study, we report the generation of a novel conditional mutant mouse line used to model NF1 pseudoarthrosis, in which Nf1 can be ablated in an inducible fashion in osteoprogenitors of postnatal mice, thus circumventing the dwarfism associated with previous mouse models where Nf1 is ablated in embryonic mesenchymal cell lineages. An ex vivo–based cell culture approach based on the use of Nf1flox/flox bone marrow stromal cells showed that loss of Nf1 impairs osteoprogenitor cell differentiation in a cell-autonomous manner, independent of developmental growth plate–derived or paracrine/hormonal influences. In addition, in vitro gene expression and differentiation assays indicated that chronic ERK activation in Nf1-deficient osteoprogenitors blunts the pro-osteogenic property of BMP2, based on the observation that only combination treatment with BMP2 and MEK inhibition promoted the differentiation of Nf1-deficient osteoprogenitors. The in vivo preclinical relevance of these findings was confirmed by the improved bone healing and callus strength observed in Nf1osx−/− mice receiving Trametinib (a MEK inhibitor) and BMP2 released locally at the fracture site via a novel nanoparticle and polyglycidol-based delivery method. Collectively, these results provide novel evidence for a cell-autonomous role of neurofibromin in osteoprogenitor cells and insights about a novel targeted approach for the treatment of NF1 pseudoarthrosis. © 2014 American Society for Bone and Mineral Research.
Vitamin D Receptor Signaling Enhances Locomotive Ability in Mice
Authors: Sakai Sadaoki , Suzuki Miho , Tashiro Yoshihito , Tanaka Keisuke , Takeda Satoshi , Aizawa Ken , Hirata Michinori , Yogo Kenji , Endo Koichi
Published: July 2014

Bone fractures markedly reduce quality of life and life expectancy in elderly people. Although osteoporosis increases bone fragility, fractures frequently occur in patients with normal bone mineral density. Because most fractures occur on falling, preventing falls is another focus for reducing bone fractures. In this study, we investigated the role of vitamin D receptor (VDR) signaling in locomotive ability. In the rotarod test, physical exercise enhanced locomotive ability of wild-type (WT) mice by 1.6-fold, whereas exercise did not enhance locomotive ability of VDR knockout (KO) mice. Compared with WT mice, VDR KO mice had smaller peripheral nerve axonal diameter and disordered AChR morphology on the extensor digitorum longus muscle. Eldecalcitol (ED-71, ELD), an analog of 1,25(OH)2D3, administered to rotarod-trained C57BL/6 mice enhanced locomotor performance compared with vehicle-treated nontrained mice. The area of AChR cluster on the extensor digitorum longus was greater in ELD-treated mice than in vehicle-treated mice. ELD and 1,25(OH)2D3 enhanced expression of IGF-1, myelin basic protein, and VDR in rat primary Schwann cells. VDR signaling regulates neuromuscular maintenance and enhances locomotive ability after physical exercise. Further investigation is required, but Schwann cells and the neuromuscular junction are targets of vitamin D3 signaling in locomotive ability. © 2014 American Society for Bone and Mineral Research.
Sonographic appearance of a dermoid cyst (mature cystic teratoma) of the spleen
Authors: Gerscovich Eugenio O. , Fananapazir Ghaneh , McGahan John P. , Hirschbein Jonah S. , Naderi Sima , Corwin Michael T. , Durham Benjamin H.
Published: July 2014

Splenic dermoids are rare, with few published case reports and no ultrasound images in the English literature. We report the case of a 57‐year‐old woman with that diagnosis and illustrate it with ultrasound, CT, and pathology images. We discuss the differential diagnosis of solid splenic lesions. © 2014 Wiley Periodicals, Inc. J Clin Ultrasound, 43:132–134, 2015
Characterization of silica distribution in rice husk using Synchrotron Radiation µCT and its implications for archaeological interpretation
Authors: Wu Yan , Yang Yimin , Xiao Tiqiao , Gu Zhou , Hill David V. , Wang Changsui
Published: July 2014

This article reports the results of a pilot project using Synchrotron Radiation µCT (computer‐aided tomography) to examine the distribution of silica within phytoliths from rice husks. Experiments indicate that computed tomography can be used to show how silica accumulates and is distributed in a distinctive zigzag pattern of long epidermal cells that are characteristic of phytoliths from rice husks. This method will help us to understand why the dry ashing method produced much more zigzag pattern of long cells phytoliths from rice husk than did the acid extraction method. Besides, the zigzag morphological pattern exhibited by long epidermal cells is characteristic of this species which makes it useful in the identification of rice husks from archaeological contexts and indicating heating process. Microsc. Res. Tech. 77:785–789, 2014. © 2014 Wiley Periodicals, Inc.
m‐CPBA‐Mediated IntramolecularAminohydroxylation of N‐Sulfonyl Aminoalkenes to Synthesize β‐Hydroxyl Cyclic Amines
Authors: Yin Yan , Zhou Hong , Sun Guofeng , Liu Xichen
Published: July 2014

A variety of structurally diverse N‐sulfonyl‐protected aminoalkenes readily reacted with m‐CPBA to produce a series of β‐hydroxyl cyclic amines in high yields through intramolecular aminohydroxylation. This metal‐free and easy‐to‐handle synthetic methodology offered an environmentally friendly alternative to vicinal difunctionalization of alkenes.
Dexamethasone reduces brain cell apoptosis and inhibits inflammatory response in rats with intracerebral hemorrhage
Authors: Lee I‐Neng , Cheng Wan‐Chun , Chung Chiu‐Yen , Lee Ming‐Hsueh , Lin Martin Hsiu‐Chu , Kuo Chia‐Hui , Weng Hsu‐Huei , Yang Jen‐Tsung
Published: July 2014

Spontaneous intracerebral hemorrhage (ICH) is associated with high rates of mortality and morbidity. Thus, the identification of novel therapeutic agents for preventing strokes and attenuating poststroke brain damage is crucial. Dexamethasone (DEX) is used clinically to reduce edema formation in patients with spinal cord injury and brain tumors. In this study, we sought to elucidate the effects of DEX treatment on apoptosis and inflammation following ICH in rats. A high dose of DEX (15 mg/kg) was administered immediately following ICH induction and again 3 days later. The inflammatory and apoptotic responses in the rat brains were evaluated by using hematoxylin‐eosin, terminal deoxynucleotidyl transferase dUTP nick end labeling, Nissl, and neurofilament‐H staining. Levels of phosphorylated neurofilaments and apoptosis‐related proteins such as B‐cell lymphoma 2 (Bcl‐2), Bcl‐2 associated X protein (Bax), caspase‐3, and P53 were analyzed by Western blotting. This study shows that rats without ICH that received DEX treatment had a fourfold higher expression of Bcl‐2 than sham‐operated rats. ICH causes an increase in Bax, cleaved caspase‐3, and P53 proteins from 4 hr to 7 days following ICH induction. In comparison with the ICH rats, the ICH/DEX rats showed significantly decreased apoptotic cell death and increased neuron survival and maintained neurofilament integrity in the perihematomal region. DEX increased the Bcl‐2/Bax ratio and lowered the expression of cleaved caspase‐3 at 12 hr and 5 days. The ICH rats were accompanied by activation of the inflammatory response, and DEX treatment modulated the expression of a variety of cell types and then decreased ICH‐induced apoptosis. © 2014 Wiley Periodicals, Inc.
Effects of combined therapy with glipizide and Aralia root bark extract on glycemic control and lipid profiles in patients with type 2 diabetes mellitus
Authors: Liu Xiao‐Hong , Li Xing‐Min , Han Cheng‐Cheng , Fang Xiang‐Feng , Ma Le
Published: July 2014

BACKGROUND

The root bark of Aralia is a rich source of bioactive components that may improve glycemic control and lipid status. In this study, 148 patients with type 2 diabetes mellitus (T2DM) were assigned randomly to receive either glipizide alone or glipizide plus Aralia root bark extract (ARBE) for 8 weeks to test the effects of ARBE plus glipizide therapy on glycemic control and lipid profiles in these patients.

RESULTS

Levels of HbA1c, fasting plasma glucose (FPG) and 2 h postprandial plasma glucose (2‐h PPG) in both groups significantly decreased from baseline. Glycated hemoglobin (HbA1c) decreased marginally significantly in participants taking glipizide plus ARBE compared with the glipizide group (P = 0.06). Participants in the combination group had significant decreases in total cholesterol (TC) and low‐density lipoprotein cholesterol (LDL‐C), and the between‐group difference achieved statistical significance for LDL‐C (P = 0.04). Reduction in HbA1c in the combination group was significantly associated with changes in TC (r = 0.32; P = 0.006) and LDL‐C (r = 0.34; P = 0.005), and the change in FPG was inversely correlated with LDL‐C reduction (r = 0.34; P = 0.004).

CONCLUSIONS

In patients with T2DM, combination therapy with glipizide and ARBE resulted in moderately lowering HbA1c and LDL‐C levels compared with glipizide alone. © 2014 Society of Chemical Industry
Does the Glass Transition of Polymers Change Upon 3D Confinement?
Authors: Martínez‐Tong Daniel E. , Cui Jing , Soccio Michelina , García Carolina , Ezquerra Tiberio A. , Nogales Aurora
Published: July 2014

The calorimetric trace of polymer spheres shows an increase of the glass‐transition temperature (Tg), with respect to its bulk value. This increase is evaluated by means of an entropy model, where the 3D confinement leads to a limiting number of repeating polymer units in the sphere, and thus to a reduction of the possible configuration states of the polymer chains. This is ultimately related to variations in the bulk value of the Tg. Also, the way the polymer nature affects how confinement takes place and how restrictions imposed affect the way a polymer forms cooperative rearranging regions at Tg are presented.

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Hybrid Polycaprolactone/Silica Porous Membranes Produced by Sol‐Gel
Authors: Pandis Christos , Trujillo Sara , Roganowicz Marcin , Gómez Ribelles José Luis
Published: July 2014

Hybrid porous membranes of polycaprolactone (PCL) and silica were obtained by a two stage procedure. First a porous PCL membrane was produced by freeze extraction technique and then a sol‐gel reaction was used to form a uniform silica coating on the pore walls. Sol‐gel reaction was performed at low pH with tetraethylorthosilicate (TEOS) as the precursor of silica. In this work we analyze the influence of several clue parameters on the silica film formation and in turn on the properties of the hybrid material. Water:TEOS molar ratio and drying protocol were considered in this study.
Nanoporous Polycyanurates Created by Chemically‐Induced Phase Separation: Structure‐Property Relationships
Authors: Grigoryeva Olga , Fainleib Alexander , Gusakova Kristina , Starostenko Olga , Saiter Jean‐Marc , Levchenko Volodymyr , Serghei Anatoli , Boiteux Gisèle , Grande Daniel
Published: July 2014

Nanoporous thermostable polycyanurate (PCN) films were generated by in‐situ metal complex‐catalyzed polycyclotrimerization of 4,4′‐ethylidenediphenyl dicyanate in the presence of 20–50 wt.% of inert high‐boiling temperature liquids as porogens, i.e. dioctyl, dibutyl or dimethyl phthalates (DOP, DBP or DMP), followed by their extraction from the densely crosslinked PCN frameworks, drying, and additional annealing at various temperatures. The nanoporous structure for all PCN‐based films developed was investigated by SEM, BET, and DSC‐based thermoporometry. Furthermore, the thermal and dielectric properties of the nanoporous films were also examined. The method developed allows producing nanoporous films for membranes with controlled thermal and dielectric properties as well as porosity parameters.
Mathematical Modeling of Molecular Weight Distributions in Vinyl Chloride Suspension Polymerizations Performed with a Bifunctional Initiator through Probability Generating Functions
Authors: Castor Carlos A. , Sarmoria Claudia , Asteasuain Mariano , Brandolin Adriana , Pinto José C.
Published: July 2014

This paper presents a mathematical model to describe the evolution of the molecular weight distribution (MWD) in vinyl chloride (VCM) free‐radical suspension polymerizations performed with a bifunctional initiator, 1,3‐di(2‐neodecanoylperoxyisopropyl) (DIPND). The model yields, as a function of time, the mass balances for the distinct phases, the monomer conversion, the number‐ and mass‐average molecular weights and the complete MWD of both the growing and dead polymer chains. In order to describe the MWD, the model uses probability generating functions (pgf) to transform the mass balance equations into a reduced and finite set of model equations. As shown throughout many examples, the MWD's of the final polymer resin is little sensitive to the presence of the linear symmetrical bifunctional initiator.
Deposition and corrosion behavior of silicate conversion coatings on aluminum alloy 2024
Authors: Kazemi M. , Danaee I. , Zaarei D.
Published: July 2014

Potassium silicate was deposited on AA2024 aluminum alloy as environmentally friendly conversion coatings and its corrosion behavior were examined by means of electrochemical impedance spectroscopy, potentiodynamic polarization and surfaces techniques. Potentiodynamic polarization curves show significant decrease in corrosion current density of silicate coated aluminum in NaCl solution. The corrosion resistance was increased with increasing silicate concentration of coating baths. The results indicated that the coating applied from 3 molar silicate baths is more uniform and continuous. The X‐ray diffraction (XRD) and energy discharge spectroscopy (EDS) spectra confirm the existence of silicate film on the AA2024 surface. The coating performance was evaluated in acidic and basic NaCl solution and the results show the stability of silicate conversion coating in these solutions.
Corrosion monitoring of galvanized steel in soil extract solutions by electrochemical impedance spectroscopy
Authors: Lopes I. M. F. , Loureiro C. R. O. , Junqueira R. M. R.
Published: July 2014

The chemical and structural complexity of soils, coupled with their heterogeneity, contributes to the increase in soil aggressiveness, which can in turn result in severe corrosion of underground materials. The understanding of corrosive processes of underground structures is important in aiding the development of methods, as well as in monitoring and maintenance, in an attempt to minimize environmental, social, and economic impacts. In this work, electrochemical impedance spectroscopy (EIS) was used to monitor the corrosive process of galvanized steel when in contact with soil extracts, aimed at evaluating the potentiality of applying electrochemical impedance spectroscopy when monitoring underground structures. To accomplish this, the behavior of the galvanized steel when undergoing corrosion was studied for 105 days, examining the variations in the eletrochemical parameter values obtained through EIS assays over this period. EIS proved to be effective in the study of corrosive processes of galvanized steel when in contact with soil extracts, identifying the different stages of the corrosive process, controlled by mass and/or charge transfer reactions.
Constructing a Foundational Platform Driven by Japan’s K Supercomputer for Next‐Generation Drug Design
Authors: Brown J. B. , Nakatsui Masahiko , Okuno Yasushi
Published: July 2014

The cost of pharmaceutical R&D has risen enormously, both worldwide and in Japan. However, Japan faces a particularly difficult situation in that its population is aging rapidly, and the cost of pharmaceutical R&D affects not only the industry but the entire medical system as well. To attempt to reduce costs, the newly launched K supercomputer is available for big data drug discovery and structural simulation‐based drug discovery. We have implemented both primary (direct) and secondary (infrastructure, data processing) methods for the two types of drug discovery, custom tailored to maximally use the 88 128 compute nodes/CPUs of K, and evaluated the implementations. We present two types of results. In the first, we executed the virtual screening of nearly 19 billion compound‐protein interactions, and calculated the accuracy of predictions against publicly available experimental data. In the second investigation, we implemented a very computationally intensive binding free energy algorithm, and found that comparison of our binding free energies was considerably accurate when validated against another type of publicly available experimental data. The common feature of both result types is the scale at which computations were executed. The frameworks presented in this article provide prospectives and applications that, while tuned to the computing resources available in Japan, are equally applicable to any equivalent large‐scale infrastructure provided elsewhere.
Microstructural information from angular double‐pulsed‐field‐gradient NMR: From model systems to nerves
Authors: Morozov Darya , Bar Leah , Sochen Nir , Cohen Yoram
Published: July 2014

Purpose

To evaluate the ability of angular double‐pulsed‐field gradient (d‐PFG) MR to provide microstructural information in complex phantoms and fixed nerves.

Methods

We modeled the signal in angular d‐PFG MR experiments performed on phantoms of increasing complexity where the ground truth is known a priori. After analyzing the microstructural features of such phantoms the same methodology was used to study microstructural features in fixed nerves.

Results

We found that our modeling is able to determine with high accuracy and with very little prior knowledge the sizes and relative fractions of the restricted components as well as the fraction of the free diffusing water molecules. The same approach was used to study nerve microstructure. We found the apparent averaged axonal diameter (AAD) to be 2.3 ± 0.2 μm. However, here the results depended, to some extent, on the parameters used to collect the data and were affected by the diffusion time.

Conclusion

Modeling of the angular d‐PFG MR signal provides a means to obtain accurate microstructural information in complex phantoms where the ground truth is known. This approach also seems to be suitable for obtaining microstructural features in fixed nerves. Magn Reson Med 74:25–32, 2015. © 2014 Wiley Periodicals, Inc.
SPH procedures for modeling multiple intersecting discontinuities in geomaterial
Authors: Pramanik R. , Deb D.
Published: July 2014

A methodology is developed in SPH framework to analyze the behavior of preexisting multiple intersecting discontinuities or joints in rock material. The procedure does not require any additional unknowns to represent discontinuities and to capture velocity jump across them. Instead, a discontinuity is represented by a set of joint particles placed along the discontinuity plane, in which relative velocity and traction vector is evaluated, obeying the Mohr–Coulomb friction law with zero tension constrain. For failure of continuous rock material, the Drucker–Prager yield criterion with tensile cracking is employed in the elastic‐plastic constitutive model. Free‐sip, no‐slip, and symmetric boundary conditions are also implemented in SPH framework for proper representation of physical system.

The paper analyzes behavior of a rock sample having a discontinuity plane under uniaxial loading and compares velocity and stress with a theoretical solution derived considering effective vertical stiffness of the joint planes. The efficacy of the proposed method is successfully demonstrated by solving another two problems of jointed rock mass under uniaxial and gravitational loading conditions.Copyright © 2014 John Wiley & Sons, Ltd.
Tribological behavior of three‐dimensional braided carbon fiber reinforced polyetheretherketone composites
Authors: Qiu Xiaowen , He Fang , Li Junjiao , Chen Lixia , Huang Yuan
Published: July 2014

Three‐dimensional (3D) braided carbon fiber reinforced polyetheretherketone (denoted as CF3D/PEEK) composites with various fiber volume fractions were prepared via hybrid woven plus vacuum heat‐pressing technology and their tribological behaviors against steel counterpart with different normal loads at dry sliding were investigated. Contrast tribological tests with different lubricants (deionized water and sea water) and counterparts made from different materials (epoxy resin, PEEK) were also conducted. The results showed that the incorporation of 3D braided carbon fiber can greatly improve the tribological properties of PEEK over a certain range of carbon fiber volume fraction (Vf) and an optimum fiber loading of ∼54% exists. The friction coefficient of the CF3D/PEEK composites decreased from 0.195 to 0.173, while the specific wear rate increased from 1.48 × 10−7 to 1.78 × 10−7 mm3 Nm−1 with the normal load increasing from 50 to 150 N. Abrasive mechanism was dominated when the composites sliding with GCr15 steel counterpart under dry and aqueous lubrication conditions. Deionized water and sea water lubricants both significantly reduced the wear of the CF3D/PEEK composites. When sliding with neat PEEK counterpart, the CF3D/PEEK composites possess lower friction coefficient than those against epoxy resin and GCr15 steel counterparts. In general, CF3D/PEEK composites possess excellent tribological properties and comprehensive mechanical performance, which makes it become a potential candidate for special heat‐resisting tribological components. POLYM. COMPOS., 36:2174–2183, 2015. © 2014 Society of Plastics Engineers