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Sample records for polyhedral oligomeric silsesquioxanes

  1. octamethyl-polyhedral oligomeric silsesquioxanes nanocomposites ...

    Indian Academy of Sciences (India)

    In this study, biodegradable poly(p-dioxanone) (PPDO)/octamethyl-polyhedral oligomeric silsesquioxanes (ome-POSS) nanocomposites were fabricated by the simple solution casting method with various ome-POSS loadings. Scanning electron microscopic observations indicate that ome-POSS is well dispersed in the ...

  2. Polybenzoxazine/Polyhedral Oligomeric Silsesquioxane (POSS Nanocomposites

    Directory of Open Access Journals (Sweden)

    Mohamed Gamal Mohamed

    2016-06-01

    Full Text Available The organic/inorganic hybrid materials from polyhedral oligomeric silsesquioxane (POSS, inorganic nanoparticles and polybenzoxazine (PBZ have received much interesting recently due to their excellent thermal and mechanical properties, flame retardance, low dielectric constant, well-defined inorganic framework at nanosized scale level, and higher performance relative to those of non-hybrid PBZs. This review describes the synthesis, dielectric constants, and thermal, rheological, and mechanical properties of covalently bonded mono- and multifunctionalized benzoxazine POSS hybrids, other functionalized benzoxazine POSS derivatives, and non-covalently (hydrogen bonded benzoxazine POSS composites.

  3. Polyhedral Oligomeric Silsesquioxane (POSS)-Containing Polymer Nanocomposites

    Science.gov (United States)

    Ayandele, Ebunoluwa; Sarkar, Biswajit; Alexandridis, Paschalis

    2012-01-01

    Hybrid materials with superior structural and functional properties can be obtained by incorporating nanofillers into polymer matrices. Polyhedral oligomeric silsesquioxane (POSS) nanoparticles have attracted much attention recently due to their nanometer size, the ease of which these particles can be incorporated into polymeric materials and the unique capability to reinforce polymers. We review here the state of POSS-containing polymer nanocomposites. We discuss the influence of the incorporation of POSS into polymer matrices via chemical cross-linking or physical blending on the structure of nanocomposites, as affected by surface functional groups, and the POSS concentration. PMID:28348318

  4. Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl Substituted Polyhedral Oligomeric Silsesquioxanes (Postprint)

    National Research Council Canada - National Science Library

    Drazowski, Daniel B; Lee, Andre; Haddad, Timothy S

    2007-01-01

    Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different styrene content were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules...

  5. Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl Substituted Polyhedral Oligomeric Silsesquioxanes (preprint)

    National Research Council Canada - National Science Library

    Drazkowski, Daniel B; Lee, Andre; Haddad, Timothy S

    2006-01-01

    Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different styrene content were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules...

  6. Preparation of polyhedral oligomeric silsesquioxane based imprinted monolith.

    Science.gov (United States)

    Li, Fang; Chen, Xiu-Xiu; Huang, Yan-Ping; Liu, Zhao-Sheng

    2015-12-18

    Polyhedral oligomeric silsesquioxane (POSS) was successfully applied, for the first time, to prepare imprinted monolithic column with high porosity and good permeability. The imprinted monolithic column was synthesized with a mixture of PSS-(1-Propylmethacrylate)-heptaisobutyl substituted (MA 0702), naproxon (template), 4-vinylpyridine, and ethylene glycol dimethacrylate, in ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4). The influence of synthesis parameters on the retention factor and imprinting effect, including the amount of MA 0702, the ratio of template to monomer, and the ratio of monomer to crosslinker, was investigated. The greatest imprinting factor on the imprinted monolithic column prepared with MA 0702 was 22, about 10 times higher than that prepared in absence of POSS. The comparisons between MIP monoliths synthesized with POSS and without POSS were made in terms of permeability, column efficiency, surface morphology and pore size distribution. In addition, thermodynamic and Van Deemter analysis were used to evaluate the POSS-based MIP monolith. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Reactive bay functionalized perylene monoimide-polyhedral oligomeric silsesquioxane organic electronic dye

    Directory of Open Access Journals (Sweden)

    Wangatia Lodrick Makokha

    2015-03-01

    Full Text Available Aggregation-induced quenching is particularly detrimental in perylene diimides, which are characterized by a near-unity fluorescence quantum yield in solution but are far less emissive in the solid state. Previously, perylene diimide has been improved by linking it to the inorganic cage of polyhedral oligomeric silsesquioxanes. As a further study on perylene diimidepolyhedral oligomeric silsesquioxanes, we report on a double functionalized molecular structure, which can be used for substitution at the bay area and as a side group in other materials. Typical solution absorption and emission features of the perylene diimide fragment have been observed in this new reactive perylene diimide-polyhedral oligomeric silsesquioxane. Moreover, reduced stacking during aggregation and spherical particles exhibiting solid fluorescence have been obtained. Organic semiconducting material with enhanced solid state photophysical properties, like solid fluorescence is a subject of great interest owing to its possible high-tech applications in optoelectronic devices.

  8. Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

    OpenAIRE

    Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

    2015-01-01

    In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic li...

  9. Hedgehog Buckyball: A High-Symmetry Complete Polyhedral Oligomeric Silsesquioxane (POSS

    Directory of Open Access Journals (Sweden)

    Yu Hu

    2016-08-01

    Full Text Available In this study, we report UV-MALDI-TOF MS evidence of a fullerene-like silsesquioxane, a high-symmetry polyhedral oligomeric silsesquioxane (POSS or SSO formulated as R60-Si60O90 or T60 (T = RSiO1.5. The T60 preparation can be performed using a normal hydrolytic condensation of [(3-methacryloxypropyl]trimethoxysilane (MPMS as an example. Theoretically, four 3sp3 hybrid orbitals (each containing an unpaired electron of a Si atom are generated before the bond formation. Then it bonds to another four atom electrons using the four generated hybrid orbitals which produced a stable configuration. This fullerene-like silsesquioxane should exhibit much more functionality, activity and selectivity and is easier to assemble than the double bonds in a fullerene.

  10. Thermo-mechanical characterization of a monochlorophenyl, hepta isobutyl polyhedral oligomeric silsesquioxane/polystyrene composite

    International Nuclear Information System (INIS)

    Blanco, Ignazio; Bottino, Francesco A.; Cicala, Gianluca; Cozzo, Giulia; Latteri, Alberta; Recca, Antonino

    2014-01-01

    The thermal and mechanical properties of a monochlorophenyl, hepta isobutyl Polyhedral Oligomeric Silsesquioxane/Polystyrene (ph,hib-POSS/PS) composite were studied and compared with those of pristine polymer. ph,hib-POSS/PS system was prepared by solubilization and precipitation of Polystyrene (PS) in the presence of POSS. Scanning Electron Microscopy (SEM) was performed to check the distribution of the filler in the polymer matrix. Dynamic Mechanical Analysis (DMA) was carried out to measure viscoelastic properties of solid samples. Degradations were carried out into a thermobalance and the obtained thermogravimetric (TG) and differential thermogravimetric (DTG) curves were discussed and interpreted

  11. Immobilization of isolated FI catalyst on polyhedral oligomeric silsesquioxane-functionalized silica for the synthesis of weakly entangled polyethylene.

    Science.gov (United States)

    Li, Wei; Yang, Huaqin; Zhang, Jingjing; Mu, Jingshan; Gong, Dirong; Wang, Xiaodong

    2016-09-25

    Polyhedral oligomeric silsesquioxanes (POSSs) were adsorbed on methylaluminoxane-activated silica for the immobilization of fluorinated bis(phenoxyimine)Ti complexes (FI catalyst). These POSSs have been characterized as horizontal spacers isolating the active sites and hindering the chain overlap in polymerization. The heterogeneous catalyst exhibits considerable activity in the synthesis of weakly entangled polyethylene.

  12. Multifunctional Mesoporous Ionic Gels and Scaffolds Derived from Polyhedral Oligomeric Silsesquioxanes.

    Science.gov (United States)

    Lee, Jin Hong; Lee, Albert S; Lee, Jong-Chan; Hong, Soon Man; Hwang, Seung Sang; Koo, Chong Min

    2017-02-01

    A new methodology for fabrication of inorganic-organic hybrid ionogels and scaffolds is developed through facile cross-linking and solution extraction of a newly developed ionic polyhedral oligomeric silsesquioxane with inorganic core. Through design of various cationic tertiary amines, as well as cross-linkable functional groups on each arm of the inorganic core, high-performance ionogels are fabricated with excellent electrochemical stability and unique ion conduction behavior, giving superior lithium ion battery performance. Moreover, through solvent extraction of the liquid components, hybrid scaffolds with well-defined, interconnected mesopores are utilized as heterogeneous catalysts for the CO 2 -catalyzed cycloaddition of epoxides. Excellent catalytic performance, as well as highly efficient recyclability are observed when compared to other previous literature materials.

  13. Efficient light-emitting devices based on platinum-complexes-anchored polyhedral oligomeric silsesquioxane materials

    KAUST Repository

    Yang, Xiaohui

    2010-08-24

    The synthesis, photophysical, and electrochemical characterization of macromolecules, consisting of an emissive platinum complex and carbazole moieties covalently attached to a polyhedral oligomeric silsesquioxane (POSS) core, is reported. Organic light-emitting devices based on these POSS materials exhibit a peak external quantum efficiency of ca. 8%, which is significantly higher than that of the analogous devices with a physical blend of the platinum complexes and a polymer matrix, and they represent noticeable improvement in the device efficiency of solution-processable phosphorescent excimer devices. Furthermore, the ratio of monomer and excimer/aggregate electroluminescent emission intensity, as well as the device efficiency, increases as the platinum complex moiety presence on the POSS macromolecules decreases. © 2010 American Chemical Society.

  14. Flow cytometry evidence of human granulocytes interaction with polyhedral oligomeric silsesquioxanes: effect of nanoparticle charge

    International Nuclear Information System (INIS)

    Renò, Filippo; Rizzi, Manuela; Pittarella, Pamela; Carniato, Fabio; Olivero, Francesco; Marchese, Leonardo

    2013-01-01

    Nanoparticles (NPs) entering the human body are immediately confronted with the innate part of human immune system. In particular, monocyte and neutrophil granulocytes readily clear particles by phagocytosis, even if in the case of NPs the uptake mechanism may be classified as macropinocytosis. Among engineered nanoparticles, in the last years, siliceous materials have emerged as promising materials for several applications ranging from catalysis to biomedical. The polyhedral oligomeric silsesquioxanes (POSS) are nanodimensional, easily synthesizable molecular compounds and POSS-based systems are promising carriers for biological molecules. In this work, the ability of human granulocytes to uptake positively and negatively charged POSS was measured using a simple flow cytometry analysis based on cell size modifications. The data obtained showed that after a 30 min exposure only positive NPs were uptaken by human granulocyte using both macropinocytosis and clathrin-mediated mechanisms as demonstrated by uptake inhibition mediated by amiloride and chlorpromazine. (paper)

  15. Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

    Science.gov (United States)

    Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

    2015-06-01

    In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g-1) and large pore volumes (up to 0.90 cm3 g-1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4‧-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405- the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

  16. A New Star-shaped Carbazole Derivative with Polyhedral Oligomeric Silsesquioxane Core: Crystal Structure and Unique Photoluminescence Property.

    Science.gov (United States)

    Xu, Zixuan; Yu, Tianzhi; Zhao, Yuling; Zhang, Hui; Zhao, Guoyun; Li, Jianfeng; Chai, Lanqin

    2016-01-01

    A new inorganic–organic hybrid material based on polyhedral oligomeric silsesquioxane (POSS) capped with carbazolyl substituents, octakis[3-(carbazol-9-yl)propyldimethylsiloxy]-silsesquioxane (POSS-8Cz), was successfully synthesized and characterized. The X-ray crystal structure of POSS-8Cz were described. The photophysical properties of POSS-8Cz were investigated by using UV–vis,photoluminescence spectroscopic analysis. The hybrid material exhibits blue emission in the solution and the solid film.The morphology and thermal stablity properties were measured by X-ray diffraction (XRD) and TG-DTA analysis.

  17. Synthesis and characterization of an octaimidazolium-based polyhedral oligomeric silsesquioxanes ionic liquid by an ion-exchange reaction.

    Science.gov (United States)

    Tan, Jinglin; Ma, Depeng; Sun, Xingrong; Feng, Shengyu; Zhang, Changqiao

    2013-04-07

    Preparation of POSS-min-DS, an octaimidazolium-based polyhedral oligomeric silsesquioxanes (POSS) room temperature ionic liquid, by an ion-exchange reaction between POSS and sodium dodecyl sulfate was reported. Octaimidazolium-based POSS was synthesized with more than 98% yield within 3 h. POSS-min-DS and octaimidazolium-based POSS were confirmed by (1)H, (13)C, and (29)Si NMR, FT-IR and elemental analysis.

  18. Coatings of molecularly imprinted polymers based on polyhedral oligomeric silsesquioxane for open tubular capillary electrochromatography.

    Science.gov (United States)

    Zhao, Qing-Li; Zhou, Jin; Zhang, Li-Shun; Huang, Yan-Ping; Liu, Zhao-Sheng

    2016-05-15

    Polyhedral oligomeric silsesquioxane (POSS) was successfully applied, for the first time, to prepare imprinted monolithic coating for capillary electrochromatography. The imprinted monolithic coating was synthesized with a mixture of PSS-(1-Propylmethacrylate)-heptaisobutyl substituted (MA 0702), S-amlodipine (template), methacrylic acid (functional monomer), and 2-methacrylamidopropyl methacrylate (crosslinker), in a porogenic mixture of toluene-isooctane. The influence of synthesis parameters on the imprinting effect and separation performance, including the amount of MA 0702, the ratio of template to monomer, and the ratio of monomer to crosslinker, was investigated. The greatest resolution for enantiomers separation on the imprinted monolithic column prepared with MA 0702 was up to 22.3, about 2 times higher than that prepared in absence of the POSS. Column efficiency on the POSS-based MIP coatings was beyond 30,000 plate m(-1). The comparisons between MIP coating synthesized with the POSS and without the POSS were made in terms of selectivity, column efficiency, and resolution. POSS-based MIP capillaries with naproxen or zopiclone was also prepared and separation of enantiomers can be achieved. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Dielectric properties of polyhedral oligomeric silsesquioxane (POSS)-based nanocomposites at 77k

    International Nuclear Information System (INIS)

    Pan, Ming-Jen; Gorzkowski, Edward; McAllister, Kelly

    2011-01-01

    The goal of this study is to develop dielectric nanocomposites for high energy density applications at liquid nitrogen temperature by utilizing a unique nano-material polyhedral oligomeric silsesquioxanes (POSS). A POSS molecule is consisted of a silica cage core with 8 silicon and 12 oxygen atoms and organic functional groups attached to the corners of the cage. In this study, we utilize POSS for the fabrication of nanocomposites both as a silica nanoparticle filler to enhance the breakdown strength and as a surfactant for effective dispersion of high permittivity ceramic nanoparticles in a polymer matrix. The matrix materials selected for the study are polyvinylidene fluoride (PVDF) and poly(methyl methacrylate) (PMMA). The ceramic nanoparticles are barium strontium titanate (BST 50/50) and strontium titanate. The dielectric properties of the solution-cast nanocomposites films were correlated to the composition and processing conditions. We determined that the addition of POSS did not provide enhanced dielectric performance in PVDF- and PMMA-based materials at either room temperature or 77K. In addition, we found that the dielectric breakdown strength of PMMA is lower at 77K than at room temperature, contradicting literature data.

  20. Structure-properties relationships of polyhedral oligomeric silsesquioxane (POSS filled PS nanocomposites

    Directory of Open Access Journals (Sweden)

    J. J. Schwab

    2012-07-01

    Full Text Available The polyhedral oligomeric silsesquioxane (POSS additivated polystyrene (PS based nanocomposites were prepared by melt processing and the structure-properties relationships of the POSS-PS systems were compared to those of the neat PS. In order to investigate the effect of these structural parameters on the final properties of the polymer nanocomposites, five different kinds of POSS samples were used, in particular, POSS with different inorganic cage and with different organic pendent groups. The rheological investigation suggests clearly that the POSS acts as a plasticizer and that the processability of the PS was positively modified. The affinity between the POSS samples and the PS matrix was estimated by the calculated theoretical solubility parameters, considering the Hoy’s method and by morphology analysis. Minor difference between the solubility parameter of POSS and the matrix means better compatibility and no aggregation tendency. Furthermore, the POSS loading leads to a decrease of the rigidity, of the glass transition temperature and of the damping factor of the nanocomposite systems. The loading of different POSS molecules with open cage leads to a more pronounced effect on all the investigated properties that the loading of the POSS molecules with closed cage. Moreover, the melt properties are significantly influenced by the type of inorganic framework, by the type of the pendent organic groups and by the interaction between the POSS organic groups and the host matrix, while, the solid state properties appears to be influenced more by the kind of cage.

  1. Photo-polymerization of photocurable resins containing polyhedral oligomeric silsesquioxane methacrylate

    International Nuclear Information System (INIS)

    Lin, Ho-May; Wu, Shi-Yin; Chang, Feng-Chih; Yen, Ying-Chieh

    2011-01-01

    Photocurable resins, bisphenol A propoxylate glycerolate diacrylate (BPA-PGDA, containing two hydroxyl) and bisphenol A propoxylate diacrylate (BPA-PDA), with fixed photoinitiator (Irgacure 907) concentration and various contents of methacrylisobutyl polyhedral oligomeric silsesquioxane (MI-POSS) were prepared and characterized by FTIR spectroscopy, scanning electron microscope and differential photocalorimetry. The MI-POSS molecules form crystals or aggregated particles in the cured resin matrix. The BPA-PGDA series photocurable resins show higher viscosity and lower photo-polymerization reactivity than the BPA-PDA series resins. The photo-polymerization rate and conversion of BPA-PGDA series are improved with increasing MI-POSS content. On the contrary, the photo-polymerization behavior of BPA-PDA series photocurable resins remains nearly unchanged by the addition of MI-POSS. Hydrogen-bonding interaction between the hydroxyl of BPA-PGDA and the siloxane of MI-POSS tends to attract and concentrate these acrylate double bonds around MI-POSS particles and thus enhances the photo-polymerization rate and conversion.

  2. Transparent cellulose/polyhedral oligomeric silsesquioxane nanocomposites with enhanced UV-shielding properties.

    Science.gov (United States)

    Feng, Ye; Zhang, Jinming; He, Jiasong; Zhang, Jun

    2016-08-20

    The solubility of eight types of polyhedral oligomeric silsesquioxane (POSS) derivatives in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) and the dispersion of POSS in cellulose matrix were examined. Only a special POSS containing both aminophenyl and nitrophenyl groups (POSS-AN, NH2:NO2=2:6) was selected to prepare nanocomposites, because of its good solubility in AmimCl and high stability during the preparation process. POSS-AN nanoparticles were uniformly dispersed in a cellulose matrix with a size of 30-40nm, and so the resultant cellulose/POSS-AN nanocomposite films were transparent. The mechanical properties of the films achieved a maximum tensile strength of 190MPa after addition of 2wt% POSS-AN. Interestingly, all of the cellulose/POSS-AN films exhibited high UV-absorbing capability. For the 15wt% cellulose/POSS-AN film, the transmittance of UVA (315-400nm) and UVB (280-315nm) was only 9.1% and nearly 0, respectively. The UV aging and shielding experiments showed that the transparent cellulose/POSS-AN nanocomposite films possessed anti-UV aging and UV shielding properties. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Polyhedral oligomeric silsesquioxane (POSS)–poly(ethylene glycol) (PEG) hybrids as injectable biomaterials

    International Nuclear Information System (INIS)

    Engstrand, Johanna; López, Alejandro; Engqvist, Håkan; Persson, Cecilia

    2012-01-01

    One of the major issues with the currently available injectable biomaterials for hard tissue replacement is the mismatch between their mechanical properties and those of the surrounding bone. Hybrid bone cements that combine the benefits of tough polymeric and bioactive ceramic materials could become a good alternative. In this work, polyhedral oligomeric silsesquioxane (POSS) was copolymerized with poly(ethylene glycol) (PEG) to form injectable in situ cross-linkable hybrid cements. The hybrids were characterized in terms of their mechanical, rheological, handling and in vitro bioactive properties. The results indicated that hybridization improves the mechanical and bioactive properties of POSS and PEG. The Young moduli of the hybrids were lower than those of commercial cements and more similar to those of cancellous bone. Furthermore, the strength of the hybrids was similar to that of commercial cements. Calcium deficient hydroxyapatite grew on the surface of the hybrids after 28 days in PBS, indicating bioactivity. The study showed that PEG–POSS-based hybrid materials are a promising alternative to commercial bone cements. (paper)

  4. In-situ photocrosslinkable nanohybrid elastomer based on polybutadiene/polyhedral oligomeric silsesquioxane

    Energy Technology Data Exchange (ETDEWEB)

    Mirmohammadi, Seyed Amin, E-mail: mirmohammadi.sa@gmail.com [Department of Polymerization Engineering, Iran Polymer and Petrochemical Institute (IPPI), P. O. Box: 14965/115, Tehran (Iran, Islamic Republic of); Nekoomanesh-Haghighi, Mehdi, E-mail: m.nekoomanesh@ippi.ac.ir [Department of Polymerization Engineering, Iran Polymer and Petrochemical Institute (IPPI), P. O. Box: 14965/115, Tehran (Iran, Islamic Republic of); Mohammadian Gezaz, Somayyeh [Department of Chemical Engineering, Payame Noor University (PNU), P. O. Box: 19395-3697, Tehran (Iran, Islamic Republic of); Bahri-Laleh, Naeimeh [Department of Polymerization Engineering, Iran Polymer and Petrochemical Institute (IPPI), P. O. Box: 14965/115, Tehran (Iran, Islamic Republic of); Atai, Mohammad [Department of Polymer Science, Iran Polymer and Petrochemical Institute (IPPI), P. O. Box: 14965/115, Tehran (Iran, Islamic Republic of)

    2016-11-01

    Hydroxyl functionalized nano-sized POSS or ethyleneglycol as diol monomers was incorporated to hydroxyl-terminated polybutadiene (HTPBD) chain in the presence of fumaryl chloride as extender. Blue light photocrosslinking system based on camphorquinone (photoinitiator) and dimethylaminoethyl methacrylate (accelerator) was applied to cure these two synthesized fumarate based macromers. Self-crosslinkability of unsaturated macromers and also crosslinking in presence of a reactive diluent were investigated in absence and presence of 1,4-butanediol dimethacrylate, respectively. Finally, photocured samples were characterized by XRD, SEM, equilibrium swelling study, TGA, DMTA, AFM and cell culture. The results showed that incorporation of POSS nanoparticle into the polymer matrix with a perfect distribution and dispersion can enhance thermal stability, mechanical and biocompatibility properties which can prove a good potential of this in-situ photocrosslinkable nanohybrid in medical applications. - Highlights: • Polyhedral oligomeric silsesquioxane was incorporated to HTPBD by fumaryl chloride as extender. • A reactive diluent was used to improve photocrosslinking process of the unsaturated nanohybrid elastomers. • Nanohybrids showed enhanced properties such as thermal stability, mechanical and biocompatibility. • Improved properties were obtained for photocured samples in presence of reactive diluent.

  5. Synthesis and characterization of polyhedral oligomeric titanized silsesquioxane: A new biocompatible cage like molecule for biomedical application

    Energy Technology Data Exchange (ETDEWEB)

    Yahyaei, Hossein [Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran (Iran, Islamic Republic of); Mohseni, Mohsen, E-mail: mmohseni@aut.ac.ir [Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran (Iran, Islamic Republic of); Ghanbari, Hossein [Department of Medical Nanotechnology, School of Advanced Technologies in Medicine, Tehran University of Medical Sciences (TUMS), Tehran (Iran, Islamic Republic of); Messori, Massimo [Dipartimento di Ingegneria ‘Enzo Ferrari’, Università di Modena e Reggio Emilia, Modena (Italy)

    2016-04-01

    Organic–inorganic hybrid materials have shown improved properties to be used as biocompatible coating in biomedical applications. Polyhedral oligomeric silsesquioxane (POSS) containing coatings are among hybrid materials showing promising properties for these applications. In this work an open cage POSS has been reacted with a titanium alkoxide to end cap the POSS molecule with titanium atom to obtain a so called polyhedral oligomeric metalized silsesquioxane (POMS). The synthesized POMS was characterized by FTIR, RAMAN and UV–visible spectroscopy as well as {sup 29}Si NMR and matrix assisted laser desorption/ionization time-of-flight (MALDI-TOF) techniques. Appearance of peaks at 920 cm{sup −1} in FTIR and 491 cm{sup −1} and 1083 cm{sup −1} in Raman spectra confirmed Si–O–Ti linkage formation. It was also demonstrated that POMS was in a monomeric form. To evaluate the biocompatibility of hybrids films, pristine POSS and synthesized POMS were used in synthesis of a polycarbonate urethane polymer. Results revealed that POMS containing hybrid, not only had notable thermal and mechanical stability compared to POSS containing one, as demonstrated by DSC and DMTA analysis, they also showed controlled surface properties in such a manner that hydrophobicity and biocompatibility were both reachable to give rise to improved cell viability in presence of human umbilical vein endothelial cells (HUVEC) and MRC-5 cells. - Highlight: • Polyhedral Oligomeric Metalized Silsesquioxane (POMS) based on titanium was synthesized. • POMS can improve mechanical properties of polyurethane. • POMS increases hydrophobicity of polyurethane. • POMS is a unique nanocage to enhance biocompatibility of polyurethane.

  6. Bioactivity and properties of a dental adhesive functionalized with polyhedral oligomeric silsesquioxanes (POSS) and bioactive glass.

    Science.gov (United States)

    Rizk, Marta; Hohlfeld, Lisa; Thanh, Loan Tao; Biehl, Ralf; Lühmann, Nicole; Mohn, Dirk; Wiegand, Annette

    2017-09-01

    This study aimed to analyze the effect of infiltrating a commercial adhesive with nanosized bioactive glass (BG-Bi) particles or methacryl-functionalized polyhedral oligomeric silsesquioxanes (POSS) on material properties and bioactivity. An acetone-based dental adhesive (Solobond Plus adhesive, VOCO GmbH, Cuxhaven, Germany) was infiltrated with nanosized bioactive glass particles (0.1 or 1wt%), or with monofunctional or multifunctional POSS particles (10 or 20wt%). Unfilled adhesive served as control. Dispersion and hydrodynamic radius of the nanoparticles were studied by dynamic light scattering. Set specimens were immersed for 28days in artificial saliva at 37°C, and surfaces were mapped for the formation of calcium phospate (Ca/P) precipitates (scanning electron microscopy/energy-dispersive X-ray spectroscopy). Viscosity (rheometry) and the structural characteristic of the networks were studied, such as degree of conversion (FTIR spectroscopy), sol fraction and water sorption. POSS particles showed a good dispersion of the particles for both types of particles being smaller than 3nm, while the bioactive glass particles had a strong tendency to agglomerate. All nanoparticles induced the formation of Ca/P precipitates. The viscosity of the adhesive was not or only slightly increased by POSS particle addition but strongly increased by the bioactive glass particles. The degree of conversion, water sorption and sol fraction showed a maintained or improved network structure and properties when filled with BG-Bi and multifunctional POSS, however, less polymerization was found when loading a monofunctional POSS. Multifunctional POSS may be incorporated into dental adhesives to provide a bioactive potential without changing material properties adversely. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  7. Structure–property relationships in hybrid dental nanocomposite resins containing monofunctional and multifunctional polyhedral oligomeric silsesquioxanes

    Directory of Open Access Journals (Sweden)

    Wang WG

    2014-02-01

    Full Text Available Weiguo Wang,1,* Xiang Sun,1,* Li Huang,2,* Yu Gao,1 Jinghao Ban,1 Lijuan Shen,1 Jihua Chen1 1Department of Prosthodontics, 2Department of General Dentistry and Emergency, School of Stomatology, Fourth Military Medical University, Xi'an, People's Republic of China*These authors contributed equally to this workAbstract: Organic-inorganic hybrid materials, such as polyhedral oligomeric silsesquioxanes (POSS, have the potential to improve the mechanical properties of the methacrylate-based composites and resins used in dentistry. In this article, nanocomposites of methacryl isobutyl POSS (MI-POSS [bears only one methacrylate functional group] and methacryl POSS (MA-POSS [bears eight methacrylate functional groups] were investigated to determine the effect of structures on the properties of dental resin. The structures of the POSS-containing networks were determined by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. Monofunctional POSS showed a strong tendency toward aggregation and crystallization, while multifunctional POSS showed higher miscibility with the dimethacrylate monomer. The mechanical properties and wear resistance decreased with increasing amounts of MI-POSS, indicating that the MI-POSS agglomerates act as the mechanical weak point in the dental resins. The addition of small amounts of MA-POSS improved the mechanical and shrinkage properties. However, samples with a higher MA-POSS concentration showed lower flexural strength and flexural modulus, indicating that there is a limited range in which the reinforcement properties of MA-POSS can operate. This concentration dependence is attributed to phase separation at higher concentrations of POSS, which affects the structural integrity, and thus, the mechanical and shrinkage properties of the dental resin. Our results show that resin with 3% MA-POSS is a potential candidate for resin-based dental materials

  8. Morphological evolution in dewetting polystyrene/polyhedral oligomeric silsesquioxane thin film bilayers.

    Science.gov (United States)

    Paul, Rituparna; Karabiyik, Ufuk; Swift, Michael C; Hottle, John R; Esker, Alan R

    2008-05-06

    Morphological evolution in dewetting thin film bilayers of polystyrene (PS) and a polyhedral oligomeric silsesquioxane (POSS), trisilanolphenyl-POSS (TPP), was studied as a function of annealing temperature and annealing time. The results demonstrate unique dewetting morphologies in PS/TPP bilayers at elevated temperatures that are significantly different from those typically observed in dewetting polymer/polymer bilayers. During temperature ramp studies by optical microscopy (OM) in the reflection mode, PS/TPP bilayers form cracks with a weak optical contrast at approximately 130 degrees C. The crack formation is attributed to tensile stresses within the upper TPP layer. The weak optical contrast of the cracks observed in the bilayers for annealing temperatures below approximately 160 degrees C is consistent with the cracking and dewetting of only the upper TPP layer from the underlying PS layer. The optical contrast of the morphological features is significantly enhanced at annealing temperatures of >160 degrees C. This observation suggests dewetting of both the upper TPP and the lower PS layers that results in the exposure of the silicon substrate. Upon annealing the PS/TPP bilayers at 200 degrees C in a temperature jump experiment, the upper TPP layer undergoes instantaneous cracking as observed by OM. These cracks in the upper TPP layer serve as nucleation sites for rapid dewetting and aggregation of the TPP layer, as revealed by OM and atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) results indicated that dewetting of the lower PS layer ensued for annealing times >5 min and progressed up to 90 min. For annealing times >90 min, OM, AFM, and XPS results revealed complete dewetting of both the layers with the formation of TPP encapsulated PS droplets.

  9. Endohedral complexes of Polyhedral Oligomeric Silsesquioxane (POSS) cages with transition metal dihydrides

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiqiao; Corn, John; Hagelberg, Frank, E-mail: hagelber@etsu.edu

    2013-11-29

    Highlights: • Comparative studies of POSS cages with endohedral metal dihydrides. • Exothermic inclusion was found for the T{sub 10} cage with MH{sub 2}, M = Ti, Ru, Os, Pt. • Within this group of metal atoms, the only exothermic MH{sub 4}@T{sub m} unit is that with M = Os. • Enhanced hydrogen atom density, as compared to free MH{sub 4}, was found in the cage. • No exothermic solutions were identified for MH{sub 6}@T{sub 10}. - Abstract: Polyhedral Oligomeric Silsesquioxane (POSS) cages are investigated in terms of their potential to enclose small metal hydrides, with the objective of defining conditions that maximize the number of encapsulated hydrogen atoms. Systems of the form MH{sub 2n}@T{sub m}, where n = 1–3, m = 8, 10, and M comprises metal atom species of the groups IV, VI, VIII, X, and XII, are studied by methods of ab initio and density functional theory (DFT). The resulting composites are categorized with respect to their structural and energetic features. For MH{sub 2}@T{sub 8}, it is found in all cases considered that including MH{sub 2} into the POSS cage is an endothermic process. For MH{sub 2}@T{sub 10} and M = Ti, Ru, Os, Pt, inclusion of the MH{sub 2} guest into the cage turns out to be exothermic, and also leaves the cage intact. For MH{sub 4}@T{sub m}, this behavior is only observed for one system, OsH{sub 4}@T{sub 10}.

  10. Composite polymer electrolyte containing ionic liquid and functionalized polyhedral oligomeric silsesquioxanes for anhydrous PEM applications.

    Science.gov (United States)

    Subianto, Surya; Mistry, Mayur K; Choudhury, Namita Roy; Dutta, Naba K; Knott, Robert

    2009-06-01

    A new type of supported liquid membrane was made by combining an ionic liquid (IL) with a Nafion membrane reinforced with multifunctional polyhedral oligomeric silsesquioxanes (POSSs) using a layer-by-layer strategy for anhydrous proton-exchange membrane (PEM) application. The POSS was functionalized by direct sulfonation, and the sulfonated POSS (S-POSS) was incorporated into Nafion 117 membranes by the infiltration method. The resultant hybrid membrane shows strong ionic interaction between the Nafion matrix and the multifunctional POSS, resulting in increased glass transition temperature and thermal stability at very low loadings of S-POSS (1%). The presence of S-POSS has also improved the proton conductivity especially at low humidities, where it shows a marked increase due to its confinement in the ionic domains and promotes water uptake by capillary condensation. In order to achieve anhydrous conductivity, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI) was incorporated into these membranes to provide proton conduction in the absence of water. Although the incorporation of an IL shows a plasticizing effect on the Nafion membrane, the S-POSS composite membrane with an IL shows a higher modulus at high temperatures compared to Nafion 117 and a Nafion-IL membrane, with significantly higher proton conductivity (5 mS/cm at 150 degrees C with 20% IL). This shows the ability of the multifunctional POSS and IL to work symbiotically to achieve the desirable proton conductivity and mechanical properties of such membranes by enhancing the ionic interaction within the material.

  11. Multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes nanocomposite preparation via cross-linking reaction in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Somasekharan, Lakshmipriya; Thomas, Sabu [Mahatma Gandhi University, International and Interuniversity Centre for Nanoscience and Nanotechnology (India); Comoy, Corinne [Université de Lorraine, SRSMC, UMR 7565 (France); Sivasankarapillai, Anilkumar [NSS Hindu College (India); Kalarikkal, Nandakumar [Mahatma Gandhi University, International and Interuniversity Centre for Nanoscience and Nanotechnology (India); Lamouroux, Emmanuel, E-mail: Emmanuel.Lamouroux@univ-lorraine.fr [Université de Lorraine, SRSMC, UMR 7565 (France)

    2016-11-15

    Multiwalled carbon nanotubes have unique properties allowing their use in a wide range of applications—from microelectronics to biomedical and polymer fields. Nevertheless, a crucial aspect for their use resides in the ease of handling them during the process. Here, we report a facile route to prepare multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes (MWCNT@POSS) nanocomposite. The method involves the formation of a covalent bond between carboxylated MWCNTs and OV-POSS using acid-catalyzed electrophilic addition reaction. The resulting nanocomposite have been characterized by Fourier transform infrared spectroscopy (FTIR), powder X-Ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results confirmed that the formation of MWCNT@POSS nanocomposite did not deteriorate MWCNT structure or morphology. Here, we used a 1:1 ratio of carboxylated MWCNTs and OV-POSS and the POSS content in the nanocomposite was 39.5 wt%.

  12. Interaction of polyhedral oligomeric silsesquioxanes and dipalmitoylphosphatidylcholine at the air/water interface: Thermodynamic and rheological study.

    Science.gov (United States)

    Skrzypiec, M; Georgiev, G As; Rojewska, M; Prochaska, K

    2017-10-01

    Polyhedral oligomeric silsesquioxanes (POSS) derivatives containing open silsesquioxane cage bear great potential for biomedical applications and therefore their lateral interactions with phospholipids, major biomembranes and drug vehicles constituent, should be studied in detail. That is why the properties of surface films by two POSS-derivatives, POSS-polyethylene glycol (POSS-PEG) and POSS-perfluoroalkyl (POSS-OFP), pure and in presence of 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) were studied using Langmuir surface balance. Side chains of opposite nature (PEG is hydrophilic; OFP is hydrophobic) were selected, so that to evaluate their impact on polymers' surface properties. Two types of measurements were performed: (i) the miscibility of POSS-derivatives with DPPC was evaluated via thermodynamic analysis of the surface pressure (π)-area (A) isotherms and (ii) the dilatational rheology of selected POSS-polymer containing films was studied by the stress relaxation method. Fourier transformation analysis of the relaxation transients allows to access films' dynamic interfacial properties in broad frequency range (10 -5 -1Hz). Film morphology was monitored with Brewster Angle Microscopy. PEG moiety enabled POSS-PEG to stably incorporate in DPPC films, modifying their equilibrium and dynamic properties. In contrast OFP chains excluded from interactions with other molecules and diminished PEG-OFP amphiphilicity. Therefore at high packing densities (π≥25mN/m) PEG-OFP was expelled from the air/water interface in DPPC/PEG-OFP mixtures, and the binary films equilibrium and dynamic surface properties were determined primarily by DPPC. Thus the choice of POSS side chains can play key role in biomedical applications depending on whether strong or weak incorporation of POSS-polymers in lipid environment is aimed for. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Fouling behaviors of polybenzimidazole (PBI)-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) hollow fiber membranes for engineering osmosis processes

    KAUST Repository

    Chen, Sicong; Fu, Xiuzhu; Chung, Neal Tai-Shung

    2014-01-01

    This paper investigated the individual effects of reverse salt flux and permeate flux on fouling behaviors of as-spun and annealed polybenzimidazole (PBI)-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) hollow fiber membranes under forward osmosis (FO) and pressure retarded osmosis (PRO) processes. Two types of membrane fouling had been studied; namely, inorganic fouling (CaSO4·2H2O gypsum scaling) during FO operations and organic fouling (sodium alginate fouling) during PRO operations. It is found that gypsum scaling on the membrane surface may be inhibited and even eliminated with an increase in reverse MgCl2 flux due to competitive formations of MgSO4° and CaSO4·2H2O. In contrast, the increase of reverse NaCl flux exhibits a slight enhancement on alginate fouling in both FO and PRO processes. Comparing to the reverse salt flux, the permeate flux always plays a dominant role in fouling. Therefore, lesser fouling has been observed on the membrane surface under the pressurized PRO process than FO process because the reduced initial flux mitigates the fouling phenomena more significantly than the enhancement caused by an increase in reverse NaCl flux. © 2013 Elsevier B.V.

  14. Development of Biodegradable Poly(citrate)-Polyhedral Oligomeric Silsesquioxanes Hybrid Elastomers with High Mechanical Properties and Osteogenic Differentiation Activity.

    Science.gov (United States)

    Du, Yuzhang; Yu, Meng; Chen, Xiaofeng; Ma, Peter X; Lei, Bo

    2016-02-10

    Biodegradable elastomeric biomaterials have attracted much attention in tissue engineering due to their biomimetic viscoelastic behavior and biocompatibility. However, the low mechanical stability at hydrated state, fast biodegradation in vivo, and poor osteogenic activity greatly limited bioelastomers applications in bone tissue regeneration. Herein, we develop a series of poly(octanediol citrate)-polyhedral oligomeric silsesquioxanes (POC-POSS) hybrids with highly tunable elastomeric behavior (hydrated state) and biodegradation and osteoblasts biocompatibility through a facile one-pot thermal polymerization strategy. POC-POSS hybrids show significantly improved stiffness and ductility in either dry or hydrated conditions, as well as good antibiodegradation ability (20-50% weight loss in 3 months). POC-POSS hybrids exhibit significantly enhanced osteogenic differentiation through upregulating alkaline phosphatase (ALP) activity, calcium deposition, and expression of osteogenic markers (ALPL, BGLAP, and Runx2). The high mechanical stability at hydrated state and enhanced osteogenic activity make POC-POSS hybrid elastomers promising as scaffolds and nanoscale vehicles for bone tissue regeneration and drug delivery. This study may also provide a new strategy (controlling the stiffness under hydrated condition) to design advanced hybrid biomaterials with high mechanical properties under physiological condition for tissue regeneration applications.

  15. Preparation of polyhedral oligomeric silsesquioxane based hybrid monoliths by ring-opening polymerization for capillary LC and CEC.

    Science.gov (United States)

    Lin, Hui; Zhang, Zhenbin; Dong, Jing; Liu, Zhongshan; Ou, Junjie; Zou, Hanfa

    2013-09-01

    A new organic-inorganic hybrid monolith was prepared by the ring-opening polymerization of octaglycidyldimethylsilyl polyhedral oligomeric silsesquioxane (POSS) with 1,4-butanediamine (BDA) using 1-propanol, 1,4-butanediol, and PEG 10,000 as a porogenic system. Benefiting from the moderate phase separation process, the resulting poly(POSS-co-BDA) hybrid monolith possessed a uniform microstructure and exhibited excellent performance in chromatographic applications. Neutral, acidic, and basic compounds were successfully separated on the hybrid monolith in capillary LC (cLC), and high column efficiencies were achieved in all of the separations. In addition, as the amino groups could generate a strong EOF, the hybrid monolith was also applied in CEC for the separation of neutral and polar compounds, and a satisfactory performance was obtained. These results demonstrate that the poly(POSS-co-BDA) hybrid monolith is a good separation media in chromatographic separations of various types of compounds by both cLC and CEC. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Structural Analysis of Polyhedral Oligomeric Silsesquioxane Coated SiC Nanoparticles and Their Applications in Thermoset Polymers

    International Nuclear Information System (INIS)

    Reza-E-Rabby, M.; Jeelani, Sh.; Rangari, V. K.

    2015-01-01

    The SiC nanoparticles (NPs) were sonochemically coated with Octa Isobutyl (OI) polyhedral oligomeric silsesquioxane (POSS) to create a compatible interface between particle and thermoset polymer. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) techniques were used to analyze the structure of OI-POSS coated SiC nanoparticles. These results revealed the formation of a covalent bonding between SiC and OI-POSS. The transmission electron microscopy (TEM) analysis of OI-POSS coated SiC nanoparticles has also shown the indication of attachment between these two nanoparticles. The OI-POSS coated SiC nanoparticles were further reinforced into a thermoset resin system in order to evaluate mechanical and thermal properties of nano composites. The flexural strength, modulus, and glass transition temperature were found to be enhanced while SiC and OI-POSS coated SiC were infused into epoxy system compared to those properties of neat epoxy resin

  17. Structural Analysis of Polyhedral Oligomeric Silsesquioxane Coated SiC Nanoparticles and Their Applications in Thermoset Polymers

    Directory of Open Access Journals (Sweden)

    Md. Reza-E-Rabby

    2015-01-01

    Full Text Available The SiC nanoparticles (NPs were sonochemically coated with OctaIsobutyl (OI polyhedral oligomeric silsesquioxane (POSS to create a compatible interface between particle and thermoset polymer. X-ray photoelectron spectroscopy (XPS, Fourier transform infrared spectroscopy (FTIR, and X-ray diffraction (XRD techniques were used to analyze the structure of OI-POSS coated SiC nanoparticles. These results revealed the formation of a covalent bonding between SiC and OI-POSS. The transmission electron microscopy (TEM analysis of OI-POSS coated SiC nanoparticles has also shown the indication of attachment between these two nanoparticles. The OI-POSS coated SiC nanoparticles were further reinforced into a thermoset resin system in order to evaluate mechanical and thermal properties of nanocomposites. The flexural strength, modulus, and glass transition temperature were found to be enhanced while SiC and OI-POSS coated SiC were infused into epoxy system compared to those properties of neat epoxy resin.

  18. Unusual Emission of Polystyrene-Based Alternating Copolymers Incorporating Aminobutyl Maleimide Fluorophore-Containing Polyhedral Oligomeric Silsesquioxane Nanoparticles

    Directory of Open Access Journals (Sweden)

    Mohamed Gamal Mohamed

    2017-03-01

    Full Text Available In this study, we synthesized an unusual 2-aminobutyl maleimide isobutyl polyhedral oligomeric silsesquioxane (MIPOSS-NHBu monomer lacking conventional fluorescent groups. We then prepared poly(styrene-alt-2-aminobutyl maleimide isobutyl POSS [poly(S-alt-MIPOSS-NHBu] and poly(4-acetoxystyrene-alt-2-aminobutyl maleimide isobutyl POSS [poly(AS-alt-MIPOSS-NHBu] copolymers through facile free radical copolymerizations using azobisisobutyronitrile as the initiator and tetrahydrofuran as the solvent. A poly(4-hydroxystyrene-alt-2-aminobutyl maleimide isobutyl POSS [poly(HS-alt-MIPOSS-NHBu] copolymer was prepared through acetoxyl hydrazinolysis of poly(AS-alt-MIPOSS-NHBu. We employed 1H, 13C, and 29Si nuclear magnetic resonance spectroscopy; Fourier transform infrared spectroscopy; differential scanning calorimetry; and photoluminescence spectroscopy to investigate the structures and the thermal and optical properties of the monomers and novel POSS-containing alternating copolymers. Intramolecular hydrogen bonding between the amino and dihydrofuran-2,5-dione group and clustering of the locked C=O groups from the POSS nanoparticles in the MIPOSS-NHBu units restricted the intramolecular motion of the polymer chain, causing it to exhibit strong light emission. As a result, the MIPOSS-NHBu monomer and the poly(AS-alt-MIPOSS-NHBu copolymer both have potential applicability in the detection of metal ions with good selectivity.

  19. Fouling behaviors of polybenzimidazole (PBI)-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) hollow fiber membranes for engineering osmosis processes

    KAUST Repository

    Chen, Sicong

    2014-02-01

    This paper investigated the individual effects of reverse salt flux and permeate flux on fouling behaviors of as-spun and annealed polybenzimidazole (PBI)-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) hollow fiber membranes under forward osmosis (FO) and pressure retarded osmosis (PRO) processes. Two types of membrane fouling had been studied; namely, inorganic fouling (CaSO4·2H2O gypsum scaling) during FO operations and organic fouling (sodium alginate fouling) during PRO operations. It is found that gypsum scaling on the membrane surface may be inhibited and even eliminated with an increase in reverse MgCl2 flux due to competitive formations of MgSO4° and CaSO4·2H2O. In contrast, the increase of reverse NaCl flux exhibits a slight enhancement on alginate fouling in both FO and PRO processes. Comparing to the reverse salt flux, the permeate flux always plays a dominant role in fouling. Therefore, lesser fouling has been observed on the membrane surface under the pressurized PRO process than FO process because the reduced initial flux mitigates the fouling phenomena more significantly than the enhancement caused by an increase in reverse NaCl flux. © 2013 Elsevier B.V.

  20. Fabrication of boronate-decorated polyhedral oligomeric silsesquioxanes grafted cotton fiber for the selective enrichment of nucleosides in urine.

    Science.gov (United States)

    Gao, Li; Wei, Yinmao

    2016-06-01

    Various cotton fiber based boronate-affinity adsorbents are recently developed for the sample pretreatment of cis-diol-containing biomolecules, but most do not have efficient capacity due to limited binding sites on the surface of cotton fibers. To increase the density of boronate groups on the surface of cotton fiber, polyhedral oligomeric silsesquioxanes were used to modify cotton fiber to provide plentiful reactive sites for subsequent functionalization with 4-formylphenylboronic acid. The new adsorbent showed special recognition ability towards cis-diols and high adsorption capacity (175 μg/g for catechol, 250 μg/g for dopamine, 400 μg/g for adenosine). The in-pipette-tip solid-phase extraction was investigated under different conditions, including pH and ionic strength of solution, adsorbent amount, pipette times, washing solvent, and elution solvent. The in-pipette-tip solid-phase extraction coupled with high-performance liquid chromatography was used to analyze four nucleosides in urine samples. Under the optimal extraction conditions, the detection limits were determined to be between 5.1 and 6.1 ng/mL (S/N  =  3), and the linearity ranged from 20 to 500 ng/mL for these analytes. The accuracy of the analytical method was examined by studying the relative recoveries of analytes in real urine samples with recoveries varying from 83 to 104% (RSD = 3.9-10.2%, n = 3). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Ultrafast preparation of a polyhedral oligomeric silsesquioxane-based ionic liquid hybrid monolith via photoinitiated polymerization, and its application to capillary electrochromatography of aromatic compounds.

    Science.gov (United States)

    Zhang, Bingyu; Lei, Xiaoyun; Deng, Lijun; Li, Minsheng; Yao, Sicong; Wu, Xiaoping

    2018-06-06

    An ionic liquid hybrid monolithic capillary column was prepared within 7 min via photoinitiated free-radical polymerization of an ionic liquid monomer (1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide); VBIMNTF 2 ) and a methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) acting as a cross-linker. The effects of composition of prepolymerization solution and initiation time on the porous structure and electroosmotic flow (EOF) of monolithic column were investigated. The hybrid monolith was characterized by scanning electron microscopy and FTIR. Owing to the introduction of a rigid nanosized POSS silica core and ionic liquids with multiple interaction sites, the monolithic column has a well-defined 3D skeleton morphology, good mechanical stability, and a stable anodic electroosmotic flow. The hybrid monolithic stationary phase was applied to the capillary electrochromatographic separation of various alkylbenzenes, phenols, anilines and polycyclic aromatic hydrocarbons (PAHs). The column efficiency is highest (98,000 plates/m) in case of alkylbenzenes. Mixed-mode retention mechanisms including hydrophobic interactions, π-π stacking, electrostatic interaction and electrophoretic mobility can be observed. This indicates the potential of this material in terms of efficient separation of analytes of different structural type. Graphical Abstract Preparation of a mixed-mode ionic liquid hybrid monolithic column via photoinitiated polymerization of methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) and 1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide (VBIMNTF 2 ) ionic liquid for use in capillary electrochromatography.

  2. Surface modification of a polyhedral oligomeric silsesquioxane poly(carbonate-urea) urethane (POSS-PCU) nanocomposite polymer as a stent coating for enhanced capture of endothelial progenitor cells.

    Science.gov (United States)

    Tan, Aaron; Farhatnia, Yasmin; Goh, Debbie; G, Natasha; de Mel, Achala; Lim, Jing; Teoh, Swee-Hin; Malkovskiy, Andrey V; Chawla, Reema; Rajadas, Jayakumar; Cousins, Brian G; Hamblin, Michael R; Alavijeh, Mohammad S; Seifalian, Alexander M

    2013-12-01

    An unmet need exists for the development of next-generation multifunctional nanocomposite materials for biomedical applications, particularly in the field of cardiovascular regenerative biology. Herein, we describe the preparation and characterization of a novel polyhedral oligomeric silsesquioxane poly(carbonate-urea) urethane (POSS-PCU) nanocomposite polymer with covalently attached anti-CD34 antibodies to enhance capture of circulating endothelial progenitor cells (EPC). This material may be used as a new coating for bare metal stents used after balloon angioplasty to improve re-endothelialization. Biophysical characterization techniques were used to assess POSS-PCU and its subsequent functionalization with anti-CD34 antibodies. Results indicated successful covalent attachment of anti-CD34 antibodies on the surface of POSS-PCU leading to an increased propensity for EPC capture, whilst maintaining in vitro biocompatibility and hemocompatibility. POSS-PCU has already been used in 3 first-in-man studies, as a bypass graft, lacrimal duct and a bioartificial trachea. We therefore postulate that its superior biocompatibility and unique biophysical properties would render it an ideal candidate for coating medical devices, with stents as a prime example. Taken together, anti-CD34 functionalized POSS-PCU could form the basis of a nano-inspired polymer platform for the next generation stent coatings.

  3. Development of a polymeric ionic liquid coating for direct-immersion solid-phase microextraction using polyhedral oligomeric silsesquioxane as cross-linker.

    Science.gov (United States)

    Chen, Chunyan; Liang, Xiaotong; Wang, Jianping; Zou, Ying; Hu, Huiping; Cai, Qingyun; Yao, Shouzhuo

    2014-06-27

    A novel solid-phase microextraction (SPME) fiber was developed by chemical binding of a crosslinked polymeric ionic liquid (PIL) on the surface of an anodized Ti wire, and was applied in direct-immersion mode for the extraction of perfluorinated compounds (PFCs) from water samples coupled with high performance liquid chromatography-tandem mass spectrometry analysis. The PIL coatings were synthesized by using 1-vinyl-3-hexylimidazolium hexafluorophosphate as monomer and methylacryloyl-substituted polyhedral oligomeric silsesquioxane (POSS) as cross-linker via free radical reaction. The proposed fiber coating exhibited high mechanical stability due to the chemical bonding between the coating and the Ti wire surface. The integration of POSS reagent enhanced the organic solvent resistance of the coating. The parameters affecting the extraction performance of the fiber coating including extraction time, pH of solution, ionic strength and desorption conditions were optimized. The developed PIL-POSS fiber showed good linearity (R<0.998) between 0.1 and 50ngmL(-1) with method detection limits ranging from 0.005 to 0.08ngmL(-1) depending on the analyte, and with relative standard deviation for single-fiber repeatability and fiber-to-fiber reproducibility less than 8.6% and 9.5%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Development of the optical sensor for discriminating isomers of fatty acids based on emissive network polymers composed of polyhedral oligomeric silsesquioxane.

    Science.gov (United States)

    Narikiyo, Hayato; Kakuta, Takahiro; Matsuyama, Hiroki; Gon, Masayuki; Tanaka, Kazuo; Chujo, Yoshiki

    2017-07-01

    It was shown that water-soluble network polymers composed of polyhedral oligomeric silsesquioxane (POSS) had hydrophobic spaces inside the network because of strong hydrophobicity of the cubic silica cage. In this study, the water-soluble POSS network polymers connected with triphenylamine derivatives (TPA-POSS) were synthesized, and their functions as a sensor for discriminating the geometric isomers of fatty acids were investigated. Accordingly, in the photoluminescence spectra, different time-courses of intensity and peak wavelengths of the emission bands were detected from the TPA-POSS-containing solution in the presence of cis- or trans-fatty acids during incubation. Furthermore, variable time-dependent changes were obtained by changing coexisting ratios between two geometric isomers. From the mechanistic investigation, it was implied that these changes could be originated from the difference in the degree of interaction between the POSS networks and each fatty acid. Our data could be applicable for constructing a sensing material for generation and proportion of trans-fatty acids in the oil. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Phenyl hepta cyclopentyl – polyhedral oligomeric silsesquioxane (ph,hcp-POSS/Polystyrene (PS nanocomposites: the influence of substituents in the phenyl group on the thermal stability

    Directory of Open Access Journals (Sweden)

    I. Blanco

    2012-12-01

    Full Text Available Some new Polystyrene (PS nanocomposites were prepared by using two Polyhedral Oligomeric Silsesquioxanes (POSSs, namely RR’7(SiO1.58 (where R = 4-methoxyphenyl or 2,4-difluorophenyl and R’ = cyclopentyl, as fillers, and their degradation was studied to investigate the effect of the electron-donor or electron-withdrawing character of the phenyl group substituents on thermal stability. Nanocomposites were synthesized by in situ polymerization of styrene in the presence of various concentrations of POSS. Proton nuclear magnetic resonance (1H NMR spectra indicated that the POSS content in the obtained nanocomposites was higher than that in reactant mixtures. Inherent viscosity (ηinh and glass transition temperature (Tg determinations indicated that the average molar mass of polymer in 4-methoxynanocomposites was the same than neat PS, while it was much lower in 2,4-difluoro derivatives. Degradations were carried out in both flowing nitrogen and static air atmospheres, in the scanning mode, at various heating rates, and temperature at 5% mass loss (T5% and the activation energy (Ea of degradation of various nanocomposites were determined. The values obtained for 4-methoxyderivatives were higher than unfilled PS thus indicating higher thermal stability. Conversely, the values found for 2,4-difluoro derivatives were lower, in some cases even than those of neat PS. The results were discussed and interpreted.

  6. Coating of Carbon Fiber with Polyhedral Oligomeric Silsesquioxane (POSS to Enhance Mechanical Properties and Durability of Carbon/Vinyl Ester Composites

    Directory of Open Access Journals (Sweden)

    Mujib Khan

    2011-09-01

    Full Text Available Our continuing quest to improve the performance of polymer composites under moist and saltwater environments has gained momentum in recent years with the reinforcement of inorganic nanoparticles into the polymer. The key to mitigate degradation of composites under such environments is to maintain the integrity of the fiber/matrix (F/M interface. In this study, the F/M interface of carbon/vinyl ester composites has been modified by coating the carbon fiber with polyhedral oligomeric silsesquioxane (POSS. POSS is a nanostructured inorganic-organic hybrid particle with a cubic structure having silicon atoms at the core and linked to oxygen atoms. The advantage of using POSS is that the silicon atoms can be linked to a substituent that can be almost any chemical group known in organic chemistry. Cubic silica cores are ‘hard particles’ and are about 0.53 nm in diameter. The peripheral organic unit is a sphere of about 1–3 nm in diameter. Further, cubic structure of POSS remains intact during the polymerization process and therefore with appropriate functional groups, if installed on the fiber surface, would provide a stable and strong F/M interface. Two POSS systems with two different functional groups; namely, octaisobutyl and trisilanolphenyl have been investigated. A set of chemical and mechanical procedures has been developed to coat carbon fibers with POSS, and to fabricate layered composites with vinyl ester resin. Interlaminar shear and low velocity impact tests have indicated around 17–38% improvement in mechanical properties with respect to control samples made without the POSS coating. Saltwater and hygrothermal tests at various environmental conditions have revealed that coating with POSS reduces water absorption by 20–30% and retains the composite properties.

  7. Electrospun poly(vinylidene fluoride) copolymer/octahydroxy-polyhedral oligomeric silsesquioxane nanofibrous mats as ionic liquid host: enhanced salt dissociation and its function in electrochromic device

    International Nuclear Information System (INIS)

    Zhou, Rui; Pramoda, Kumari Pallathadka; Liu, Wanshuang; Zhou, Dan; Ding, Guoqiang; He, Chaobin; Leong, Yew Wei; Lu, Xuehong

    2014-01-01

    Highlights: • The well dispersed POSS-OH promotes the dissociation of both LiClO 4 and BMIM + BF 4 − . • POSS-OH significantly increases the ionic conductivity and lithium transference number. • POSS-OH containing electrolyte improves the optical contrast of electrochromic device. - Abstract: Electrospun polymer nanofibrous mats loaded with ionic liquids (ILs) and lithium salts are promising non-volatile electrolytes owing to their high ionic conductivities. However, the large cations of ILs are difficult to diffuse into solid electrodes, whereas the lithium ions in ILs tend to form anionic complexes with the IL anions, reducing the number of free lithium ions. To address these issues, octa(3-hydroxy-3-methylbutyldimethylsiloxy) polyhedral oligomeric silsesquioxane (POSS-OH), which has large specific surface area and functionality number, is incorporated into electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) nanofibrous mats, and the mats are used to host LiClO 4 /1-butyl-3-methylimidazolium tetrafluoroborate (BMIM + BF 4 − ). It is found that POSS-OH can significantly increase both ionic conductivity and lithium transference number of the electrolytes owing to the Lewis acid-base interactions of POSS-OH with ClO 4 − and BF 4 − . The electrochromic device using the hybrid mat (with 5 wt% POSS-OH) loaded with LiClO 4 /BMIM + BF 4 − as the electrolyte shows significantly improved transmittance contrast and switching time, as a result of increased number of free lithium ions

  8. Facile synthesis of a boronate affinity sorbent from mesoporous nanomagnetic polyhedral oligomeric silsesquioxanes composite and its application for enrichment of catecholamines in human urine

    Energy Technology Data Exchange (ETDEWEB)

    He, Haibo, E-mail: hbhe2006@shu.edu.cn [Department of Chemistry, Shanghai University, Shanghai 200444 (China); Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072 (China); Zhou, Ziqing; Dong, Chen; Wang, Xin [Department of Chemistry, Shanghai University, Shanghai 200444 (China); Yu, Qiong-wei [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072 (China); Lei, Yunyi; Luo, Liqiang [Department of Chemistry, Shanghai University, Shanghai 200444 (China); Feng, Yuqi [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072 (China)

    2016-11-09

    A boronate-decorated nanomagnetic organic-inorganic hybrid material was facilely synthesized by utilizing the nanomagnetic polyhedral oligomeric silsesquioxanes (POSS) composite (Fe{sub 3}O{sub 4}@POSS) as the base platform. A simple copolymerization occurred between 3-acrylamidophenylboronic acid (AAPBA) and the residual end vinyl groups supplied by the substrate. Here the special emphasis was placed on the octavinyl POSS, which not only acted as the building blocks for a hybrid architecture but also facilitated the process of grafting boronate groups onto the surface of POSS based nanomagnetic composite (Fe{sub 3}O{sub 4}@POSS). The successful immobilization of affinity ligand-AAPBA on the Fe{sub 3}O{sub 4}@POSS was confirmed by Fourier transform infrared (FT-IR), elemental analysis, inductively coupled plasma atomic emission spectrometer (ICP-AES), field emission scanning electron microscope. A magnetic solid-phase extraction (MSPE) for cis-diols enrichment was developed using the as-prepared Fe{sub 3}O{sub 4}@POSS-AAPBA material as an affinity sorbent and three catecholamines (CAs), namely noradrenaline, epinephrine and isoprenaline, as model analytes. Under the optimal extraction conditions, sensitive and simultaneous analysis of three CAs from the urine sample was achieved by high-performance liquid chromatography with UV detection (HPLC-UV). The limits of detection (LOD, S/N = 3) and the limits of quantitation (LOQ, S/N = 10) for the target analytes were 0.81–1.32 ng mL{sup −1} and 2.70–4.40 ng mL{sup −1}, respectively. Also good recoveries (85.5–101.7%) and repeatability (RSD≤10.1%) were obtained by this method. This work not only showed a facility for the utilization of Fe{sub 3}O{sub 4}@POSS as a substrate for constructing a boronate functionalized nanomagnetic sorbent, but also demonstrated the capability of the derived material for recognition of trace amount of cis-diols biomolecules presented in complicated biological matrices

  9. The effect of polyhedral oligomeric silsesquioxane dispersant and low surface energy additives on spectrally selective paint coatings with self-cleaning properties

    Energy Technology Data Exchange (ETDEWEB)

    Jerman, Ivan; Kozelj, Matjaz; Orel, Boris [National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana (Slovenia)

    2010-02-15

    Thickness-Insensitive Spectrally Selective (TISS) paint coatings were made of fluoropolymer resin binder (Lumiflon (LF), Asahi Glass Co., Ltd., Japan) and their water- and oil-repellent properties were obtained (contact angle: {theta}{sub water}{proportional_to}150 , {theta}{sub n-hexadecane}{proportional_to}55 ) by the addition of Polyhedral Oligomeric Silsesquioxane (POSS) characterized by amino (AP), isooctyl (IO) and perfluoro (PF) groups (i.e. AP{sub 2}IO{sub 4}PF{sub 2}) attached on the silsesquioxane cube (-SiO{sub 3/2}){sub 8}. Paint dispersions were made by modifying of black spinel pigment with trisilanol isobutyl (IB{sub 7}T{sub 7}(OH){sub 3}) POSS dispersant and with a single-capped silane isobutyltrimethoxysilane (IBTMS). Infrared and {sup 29}Si NMR spectra measurements were used for the identification of the structural characteristic of the corresponding POSS compounds. Surface free energy values of the pure cross-linked (no pigment added) LF binder which was determined from the measured contact angles for water, diiodomethane and formamide revealed the {gamma}{sup tot} value of the LF unpigmented resin with added AP{sub 2}IO{sub 4}PF{sub 2} T{sub 8} POSS was about 16.4 mN/m, which led to the {theta}{sub water}{proportional_to}110 , indicating enhancement of the hydrophobicity of the pure LF resin binder ({theta}{sub water}{proportional_to}89 ). SEM micrographs, which were used for the assessment of the TISS paint coating surface morphology confirmed the beneficial dispersive effect of IB{sub 7} T{sub 7}(OH){sub 3} dispersant as compared to the IBTMS silane. The presence of large Aluminium flake pigment and finely ground black pigment led to the formation of TISS paint coating surface, which exhibited bi-hierarchical roughness, resulting in water sliding angles of less than 10 , indicating the possible self-cleaning effect ({theta}{sub water}>150 and {theta}{sub n-hexadecane}{proportional_to}55 ). The use of POSS dispersant and POSS low surface energy

  10. An investigation of the use of cerium and polyhedral oligomeric silsesquioxanes for the protection of polymeric epoxy compounds in the low Earth orbit environment

    Science.gov (United States)

    Piness, Jessica Miriam

    Low Earth orbit presents many hazards for composites including atomic oxygen, UV radiation, thermal cycling, micrometeoroids, and high energy protons. Atomic oxygen and vacuum ultraviolet radiation are of concern for space-bound polymeric materials as they degrade the polymers used as matrices for carbon fiber composites, which are used in satellites and space vehicles due to their high strength to weight ratios. Epoxy-amine thermosets comprise a common class of matrix due to processability and good thermal attributes. Polyhedral oligomeric silsesquioxanes (POSS) have shown the ability to reduce erosion in polyimides, polyurethanes, and other polymers when exposed to atomic oxygen. The POSS particle is composed of a SiO1.5 cage from which up to eight organic pendant groups are attached at the silicon corners of the cage. POSS reduced atomic oxygen impact on polymers by a process known as glassification wherein the organic pendants are removed from the cage upon atomic oxygen exposure and then the cage rearranges to a passive silica network. In addition, POSS shows good UV absorbance in the UVb and UVc ranges and POSS can aid dispersion of titanium dioxide in a nanocomposite. In this work, Chapter I focuses on hazards in low Earth orbit, strategies for protecting organic material in orbit, and the capabilities of POSS. Chapter II details the experimental practices used in this work. Chapter III focuses on work to induce POSS phase separation and layering at the surface of an epoxy-amine thermoset. Generally, POSS is dispersed throughout a nanocomposite, and in the process of erosion by atomic oxygen, some polymer mass loss is lost before enough POSS is exposed to begin glassification. Locating POSS at a surface of composite could possibly reduce this mass loss and the objective of this research was to investigate the formation of POSS-rich surfaces. Three POSS derivatives with different pendant groups were chosen. The POSS derivatives had a range of miscibilities

  11. Synthesis and Characterization of Polyfunctional Polyhedral Silsesquioxane Cages

    Science.gov (United States)

    Sulaiman, Santy

    Recent studies on octameric polyhedral silsesquioxanes, (RSiO1.5 )8, indicate that the silsesquioxane cage is not just a passive component but appears to be involved in electron delocalization with conjugated organic tethers in the excited state. This dissertation presents the synthesis and characterization of (RSiO1.5)8 molecules with unique photophysical properties that provide support for the existence of conjugation that involves the (RSiO1.5)8 cage. The dissertation first discusses the elaboration of octavinylsilsesquioxane via cross-metathesis to form styrenyl-functionalized octasilsesquioxane molecules. Subsequent Heck coupling reactions of p-bromostyrenyl derivative provides vinylstilbene-functionalized octasilsesquioxane. The amino derivative, NH2VinylStilbeneOS, show highly red-shifted emission spectrum (100 nm from the simple organic analog p-vinylstilbene) and high two-photon absorption (TPA) cross-section value (100 GM/moiety), indicating charge-transfer processes involving the silsesquioxane cage as the electron acceptor. The unique photophysical properties of polyfunctional luminescent cubic silsesquioxanes synthesized from ortho-8-, (2,5)-16-, and 24-brominated octaphenylsilsesquioxane (OPS) via Heck coupling show how the steric interactions of the organic tethers at the silsesquioxane cage corner affect conjugation with the silsesquioxane cage. Furthermore, the high TPA cross-section (10 GM/moiety) and photoluminescence quantum yield (20%) of OPS functionalized with 24 acetoxystyrenyl groups suggest that the existence excited states in these molecules with similar energies and decay rates: normal radiative pi- pi* transition and charge transfer involving the silsesquioxane cage. The fluoride ion-catalyzed rearrangement reactions of cage and polymeric silsesquioxanes provide a convenient route to a mixture of deca- and dodecameric silsesquioxane molecules in high yields, giving us the opportunity to investigate the effect of silsesquioxane cage

  12. Polyhedral Oligomeric Silsesquioxane (POSS) Styrene Macromers

    National Research Council Canada - National Science Library

    Haddad, Timothy

    2001-01-01

    .... Cyclohexyl, cyclopentyl and isobutyl substituted POSS-stryenes (at 30 weight % loadings) undergo free radical bulk polymerizations with styrene to produce polymers with an enhanced modulus above the glass transition temperature...

  13. Thermal Degradation Mechanism of a Thermostable Polyester Stabilized with an Open-Cage Oligomeric Silsesquioxane

    Directory of Open Access Journals (Sweden)

    Yolanda Bautista

    2017-12-01

    Full Text Available A polyester composite was prepared through the polymerization of an unsaturated ester resin with styrene and an open-cage oligomeric silsesquioxane with methacrylate groups. The effect of the open-cage oligomeric silsesquioxane on the thermal stability of the thermostable polyester was studied using both thermogravimetric analysis and differential thermal analysis. The results showed that the methacryl oligomeric silsesquioxane improved the thermal stability of the polyester. The decomposition mechanism of the polyester/oligomer silsesquioxane composite was proposed by Fourier transform infrared spectroscopy (FTIR analysis of the volatiles.

  14. Preparation and characterization of polyhedral oligomer silsesquioxane nanocomposites incorporated in epoxy resin

    International Nuclear Information System (INIS)

    Longhi, Marielen; Zini, Lucas Pandolphi; Birriel, Eliena Jonko; Kunst, Sandra Raquel; Zattera, Ademir Jose

    2015-01-01

    The incorporation of nanofiller in thermosetting like epoxy resin as has been studied in order to modify its properties. In this research, nanocomposites were obtained by incorporating 5% by weight of three polyhedral oligomeric silsesquioxane (POSS) with different number of functionalization: Glicidilisobutil-POSS, Triglicidilisobutil- POSS and Glicicil POSS in an epoxy matrix by sonification process. The nanocomposites were characterized by analysis of X-ray diffraction (DRX), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The DRX analysis showed the characteristic peak of POSS and TEM images showed that there is a difference in the dispersion of nanocages for the difference in the number of epoxy groups on the POSS. The incorporation of Glicidilisobutil-POSS showed a significant increase in the glass transition temperature (Tg) value, and also that the most effective from the viewpoint of the dispersion, on the other hand, the Glycidyl-POSS had a greater influence on the thermal stability demonstrating that the dispersion medium is an important characteristic to define the most desirable properties. (author)

  15. Polymer Nanocomposites Designed with Polyhedral Oligomeric Silsesquioxanes (POSS) and Plastics

    National Research Council Canada - National Science Library

    Haddad, Timothy; Mabry, Joseph

    2005-01-01

    .... These applications include space-survivable coatings and fire-resistant materials. Due to their physical size, POSS incorporation in polymers generally serves to reduce chain mobility, thus affecting both thermal and mechanical properties...

  16. Preparation and characterization of polyhedral oligomer silsesquioxane nanocomposites incorporated in epoxy resin; Elaboracao e caracterizacao de nanocompositos de oligomero poliedrico de silsesquioxano incorporados na resina epoxidica

    Energy Technology Data Exchange (ETDEWEB)

    Longhi, Marielen; Zini, Lucas Pandolphi; Birriel, Eliena Jonko; Kunst, Sandra Raquel; Zattera, Ademir Jose, E-mail: marielen_longhi@hotmail.com [Universidade de Caxias do Sul (LPOL/UCS), RS (Brazil). Laboratorio de Polimeros; Pistor, Vinicius [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil)

    2015-07-01

    The incorporation of nanofiller in thermosetting like epoxy resin as has been studied in order to modify its properties. In this research, nanocomposites were obtained by incorporating 5% by weight of three polyhedral oligomeric silsesquioxane (POSS) with different number of functionalization: Glicidilisobutil-POSS, Triglicidilisobutil- POSS and Glicicil POSS in an epoxy matrix by sonification process. The nanocomposites were characterized by analysis of X-ray diffraction (DRX), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The DRX analysis showed the characteristic peak of POSS and TEM images showed that there is a difference in the dispersion of nanocages for the difference in the number of epoxy groups on the POSS. The incorporation of Glicidilisobutil-POSS showed a significant increase in the glass transition temperature (Tg) value, and also that the most effective from the viewpoint of the dispersion, on the other hand, the Glycidyl-POSS had a greater influence on the thermal stability demonstrating that the dispersion medium is an important characteristic to define the most desirable properties. (author)

  17. Polyhedral oligomeric silsequioxane monolayer as a nanoporous interlayer for preparation of low-k dielectric films

    International Nuclear Information System (INIS)

    Liu, Y-L; Liu, C-S; Cho, C-I; Hwu, M-J

    2007-01-01

    Polyhedral oligomeric silsequioxane (POSS) monomer was fixed to a silicon surface by reacting octakis(glycidyldimethylsiloxy)octasilsesquioxane (OG-POSS) with the OH-terminated silicon surface in the presence of tin (II) chloride. The POSS cage layer then served as a nanoporous interlayer to reduce the dielectric constants of polyimide films on silicon surfaces. The chemical structure and surface morphology of OG-POSS modified silicon surfaces were characterized with XPS. With the introduction of a POSS nanopored interlayer, the dielectric constants of polyimide films were reduced

  18. Polymer dynamics in rubbery epoxy networks/polyhedral oligomeric silsesquioxanes nanocomposites

    Czech Academy of Sciences Publication Activity Database

    Kourkoutsaki, T.; Logakis, E.; Kroutilová, Irena; Matějka, Libor; Nedbal, J.; Pissis, P.

    2009-01-01

    Roč. 113, č. 4 (2009), s. 2569-2582 ISSN 0021-8995 R&D Projects: GA AV ČR IAA400500701 Institutional research plan: CEZ:AV0Z40500505 Keywords : nanocomposites * dielectric properties * rubbery epoxy networks Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.203, year: 2009

  19. Epoxy networks reinforced with polyhedral oligomeric silsesquioxanes (POSS). 1. Structure and morphology

    Czech Academy of Sciences Publication Activity Database

    Matějka, Libor; Strachota, Adam; Pleštil, Josef; Whelan, P.; Steinhart, Miloš; Šlouf, Miroslav

    2004-01-01

    Roč. 37, č. 25 (2004), s. 9449-9456 ISSN 0024-9297 R&D Projects: GA AV ČR IAA4050008 Grant - others:European Community's Human Potential Programme(XE) HPRN/CT-2002-00306 Institutional research plan: CEZ:AV0Z4050913 Keywords : POSS * epoxy network * structure of nanocomposites Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.898, year: 2004

  20. Determination of Mechanical and Surface Properties of Semicrystalline Polyhedral Oligomeric Silsesquioxane (POSS) Nanocomposites

    National Research Council Canada - National Science Library

    Moody, Laura E; Marchant, Darrell; Grabow, Wade W; Lee, Andre Y; Mabry, Joseph M

    2005-01-01

    INTRODUCTION: (1) Nanomodification of semicrystalline polymers -- unequalled thermal, mechanical and surface properties at low volume fractions that cannot be obtained using conventional fillers; (2...

  1. Morphology and Viscoelastic Properties of Polystyrene Blended with Fully Condensed Polyhedral Oligomeric Silsesquioxanes

    National Research Council Canada - National Science Library

    Namani, Madhu; Geng, Hai-Ping; Lee, Andre; Blanski, Rusty L

    2004-01-01

    .... Experiments were performed using a nearly-monodisperse molecular weight polystyrene (PS) blended with varying amounts of two fully condensed POSS molecules surrounded with phenethyl and styrenyl groups...

  2. Morphology and Viscoelastic Properties of Polystyrene Blended with Fully Condensed Polyhedral Oligomeric Silsesquioxanes

    Science.gov (United States)

    2004-10-18

    NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR( S ) Madhu Namani ; Hai-Ping Geng; Andre Lee; Rusty Blanski 5d. PROJECT NUMBER 4847 5e...TASK NUMBER 0249 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME( S ) AND ADDRESS(ES) Air Force Research Laboratory (AFMC),AFRL/PRSM,10 E...Saturn Blvd.,Edwards AFB,CA,93524-7680 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING AGENCY NAME( S ) AND ADDRESS(ES) 10. SPONSOR

  3. Crystal engineering of giant molecules based on perylene diimide conjugated polyhedral oligomeric silsesquioxane nano-atom

    Science.gov (United States)

    Ren, He

    Molecular architectures and topologies are found contributing to the formation of supramolecular structures of giant molecules. Dr. Cheng's research group developed a diverse of giant molecules via precisely controlled chemistry synthetic routes. These giant molecules can be categorized into several different families, namely giant surfactants, giant shape amphiphiles and giant polyhedron. By analyzing the hierarchical structures of these carefully designed and precisely synthesized giant molecules, the structural factors which affect, or even dominates, in some cases, the formation of supramolecular structures are revealed in these intensive researches. The results will further contribute to the understanding of dependence of supramolecular structures on molecular designs as well as molecular topology, and providing a practical solution to the scaling up of microscopic molecular functionalities to macroscopic material properties. Molecular Nano Particles (MNPs), including fullerene (C60), POSS, Polyoxometalate (POM) and proteins etc., is defined and applied as a specific type of building blocks in the design and synthesis of giant molecules. The persistence in shape and symmetry is considered as one of the major properties of MNPs. This persistence will support the construction of giant molecules for further supramolecular structures' study by introducing specific shapes, or precisely located side groups which will facilitate self-assembling behaviors with pre-programmed secondary interactions. Dictating material physical properties by its chemical composition is an attractive yet currently failed approach in the study of materials. However, the pursuit of determining material properties by microscopic molecular level properties is never seized, and found its solution when the idea of crystal engineering is raised: should each atom in the material is located exactly where it is designed to be and is properly bonded, the property of the material is hence determined. In such "bottom-up" approach, the precise fabrication of 2 nm 100 nm nanostructures, is of great research interest. In this thesis, crystal engineering of giant molecules based on PDI conjugated POSS Nano-Atom (PDI-BPOSS) nano-atoms via self-assembly is performed and studied. Herein, three different giant molecules were synthesized: shape amphiphile, m-phenyl-(PDI-BPOSS)2 (S1) and tetrahedron, R-(PDI-BPOSS)4 (S2) and S-(PDI-BPOSS)4 (S3). Single crystals were grown for S1 and S2, X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and transmission electron microscopy (TEM) were performed, and crystal structures of these samples were determined, while hexagonal superlattice without crystal order can be observed for S3 to exhibit crystal-like morphology.

  4. Functionalization of Fluoroalkyl Polyhedral Oligomeric Silsesquioxanes (F-POSS) (Post Print)

    Science.gov (United States)

    2012-08-01

    7Si7O9(ONa)3, has been derivatized with long-chain fluorinated trichlorosilanes to produce low surface energy materials (8). However, these shorter propyl ...such as tetrahydrofuran and chloroform . Currently a more in-depth analysis of these polymerizations is being undertaken. Figure 16. Static contact

  5. Polyhedral Oligomeric Silsesquioxane (POSS) Dianiline as a Replacement for Toxic Methylenedianiline in PMR-15: Chemistry and Properties

    Science.gov (United States)

    2016-08-22

    integrals in the 5.9-6.3ppm region, which correspond to the pair of protons on the double bond of the nadic anhydride endcap, were calibrated to 4. This was...Chapter 4. A piston was inserted into the mold cavity and the mold assembly was placed into a 1-ton heated press to cure. With minimal pressure applied...5824. Web. Wu, S. “Synthesis and Characterization of Semiaromatic Polyimides Containing POSS in Main Chain Derived from Double -Decker-Shaped

  6. Epoxy networks reinforced with polyhedral oligomeric silsesquioxanes: structure and segmental dynamics as studied by solid-state NMR

    Czech Academy of Sciences Publication Activity Database

    Brus, Jiří; Urbanová, Martina; Strachota, Adam

    2008-01-01

    Roč. 41, č. 2 (2008), s. 372-386 ISSN 0024-9297 R&D Projects: GA AV ČR IAA400500602 Institutional research plan: CEZ:AV0Z40500505 Keywords : solid-state NMR * polymer networks * polysilsequioxanes Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.407, year: 2008

  7. Effect of Polyhedral Oligomeric Silsesquioxane (POSS) Substituents on the Rheological Behavior in Butyl Methacrylate/POSS Copolymers

    Science.gov (United States)

    2008-10-27

    was repeated twice, dissolving the product in chloroform and diethyl ether, respectively. The polymer was dried at 60 °C under vacuum overnight...the Tg of the i Bu remains the same. Table 1. Tg for Butyl Methacrylate-co- Propyl Methacryl POSS Polymers with Various POSS Substituents

  8. Toughening of Epoxy Adhesives by Combined Interaction of Carbon Nanotubes and Silsesquioxanes

    Directory of Open Access Journals (Sweden)

    Giuseppina Barra

    2017-09-01

    Full Text Available The extensive use of adhesives in many structural applications in the transport industry and particularly in the aeronautic field is due to numerous advantages of bonded joints. However, still many researchers are working to enhance the mechanical properties and rheological performance of adhesives by using nanoadditives. In this study the effect of the addition of Multi-Wall Carbon Nanotubes (MWCNTs with Polyhedral Oligomeric Silsesquioxane (POSS compounds, either Glycidyl Oligomeric Silsesquioxanes (GPOSS or DodecaPhenyl Oligomeric Silsesquioxanes (DPHPOSS to Tetraglycidyl Methylene Dianiline (TGMDA epoxy formulation, was investigated. The formulations contain neither a tougher matrix such as elastomers nor other additives typically used to provide a closer match in the coefficient of thermal expansion in order to discriminate only the effect of the addition of the above-mentioned components. Bonded aluminium single lap joints were made using both untreated and Chromic Acid Anodisation (CAA-treated aluminium alloy T2024 adherends. The effects of the different chemical functionalities of POSS compounds, as well as the synergistic effect between the MWCNT and POSS combination on adhesion strength, were evaluated by viscosity measurement, tensile tests, Dynamic Mechanical Analysis (DMA, single lap joint shear strength tests, and morphological investigation. The best performance in the Lap Shear Strength (LSS of the manufactured joints has been found for treated adherends bonded with epoxy adhesive containing MWCNTs and GPOSS. Carbon nanotubes have been found to play a very effective bridging function across the fracture surface of the bonded joints.

  9. Polyhedral patterns

    KAUST Repository

    Jiang, Caigui; Tang, Chengcheng; Vaxman, Amir; Wonka, Peter; Pottmann, Helmut

    2015-01-01

    We study the design and optimization of polyhedral patterns, which are patterns of planar polygonal faces on freeform surfaces. Working with polyhedral patterns is desirable in architectural geometry and industrial design. However, the classical

  10. An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15.

    Science.gov (United States)

    Zhang, Lei; Abbenhuis, Hendrikus C L; Gerritsen, Gijsbert; Bhriain, Nollaig Ní; Magusin, Pieter C M M; Mezari, Brahim; Han, Wei; van Santen, Rutger A; Yang, Qihua; Li, Can

    2007-01-01

    A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active center, was immobilized successfully by in-situ copolymerization on a mesoporous SBA-15-supported polystyrene polymer. The resulting hybrid materials exhibit attractive textural properties (highly ordered mesostructure, large specific surface area (>380 m2 g-1) and pore volume (>or==0.46 cm3 g-1)), and high activity in the epoxidation of alkenes. In the epoxidation of cyclooctene with tert-butyl hydrogen peroxide (TBHP), the hybrid catalysts have rate constants comparable with that of their homogeneous counterpart, and can be recycled at least seven times. They can also catalyze the epoxidation of cyclooctene with aqueous H2O2 as the oxidant. In two-phase reaction media, the catalysts show much higher activity than their homogeneous counterpart due to the hydrophobic environment around the active centers. They behave as interfacial catalysts due to their multifunctionality, that is, the hydrophobicity of polystyrene and the polyhedral oligomeric silsesquioxanes (POSS), and the hydrophilicity of the silica and the mesoporous structure. Combination of the immobilization of homogeneous catalysts on two conventional supports, inorganic solid and organic polymer, is demonstrated to achieve novel heterogeneous catalytic ensembles with the merits of attractive textural properties, tunable surface properties, and optimized environments around the active sites.

  11. Polyhedral patterns

    KAUST Repository

    Jiang, Caigui

    2015-10-27

    We study the design and optimization of polyhedral patterns, which are patterns of planar polygonal faces on freeform surfaces. Working with polyhedral patterns is desirable in architectural geometry and industrial design. However, the classical tiling patterns on the plane must take on various shapes in order to faithfully and feasibly approximate curved surfaces. We define and analyze the deformations these tiles must undertake to account for curvature, and discover the symmetries that remain invariant under such deformations. We propose a novel method to regularize polyhedral patterns while maintaining these symmetries into a plethora of aesthetic and feasible patterns.

  12. Hansen Solubility Parameters for Octahedral Oligomeric Silsesquioxanes

    Science.gov (United States)

    2012-08-28

    1997, 80, 386-&. 5. Hansen, C. M. The three-dimensional solubility parameter -- key to paint component affinities I. J. Paint Technol. 1967, 39, 104...Chai, J.; Zhang, Q. X.; Han, D. X.; Niu, L. Synthesis and Application of Widely Soluble Graphene Sheets. Langmuir 2010, 26, 12314-12320. 12. Hansen, C

  13. Preparation and Physicochemical Properties of Functionalized Silica/Octamethacryl-Silsesquioxane Hybrid Systems

    Directory of Open Access Journals (Sweden)

    Karolina Szwarc-Rzepka

    2013-01-01

    Full Text Available Alkoxysilane-grafted silica/polyhedral oligomeric silsesquioxane with methacryl substituents (SiO2/silane/POSS hybrid material was synthesized according to hydrolyzation and condensation reactions in the so-called “bifunctionalization process.” It is a new attractive system because of its physicochemical, especially thermal and structural, properties. This innovative method of preparation as well as specific physicochemical and useful properties determine the potential applications of such products in many industries. The structure and physicochemical parameters of obtained hybrid systems were characterized using infrared spectroscopy (FTIR, 13C and 29Si solid-state nuclear magnetic resonance (CP MAS NMR, and thermal analysis. The mechanism of bifunctionalization reaction was proposed. The chemical immobilization of silane coupling agent and Methacryl POSS onto silica support surface was noted during the study. Those changes caused a significant increase in the hydrophobic character of fillers obtained. Moreover, changes in thermal stability of SiO2/silane/POSS hybrid systems in comparison to pure POSS modifier were also observed.

  14. Smooth polyhedral surfaces

    KAUST Repository

    Gü nther, Felix; Jiang, Caigui; Pottmann, Helmut

    2017-01-01

    Polyhedral surfaces are fundamental objects in architectural geometry and industrial design. Whereas closeness of a given mesh to a smooth reference surface and its suitability for numerical simulations were already studied extensively, the aim of our work is to find and to discuss suitable assessments of smoothness of polyhedral surfaces that only take the geometry of the polyhedral surface itself into account. Motivated by analogies to classical differential geometry, we propose a theory of smoothness of polyhedral surfaces including suitable notions of normal vectors, tangent planes, asymptotic directions, and parabolic curves that are invariant under projective transformations. It is remarkable that seemingly mild conditions significantly limit the shapes of faces of a smooth polyhedral surface. Besides being of theoretical interest, we believe that smoothness of polyhedral surfaces is of interest in the architectural context, where vertices and edges of polyhedral surfaces are highly visible.

  15. Smooth polyhedral surfaces

    KAUST Repository

    Günther, Felix

    2017-03-15

    Polyhedral surfaces are fundamental objects in architectural geometry and industrial design. Whereas closeness of a given mesh to a smooth reference surface and its suitability for numerical simulations were already studied extensively, the aim of our work is to find and to discuss suitable assessments of smoothness of polyhedral surfaces that only take the geometry of the polyhedral surface itself into account. Motivated by analogies to classical differential geometry, we propose a theory of smoothness of polyhedral surfaces including suitable notions of normal vectors, tangent planes, asymptotic directions, and parabolic curves that are invariant under projective transformations. It is remarkable that seemingly mild conditions significantly limit the shapes of faces of a smooth polyhedral surface. Besides being of theoretical interest, we believe that smoothness of polyhedral surfaces is of interest in the architectural context, where vertices and edges of polyhedral surfaces are highly visible.

  16. Nanomodified Carbon/Carbon Composites for Intermediate Temperature

    Science.gov (United States)

    2007-08-31

    7] Properties Values Appearance Light yellow liquid (material is waxy at room temperature) Specific Gravity 1.245 Ionic Cl (ppm) ᝺ Ionic Na and K...and several types of nanoparticles: chemically modified montmorillonite (MMT) organoclays, polyhedral oligomeric silsesquioxanes (POSS®), carbon...montmorillonite (MMT) organoclays, carbon nanofibers, polyhedral oligomeric silsesquioxanes (POSS®), nanosilica, nano- silicon carbide (n-SiC), and

  17. Silsesquioxane-derived ceramic fibres

    Science.gov (United States)

    Hurwitz, F. I.; Farmer, S. C.; Terepka, F. M.; Leonhardt, T. A.

    1991-01-01

    Fibers formed from blends of silsesquioxane polymers were characterized to study the pyrolytic conversion of these precursors to ceramics. The morphology of fibers pyrolyzed to 1400 C revealed primarily amorphous glasses whose conversion to beta-SiC is a function of both blend composition and pyrolysis conditions. Formation of beta-SiC crystallites within the glassy phase is favored by higher than stoichiometric C/Si ratios, while carbothermal reduction of Si-O bonds to form SiC with loss of SiO and CO occurs at higher methyl/phenylpropyl silsesquioxane (lower C/Si) ratios. As the carbothermal reduction is assumed to be diffusion controlled, the fibers can serve as model systems to gain understanding of the silsesquioxane pyrolysis behavior, and therefore are useful in the development of polysilsesquioxane-derived ceramic matrices and coatings as well.

  18. The anti-calcification potential of a silsesquioxane nanocomposite polymer under in vitro conditions: potential material for synthetic leaflet heart valve.

    Science.gov (United States)

    Ghanbari, Hossein; Kidane, Asmeret G; Burriesci, Gaetano; Ramesh, Bala; Darbyshire, Arnold; Seifalian, Alexander M

    2010-11-01

    Calcification currently represents a major cause of failure of biological tissue heart valves. It is a complex phenomenon influenced by a number of biochemical and mechanical factors. Recent advances in material science offer new polymers with improved properties, potentially suitable for synthetic leaflets heart valves manufacturing. In this study, the calcification-resistance efficacy and mechanical and surface properties of a new nanocomposite polymeric material (polyhedral oligomeric silsesquioxane-poly(carbonate-urea)urethane; POSS-PCU) which has been developed by our group are assessed by means of in vitro testing. In particular, thin sheets of nanocomposite, glutaraldehyde-fixed bovine pericardium (BP) and polyurethane (PU) were exposed to a calcium solution into a specially designed in vitro accelerated physiological pulsatile pressure system for a period of 31days and a total of 4×10(7) cycles. The samples were investigated for signs of calcification after exposure to calcium solution by means of X-ray, microscopic and chemical inspections. Mechanical and surface properties were also studied using stress-strain behaviour and surface morphology and hydrophobicity. Comparison shows that, in the experimental conditions, the level of calcification for the nanocomposite is considerably lower than for the fixed BP (p=0.008) and PU samples (p=0.015). Also, mechanical properties were unchanged in POSS-PCU, while there was a significant deterioration in PU samples (pnanocomposite remained more hydrophobic than the PU sample (pnanocomposite in synthetic leaflets heart valves may lead to potential advantages in terms of long-term performances and durability. Copyright © 2010. Published by Elsevier Ltd.

  19. Versatile phosphite ligands based on silsesquioxane backbones

    NARCIS (Netherlands)

    van der Vlugt, JI; Ackerstaff, J; Dijkstra, TW; Mills, AM; Kooijman, H; Spek, AL; Meetsma, A; Abbenhuis, HCL; Vogt, D

    Silsesquioxanes are employed as ligand backbones for the synthesis of novel phosphite compounds with 3,3'-5,5'-tetrakis(tert-butyl)-2,2'-di-oxa-1,1'-biphenyl substituents. Both mono- and bidentate phosphites are prepared in good yields. Two types of silsesquioxanes are employed as starting

  20. Oligomerization process

    Science.gov (United States)

    Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

    1991-03-26

    A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled. 2 figures.

  1. Hamiltonian cycles in polyhedral maps

    Indian Academy of Sciences (India)

    We present a necessary and sufficient condition for existence of a contractible, non-separating and non-contractible separating Hamiltonian cycle in the edge graph of polyhedral maps on surfaces.We also present algorithms to construct such cycles whenever it exists where one of them is linear time and another is ...

  2. Space-filling polyhedral sorbents

    Energy Technology Data Exchange (ETDEWEB)

    Haaland, Peter

    2016-06-21

    Solid sorbents, systems, and methods for pumping, storage, and purification of gases are disclosed. They derive from the dynamics of porous and free convection for specific gas/sorbent combinations and use space filling polyhedral microliths with facial aplanarities to produce sorbent arrays with interpenetrating interstitial manifolds of voids.

  3. Polyhedral combinatorics of UPGMA cones

    OpenAIRE

    Davidson, Ruth; Sullivant, Seth

    2013-01-01

    Distance-based methods such as UPGMA (Unweighted Pair Group Method with Arithmetic Mean) continue to play a significant role in phylogenetic research. We use polyhedral combinatorics to analyze the natural subdivision of the positive orthant induced by classifying the input vectors according to tree topologies returned by the algorithm. The partition lattice informs the study of UPGMA trees. We give a closed form for the extreme rays of UPGMA cones on n taxa, and compute the normalized volume...

  4. Silsesquioxane nanoparticles with reactive internal functional groups

    Energy Technology Data Exchange (ETDEWEB)

    Brozek, Eric M . [University of Utah, Department of Chemistry (United States); Washton, Nancy M.; Mueller, Karl T. [Environmental Molecular Sciences Laboratory (United States); Zharov, Ilya, E-mail: i.zharov@utah.edu [University of Utah, Department of Chemistry (United States)

    2017-02-15

    A series of silsesquioxane nanoparticles containing reactive internal organic functionalities throughout the entire particle body have been synthesized using a surfactant-free method with organosilanes as the sole precursors and a base catalyst. The organic functional groups incorporated are vinyl, allyl, mercapto, cyanoethyl, and cyanopropyl groups. The sizes and morphologies of the particles were characterized using SEM and nitrogen adsorption, while the compositions were confirmed using TGA, FT-IR, solid state NMR, and elemental analysis. The accessibility and reactivity of the functional groups inside the particles were demonstrated by performing bromination and reduction reactions in the interior of the particles.

  5. Interactive volume visualization of general polyhedral grids

    KAUST Repository

    Muigg, Philipp; Hadwiger, Markus; Doleisch, Helmut; Grö ller, Eduard M.

    2011-01-01

    This paper presents a novel framework for visualizing volumetric data specified on complex polyhedral grids, without the need to perform any kind of a priori tetrahedralization. These grids are composed of polyhedra that often are non

  6. Mesophase behaviour of polyhedral particles

    KAUST Repository

    Agarwal, Umang

    2011-02-13

    Translational and orientational excluded-volume fields encoded in particles with anisotropic shapes can lead to purely entropy-driven assembly of morphologies with specific order and symmetry. To elucidate this complex correlation, we carried out detailed Monte Carlo simulations of six convex space-filling polyhedrons, namely, truncated octahedrons, rhombic dodecahedrons, hexagonal prisms, cubes, gyrobifastigiums and triangular prisms. Simulations predict the formation of various new liquid-crystalline and plastic-crystalline phases at intermediate volume fractions. By correlating these findings with particle anisotropy and rotational symmetry, simple guidelines for predicting phase behaviour of polyhedral particles are proposed: high rotational symmetry is in general conducive to mesophase formation, with low anisotropy favouring plastic-solid behaviour and intermediate anisotropy (or high uniaxial anisotropy) favouring liquid-crystalline behaviour. It is also found that dynamical disorder is crucial in defining mesophase behaviour, and that the apparent kinetic barrier for the liquid-mesophase transition is much lower for liquid crystals (orientational order) than for plastic solids (translational order). © 2011 Macmillan Publishers Limited. All rights reserved.

  7. Mesophase behaviour of polyhedral particles

    KAUST Repository

    Agarwal, Umang; Escobedo, Fernando A.

    2011-01-01

    Translational and orientational excluded-volume fields encoded in particles with anisotropic shapes can lead to purely entropy-driven assembly of morphologies with specific order and symmetry. To elucidate this complex correlation, we carried out detailed Monte Carlo simulations of six convex space-filling polyhedrons, namely, truncated octahedrons, rhombic dodecahedrons, hexagonal prisms, cubes, gyrobifastigiums and triangular prisms. Simulations predict the formation of various new liquid-crystalline and plastic-crystalline phases at intermediate volume fractions. By correlating these findings with particle anisotropy and rotational symmetry, simple guidelines for predicting phase behaviour of polyhedral particles are proposed: high rotational symmetry is in general conducive to mesophase formation, with low anisotropy favouring plastic-solid behaviour and intermediate anisotropy (or high uniaxial anisotropy) favouring liquid-crystalline behaviour. It is also found that dynamical disorder is crucial in defining mesophase behaviour, and that the apparent kinetic barrier for the liquid-mesophase transition is much lower for liquid crystals (orientational order) than for plastic solids (translational order). © 2011 Macmillan Publishers Limited. All rights reserved.

  8. n-th Roots in finite polyhedral and centro-polyhedral groups

    Indian Academy of Sciences (India)

    Probability in finite groups; roots of elements; polyhedral groups; centro- polyhedral groups. 2010 Mathematics ... An element g of a finite group G is said to have an n-th root if there exists an element h ∈ G such that g = hn (n is a ..... For the proof of the fourth part, we must consider two cases: (i) m is odd and 4|d,. (ii) m, d are ...

  9. OLIGOMERIZATION AND LIQUEFACTION OF ETHYLENE

    African Journals Online (AJOL)

    oligomerize ethylene gas in a packed bed reactor operated at 100-300°C under apressure of 500psi and ... The gas flow was then switched back to N, gas and temperature controller was simultaneously set to the desired reaction temperature. Once the desired .... be considered non-ideal for ethylene oligomerization.

  10. Determination of Mechanical and Surface Properties of Semicrystalline Polyhedral Oligomeric Silsequioxane (POSS) Nanocomposites

    National Research Council Canada - National Science Library

    Moody, Laura E; Marchant, Darrell; Grabow, Wade W; Lee, Andre Y; Mabry, Joseph M

    2005-01-01

    .... This study examines the ability of POSS to improve the mechanical and surface properties of three semicrystalline polymers, fluorinated ethylene-propylene (FEP), poly(vinylidene fluoride) (PVDF...

  11. Oligomerization in health and disease

    CERN Document Server

    Giraldo, Jesus

    2013-01-01

    This special volume of Progress in Molecular Biology and Translational Science focuses on oligomerization in health and disease. Contributions from leading authorities Informs and updates on all the latest developments in the field.

  12. Biophysical characterization of GPCR oligomerization

    DEFF Research Database (Denmark)

    Mathiasen, Signe

    level, and revealed the existence of several dimerization interfaces, each with specific kinetics. Finally we investigated how a property of the membrane solubilizing GPCRs affected oligomerization. We observed a dramatic decrease in oligomer stability with increasing geometrical membrane curvature. We...

  13. n-th Roots in finite polyhedral and centro-polyhedral groups

    Indian Academy of Sciences (India)

    The probability that a randomly chosen element in a non-abelian finite group has a square root, has been investigated by certain authors in recent years. In this paper, this probability will be generalized for the -th roots when ≥ 2 and it will be computed for every finite polyhedral group and all of the finite ...

  14. Flexible Polyhedral Surfaces with Two Flat Poses

    Directory of Open Access Journals (Sweden)

    Hellmuth Stachel

    2015-05-01

    Full Text Available We present three types of polyhedral surfaces, which are continuously flexible and have not only an initial pose, where all faces are coplanar, but pass during their self-motion through another pose with coplanar faces (“flat pose”. These surfaces are examples of so-called rigid origami, since we only admit exact flexions, i.e., each face remains rigid during the motion; only the dihedral angles vary. We analyze the geometry behind Miura-ori and address Kokotsakis’ example of a flexible tessellation with the particular case of a cyclic quadrangle. Finally, we recall Bricard’s octahedra of Type 3 and their relation to strophoids.

  15. Interactive volume visualization of general polyhedral grids

    KAUST Repository

    Muigg, Philipp

    2011-12-01

    This paper presents a novel framework for visualizing volumetric data specified on complex polyhedral grids, without the need to perform any kind of a priori tetrahedralization. These grids are composed of polyhedra that often are non-convex and have an arbitrary number of faces, where the faces can be non-planar with an arbitrary number of vertices. The importance of such grids in state-of-the-art simulation packages is increasing rapidly. We propose a very compact, face-based data structure for representing such meshes for visualization, called two-sided face sequence lists (TSFSL), as well as an algorithm for direct GPU-based ray-casting using this representation. The TSFSL data structure is able to represent the entire mesh topology in a 1D TSFSL data array of face records, which facilitates the use of efficient 1D texture accesses for visualization. In order to scale to large data sizes, we employ a mesh decomposition into bricks that can be handled independently, where each brick is then composed of its own TSFSL array. This bricking enables memory savings and performance improvements for large meshes. We illustrate the feasibility of our approach with real-world application results, by visualizing highly complex polyhedral data from commercial state-of-the-art simulation packages. © 2011 IEEE.

  16. Organosilica hybrid nanomaterials with a high organic content: syntheses and applications of silsesquioxanes

    KAUST Repository

    Croissant, Jonas G.

    2016-11-07

    Organic-inorganic hybrid materials garner properties from their organic and inorganic matrices as well as synergistic features, and therefore have recently attracted much attention at the nanoscale. Non-porous organosilica hybrid nanomaterials with a high organic content such as silsesquioxanes (R-SiO, with R organic groups) and bridged silsesquioxanes (OSi-R-SiO) are especially attractive hybrids since they provide 20 to 80 weight percent of organic functional groups in addition to the known chemistry and stability of silica. In the organosilica family, silsesquioxanes (R-SiO) stand between silicas (SiO) and silicones (RSiO), and are variously called organosilicas, ormosil (organically-modified silica), polysilsesquioxanes and silica hybrids. Herein, we comprehensively review non-porous silsesquioxane and bridged silsesquioxane nanomaterials and their applications in nanomedicine, electro-optics, and catalysis.

  17. Zero point energy of polyhedral water clusters.

    Science.gov (United States)

    Anick, David J

    2005-06-30

    Polyhedral water clusters (PWCs) are cage-like (H2O)n clusters where every O participates in exactly three H bonds. For a database of 83 PWCs, 8 zero point energy (ZPE) was calculated at the B3LYP/6-311++G** level. ZPE correlates negatively with electronic energy (E0): each increase of 1 kcal/mol in E0 corresponds to a decrease of about 0.11 kcal/mol in ZPE. For each n, a set of four connectivity parameters accounts for 98% or more of the variance in ZPE. Linear regression of ZPE against n and this set gives an RMS error of 0.13 kcal/mol. The contributions to ZPE from stretch modes only (ZPE(S)) and from torsional modes only (ZPE(T)) also correlate strongly with E0 and with each other.

  18. Preparation and Characterization of Polyhedral Oligosilsesquioxanes

    Science.gov (United States)

    Cordes, David B.; Lickiss, Paul D.

    Polyhedral OligoSilSesquioxanes are often abbreviated by the acronym POS or POSS® and are compounds of the general formula Sin O3n/2Rn (often denoted as TnRn). The commonest of these compounds are the cubic T8R8 POS species since many hydrolysis/condensation reactions of simple RSiX3 compounds (X = Cl, OMe or OEt) give the T8R8 cage as a major product, usually along with small amounts of other TnRn cages and polymeric by-products. Few T4R4 POS have been prepared as they seem to require very bulky R-groups to stabilize the strained POS system and to prevent formation of larger, more stable POS cages.

  19. Fernando Cassinello Pérez, polyhedral architect

    Directory of Open Access Journals (Sweden)

    M. Centellas Soler

    2017-03-01

    Full Text Available The work of architect Fernando Cassinello Pérez (Almería, 1928-Madrid, 1975 rests on three pillars: architectural production focused on the design and construction of housing and hotel establishments, academic activity as Professor of Construction at the Escuela de Arquitectura de Madrid, and research concern developed in the IETcc of which he became director, and exercised as an author of books and research papers, as disseminator lecturer, speaker at major conferences or as an active member of international associations linked to construction with concrete. This article will review his prolific activity as polyhedral architect and will find interesting works that designed and built by relying on extensive contemporary and international architectural culture.

  20. Theoretical Studies of Group IVA and Group IVB Chemistry

    Science.gov (United States)

    2012-01-13

    novel ionic liquids . We have performed very high level CCSD(T) calculations on one such species, Al13- to predict its ionization potential in nearly...Precursors. Polyhedral oligomeric silsesquioxanes (POSS) are three- dimensional Si-O cage compounds that have many uses, because of their resistance

  1. MURI Center for Materials Chemistry in the Space Environment

    Science.gov (United States)

    2006-11-30

    ionic species in relevant reaction environments, surface photochemistry expertise, synchrotron-based measurement and irradiation, synthesis of structural...and Ne+ ions with dodecanethiolate and semifluorinated dodecanethiolate self-assembled monolayers (SAM), polyhedral oligomeric silsesquioxane (POSS...POSS/Kapton models as gas phase species, and with alkane thiol self assembled monolayers on gold surfaces, and with liquid squalane. We have also

  2. Clustered deep shadow maps for integrated polyhedral and volume rendering

    KAUST Repository

    Bornik, Alexander; Knecht, Wolfgang; Hadwiger, Markus; Schmalstieg, Dieter

    2012-01-01

    This paper presents a hardware-accelerated approach for shadow computation in scenes containing both complex volumetric objects and polyhedral models. Our system is the first hardware accelerated complete implementation of deep shadow maps, which

  3. Hybrid Organic-Inorganic Bridged Silsesquioxane Nanoparticles for Cancer Nanomedicine

    KAUST Repository

    Fatieiev, Yevhen

    2017-10-01

    It is well established that cancer is one of the leading causes of death globally. Its complete eradication requires early detection and intensive drug treatment. In many cases it might also require surgery. Unfortunately, current medicine is still more focused on cancer treatment rather than elimination of its reason. The mechanism of tumor emergence and development is quite complicated, although, we are constantly advancing in this field. Nanomedicine is envisioned as the silver bullet against cancer. Thus, nanoscale systems with therapeutic and diagnostic modalities can simultaneously perform several functions: accurate detection of tumor site, precise targeting, and controlled drug release inside abnormal cells and tissues while being nontoxic to healthy ones. Moreover, surface modification of such nanoparticles allows them to be invisible to the immune system and have longer blood circulating time. The performed research in this dissertation is completely based on hybrid organicinorganic bridged silsesquioxane (also known as organosilica) nanomaterials, therefore comprising "soft" organic/bioorganic part which can imitate certain biorelevant structures and facilitates successful escape from the immune system for more efficient accumulation in cancer cells, while "hard" inorganic part serves as a rigid and stable basis for the creation of cargo nanocarriers and imaging agents. This dissertation discusses the 5 critical points of safe biodegradable nanoplatforms, delivery of large biomolecules, and cytotoxicity regarding the shape of nanoparticles. As a result novel fluorescent biodegradable oxamide-based organosilica nanoparticles were developed, light-triggered surface charge reversal for large biomolecule delivery was applied with hollow bridged silsesquioxane nanomaterials, and biocompatibility of periodic mesoporous organosilicas with different morphologies was studied. Furthermore, the current achievements and future perspectives of mesoporous silica

  4. Hybrid Organic-Inorganic Bridged Silsesquioxane Nanoparticles for Cancer Nanomedicine

    KAUST Repository

    Fatieiev, Yevhen

    2017-01-01

    It is well established that cancer is one of the leading causes of death globally. Its complete eradication requires early detection and intensive drug treatment. In many cases it might also require surgery. Unfortunately, current medicine is still more focused on cancer treatment rather than elimination of its reason. The mechanism of tumor emergence and development is quite complicated, although, we are constantly advancing in this field. Nanomedicine is envisioned as the silver bullet against cancer. Thus, nanoscale systems with therapeutic and diagnostic modalities can simultaneously perform several functions: accurate detection of tumor site, precise targeting, and controlled drug release inside abnormal cells and tissues while being nontoxic to healthy ones. Moreover, surface modification of such nanoparticles allows them to be invisible to the immune system and have longer blood circulating time. The performed research in this dissertation is completely based on hybrid organicinorganic bridged silsesquioxane (also known as organosilica) nanomaterials, therefore comprising "soft" organic/bioorganic part which can imitate certain biorelevant structures and facilitates successful escape from the immune system for more efficient accumulation in cancer cells, while "hard" inorganic part serves as a rigid and stable basis for the creation of cargo nanocarriers and imaging agents. This dissertation discusses the 5 critical points of safe biodegradable nanoplatforms, delivery of large biomolecules, and cytotoxicity regarding the shape of nanoparticles. As a result novel fluorescent biodegradable oxamide-based organosilica nanoparticles were developed, light-triggered surface charge reversal for large biomolecule delivery was applied with hollow bridged silsesquioxane nanomaterials, and biocompatibility of periodic mesoporous organosilicas with different morphologies was studied. Furthermore, the current achievements and future perspectives of mesoporous silica

  5. Enzymatically Degradable Hybrid Organic-Inorganic Bridged Silsesquioxane Nanoparticles for In-Vitro Imaging

    KAUST Repository

    Fatieiev, Yevhen; Croissant, Jonas G.; Julfakyan, Khachatur; Deng, Lin; Anjum, Dalaver H.; Gurinov, Andrei; Khashab, Niveen M.

    2015-01-01

    Non-aggregated dense bridged silsesquioxane (BS) nanoparticles based on nature-inspired oxamide bridges are shown to degrade in simulated biological media upon cleavage with endopeptidase. Fluorescent BS nanoprobes with incorporated fluorescein dyes

  6. Organosilica hybrid nanomaterials with a high organic content: syntheses and applications of silsesquioxanes

    KAUST Repository

    Croissant, Jonas G.; Cattoë n, Xavier; Durand, Jean Olivier; Wong Chi Man, Michel; Khashab, Niveen M.

    2016-01-01

    chemistry and stability of silica. In the organosilica family, silsesquioxanes (R-SiO) stand between silicas (SiO) and silicones (RSiO), and are variously called organosilicas, ormosil (organically-modified silica), polysilsesquioxanes and silica hybrids

  7. [Formian 2 and a Formian Function for Processing Polyhedric Configurations

    Science.gov (United States)

    Nooshin, H.; Disney, P. L.; Champion, O. C.

    1996-01-01

    The work began in October 1994 with the following objectives: (1) to produce an improved version of the programming language Formian; and (2) to create a means for computer aided handling of polyhedric configurations including the geodesic forms of all kinds. A new version of Formian, referred to as Formian 2, is being implemented to operate in the Windows 95 environment. It is an ideal tool for configuration management in a convenient and user-friendly manner. The second objective was achieved by creating a standard Formian function that allows convenient handling of all types of polyhedric configurations. In particular, the focus of attention is on polyhedric configurations that are of importance in architectural and structural engineering fields. The natural medium for processing of polyhedric configurations is a programming language that incorporates the concepts of 'formex algebra'. Formian is such a programming language in which the processing of polyhedric configurations can be carried out using the standard elements of the language. A description of this function is included in a chapter for a book entitled 'Beyond the Cube: the Architecture of space Frames and Polyhedra'. A copy of this chapter is appended.

  8. A simple gel electrophoresis method for separating polyhedral gold nanoparticles

    Science.gov (United States)

    Kim, Suhee; Lee, Hye Jin

    2015-07-01

    In this paper, a simple approach to separate differently shaped and sized polyhedral gold nanoparticles (NPs) within colloidal solutions via gel electrophoresis is described. Gel running parameters for separating efficiently gold NPs including gel composition, added surfactant types and applied voltage were investigated. The plasmonic properties and physical structure of the separated NPs extracted from the gel matrix were then investigated using transmission electron microscopy (TEM) and UV-vis spectrophotometry respectively. Data analysis revealed that gel electrophoresis conditions of a 1.5 % agarose gel with 0.1 % sodium dodecyl sulfate (SDS) surfactant under an applied voltage of 100 V resulted in the selective isolation of ~ 50 nm polyhedral shaped gold nanoparticles. Further efforts are underway to apply the method to purify biomolecule-conjugated polyhedral Au NPs that can be readily used for NP-enhanced biosensing platforms.

  9. Tailoring the Kinetics of the Photoinitiated Cationic Polymerization of Polyoctahedral Oligomeric Silsesquioxane (POSS)-Containing Epoxy Monomers

    Science.gov (United States)

    Iordanov, Liubomir

    Within the aircraft industry, high strength steels have been used for aircraft components (e.g., main landing gear, fasteners, etc). These steels have traditionally been protected using cadmium electroplating. As a result of the carcinogenic nature of cadmium, its use has been severely restricted. Electroplated ZnNi has been identified as a replacement material for the cadmium coating. Demonstration plating lines have been implemented in both Air Force and NAVAIR depots. However, the effects of hydrogen generated from differences in electrochemical potential between the ZnNi coating and exposed steel at a defect site have raised concern. The objective of this work is to determine the potential effect of hydrogen on the susceptibility of ZnNi coated 4340 steel to Hydrogen Embrittlement. In this work, susceptibility of the substrate AISI 4340 steel to HE as a function of cathodic potential will be shown. Slow strain rate tests (SSRT) of smooth bar samples made of high strength AISI 4340 are being conducted to determine susceptibility to HE. In the first set of SSR experiments, bare steel samples were exposed to a NaCl immersion environment while being held at one of five different electrochemical potentials. The effect of potential on time to failure and other properties will be explored. A second set of SSR tests were performed under atmospheric exposure conditions at 84% RH. This value of RH is above the deliquescence point of NaCl and was controlled within the enclosed SSR test cell using a saturated solution of Sodium Sulfate at the bottom of the cell. NaCl salt was deposited on the SSR sample gauge section by a salt spray technique. Filter paper soaked in saturated NaCl solution was used to act as a salt bridge for the reference and counter electrodes under atmospheric condition. The effect of electrochemical potential on the cracking behavior of the atmospherically exposed samples will also be described. SEM characterization of the fractured samples was performed to validate embrittlement. Results from this effort will be used by both the Air Force and Navy to assess the need for enhanced risk based inspection of ZnNi coated steel parts. Engineering modeling was done for different defect sizes on the sample and results were used to validate engineering modeling approaches to predict corrosion and cracking performance during system design.

  10. Constitutive equations for discrete electromagnetic problems over polyhedral grids

    International Nuclear Information System (INIS)

    Codecasa, Lorenzo; Trevisan, Francesco

    2007-01-01

    In this paper a novel approach is proposed for constructing discrete counterparts of constitutive equations over polyhedral grids which ensure both consistency and stability of the algebraic equations discretizing an electromagnetic field problem. The idea is to construct discrete constitutive equations preserving the thermodynamic relations for constitutive equations. In this way, consistency and stability of the discrete equations are ensured. At the base, a purely geometric condition between the primal and the dual grids has to be satisfied for a given primal polyhedral grid, by properly choosing the dual grid. Numerical experiments demonstrate that the proposed discrete constitutive equations lead to accurate approximations of the electromagnetic field

  11. How to collect and process large polyhedral viruses of insects

    Science.gov (United States)

    W. D. Rollinson; F. B. Lewis

    1962-01-01

    Polyhedral viruses have proved highly effective and very practical for control of certain pine sawflies; and a method of collecting and processing the small polyhedra (5 microns or less) characteristic of sawflies has been described. There is experimental evidence that the virus diseases of many Lepidopterous insects can be used similarly for direct control. The...

  12. A Novel Type of Polyhedral Viruses Infecting Hyperthermophilic Archaea.

    Science.gov (United States)

    Liu, Ying; Ishino, Sonoko; Ishino, Yoshizumi; Pehau-Arnaudet, Gérard; Krupovic, Mart; Prangishvili, David

    2017-07-01

    Encapsidation of genetic material into polyhedral particles is one of the most common structural solutions employed by viruses infecting hosts in all three domains of life. Here, we describe a new virus of hyperthermophilic archaea, Sulfolobus polyhedral virus 1 (SPV1), which condenses its circular double-stranded DNA genome in a manner not previously observed for other known viruses. The genome complexed with virion proteins is wound up sinusoidally into a spherical coil which is surrounded by an envelope and further encased by an outer polyhedral capsid apparently composed of the 20-kDa virion protein. Lipids selectively acquired from the pool of host lipids are integral constituents of the virion. None of the major virion proteins of SPV1 show similarity to structural proteins of known viruses. However, minor structural proteins, which are predicted to mediate host recognition, are shared with other hyperthermophilic archaeal viruses infecting members of the order Sulfolobales The SPV1 genome consists of 20,222 bp and contains 45 open reading frames, only one-fifth of which could be functionally annotated. IMPORTANCE Viruses infecting hyperthermophilic archaea display a remarkable morphological diversity, often presenting architectural solutions not employed by known viruses of bacteria and eukaryotes. Here we present the isolation and characterization of Sulfolobus polyhedral virus 1, which condenses its genome into a unique spherical coil. Due to the original genomic and architectural features of SPV1, the virus should be considered a representative of a new viral family, "Portogloboviridae." Copyright © 2017 American Society for Microbiology.

  13. Rheological Behavior of Entangled Polystyrene-Polyhedral Oligosilsesquioxane (POSS) Copolymer

    National Research Council Canada - National Science Library

    Wu, Jian; Mather, Patrick T; Haddad, Timothy S; Kim, Gyeong-Man

    2006-01-01

    ...: random copolymers of polystyrene (PS) and styryl-based polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(C6H4CH=CH2), with R = isobutyl (iBu). A series of styrene-styryl POSS random copolymers with 0, 6, 15, 30, 50 wt...

  14. Dimerization and oligomerization of the chaperone calreticulin

    DEFF Research Database (Denmark)

    Jørgensen, Charlotte S; Ryder, L Rebekka; Steinø, Anne

    2003-01-01

    protein. Using PAGE, urea gradient gel electrophoresis, capillary electrophoresis and MS, we show that dimerization through the SH group can be induced by lowering the pH to 5-6, heating, or under conditions that favour partial unfolding such as urea concentrations above 2.6 m or SDS concentrations above...... that favour partial unfolding or an intramolecular local conformational change that allows oligomerization, resulting in a heterogeneous mixture of oligomers consisting of up to 10 calreticulin monomers. The oligomeric calreticulin was very stable, but oligomerization was partially reversed by addition of 8 m...

  15. Photoresponsive Bridged Silsesquioxane Nanoparticles with Tunable Morphology for Light-Triggered Plasmid DNA Delivery

    KAUST Repository

    Fatieiev, Yevhen; Croissant, Jonas G.; Alsaiari, Shahad K.; Moosa, Basem; Anjum, Dalaver H.; Khashab, Niveen M.

    2015-01-01

    Bridged silsesquioxane nanocomposites with tunable morphologies incorporating o-nitrophenylene-ammonium bridges are described. The systematic screening of the sol-gel parameters allowed the material to reach the nanoscale –unlike most reported bridged silsesquioxane materials– with controlled dense and hollow structures of 100 to 200 nm. The hybrid composition of silsesquioxanes with 50% of organic content homogenously distributed in the nanomaterials endowed them with photoresponsive properties. Light irradiation was performed to reverse the surface charge of nanoparticles from +46 to -39 mV via the photoreaction of the organic fragments within the particles, as confirmed by spectroscopic monitorings. Furthermore, such NPs were ap-plied for the first time for the on-demand delivery of plasmid DNA in HeLa cancer cells via light actuation.

  16. Photoresponsive Bridged Silsesquioxane Nanoparticles with Tunable Morphology for Light-Triggered Plasmid DNA Delivery

    KAUST Repository

    Fatieiev, Yevhen

    2015-09-25

    Bridged silsesquioxane nanocomposites with tunable morphologies incorporating o-nitrophenylene-ammonium bridges are described. The systematic screening of the sol-gel parameters allowed the material to reach the nanoscale –unlike most reported bridged silsesquioxane materials– with controlled dense and hollow structures of 100 to 200 nm. The hybrid composition of silsesquioxanes with 50% of organic content homogenously distributed in the nanomaterials endowed them with photoresponsive properties. Light irradiation was performed to reverse the surface charge of nanoparticles from +46 to -39 mV via the photoreaction of the organic fragments within the particles, as confirmed by spectroscopic monitorings. Furthermore, such NPs were ap-plied for the first time for the on-demand delivery of plasmid DNA in HeLa cancer cells via light actuation.

  17. Protein dimerization and oligomerization in biology

    National Research Council Canada - National Science Library

    Matthews, Jacqueline M

    2012-01-01

    .... However, protein function is so often linked to both homo- and hetero-oligomerization and many heterologous interactions likely evolved from homologous interaction, so this volume also covers many...

  18. Reversible peptide oligomerization over nanoscale gold surfaces

    Directory of Open Access Journals (Sweden)

    Kazushige Yokoyama

    2015-11-01

    Full Text Available A selective oligomeric formation of amyloid beta 1-40 (Ab1-40 monomers over a nanogold colloidal surface was investigated. An unfolded Ab1-40 monomer is considered to construct a dimer or trimer based oligomeric form with its hydrophobic segment placing outward under an acidic condition. Under a basic condition, a conformation of Ab is expected to take a folded monomeric form with its hydrophilic segment folded inward, avoiding the networking with residual colloidal particles. The most probable oligomeric form constructed over a 20 nm gold colloidal surface within a 25 ℃ to 65 ℃ temperature range is a dimer based unit and that over 30 or 40 nm gold colloidal surface below 15 ℃ is concluded to be a trimer based unit. However, selective oligomerization was not successfully reproduced under the rest of the conditions. A dipole-induced dipole interaction must cause a flexible structural change between folded and unfolded forms.

  19. Exposure parameters in proton beam writing for hydrogen silsesquioxane

    International Nuclear Information System (INIS)

    Kan, J.A. van; Zhang, F.; Zhang, C.; Bettiol, A.A.; Watt, F.

    2008-01-01

    In proton beam writing (PBW) a focused MeV proton beam is scanned in a predetermined pattern over a resist (e.g. PMMA, SU-8 or HSQ), which is subsequently chemically developed. In e-beam writing as well as p-beam writing the energy loss of the primary beam is dominated by energy transfer to substrate electrons. Unlike the high energy secondary electrons generated during e-beam writing the secondary electrons induced by the primary proton beam have low energy and therefore a limited range, resulting in minimal proximity effects. The low proximity effects exhibited by p-beam writing coupled with the straight trajectory and high penetration of the proton beam enables the production of high aspect ratio, high density 3D micro and nanostructures with well defined smooth side walls to be directly written into resist materials. This property together with the stability and focusing power of the end station ensures even exposures with nm smoothness and allows fabrication of details down to the 20 nm level. In this paper, we present results like contrast and sensitivity for PBW using, hydrogen silsesquioxane (HSQ) and XR-1541, both are non-C based resists. Unlike PMMA and SU-8 resist HSQ shows aging effects, requiring optimized processing parameters in PBW

  20. Form-finding with polyhedral meshes made simple

    KAUST Repository

    Tang, Chengcheng; Sun, Xiang; Gomes, Maria Alexandra; Wallner, Johannes; Pottmann, Helmut

    2014-01-01

    We solve the form-finding problem for polyhedral meshes in a way which combines form, function and fabrication; taking care of user-specified constraints like boundary interpolation, planarity of faces, statics, panel size and shape, enclosed volume, and last, but not least, cost. Our main application is the interactive modeling of meshes for architectural and industrial design. Our approach can be described as guided exploration of the constraint space whose algebraic structure is simplified by introducing auxiliary variables and ensuring that constraints are at most quadratic. Computationally, we perform a projection onto the constraint space which is biased towards low values of an energy which expresses desirable "soft" properties like fairness. We have created a tool which elegantly handles difficult tasks, such as taking boundary-alignment of polyhedral meshes into account, planarization, fairing under planarity side conditions, handling hybrid meshes, and extending the treatment of static equilibrium to shapes which possess overhanging parts.

  1. Form-finding with polyhedral meshes made simple

    KAUST Repository

    Tang, Chengcheng

    2014-07-27

    We solve the form-finding problem for polyhedral meshes in a way which combines form, function and fabrication; taking care of user-specified constraints like boundary interpolation, planarity of faces, statics, panel size and shape, enclosed volume, and last, but not least, cost. Our main application is the interactive modeling of meshes for architectural and industrial design. Our approach can be described as guided exploration of the constraint space whose algebraic structure is simplified by introducing auxiliary variables and ensuring that constraints are at most quadratic. Computationally, we perform a projection onto the constraint space which is biased towards low values of an energy which expresses desirable "soft" properties like fairness. We have created a tool which elegantly handles difficult tasks, such as taking boundary-alignment of polyhedral meshes into account, planarization, fairing under planarity side conditions, handling hybrid meshes, and extending the treatment of static equilibrium to shapes which possess overhanging parts.

  2. Clustered deep shadow maps for integrated polyhedral and volume rendering

    KAUST Repository

    Bornik, Alexander

    2012-01-01

    This paper presents a hardware-accelerated approach for shadow computation in scenes containing both complex volumetric objects and polyhedral models. Our system is the first hardware accelerated complete implementation of deep shadow maps, which unifies the computation of volumetric and geometric shadows. Up to now such unified computation was limited to software-only rendering . Previous hardware accelerated techniques can handle only geometric or only volumetric scenes - both resulting in the loss of important properties of the original concept. Our approach supports interactive rendering of polyhedrally bounded volumetric objects on the GPU based on ray casting. The ray casting can be conveniently used for both the shadow map computation and the rendering. We show how anti-aliased high-quality shadows are feasible in scenes composed of multiple overlapping translucent objects, and how sparse scenes can be handled efficiently using clustered deep shadow maps. © 2012 Springer-Verlag.

  3. Image of the World on polyhedral maps and globes

    Directory of Open Access Journals (Sweden)

    Pędzich Paweł

    2016-12-01

    Full Text Available Application of polyhedrons as image surface in cartographic projections has a tradition of more than 200 years. The first maps relying on polyhedrons appeared in the 19th century. One of the first maps which based on an original polyhedral projection using a regular octahedron was constructed by the Californian architect Bernard Cahill in 1909. Other well known polyhedral projections and maps included Buckminster Fuller’s projection and map into icosahedron from 1954 and S. Waterman’s projection into truncated octahedron from 1996, which resulted in the “butterfly” map. Polyhedrons as image surface have the advantage of allowing a continuous image of continents of the Earth with low projection distortion. Such maps can be used for many purposes, such as presentation of tectonic plates or geographic discoveries.

  4. Topology, isomorphic smoothness and polyhedrality in Banach spaces

    OpenAIRE

    Smith, Richard J.

    2018-01-01

    In recent decades, topology has come to play an increasing role in some geometric aspects of Banach space theory. The class of so-called $w^*$-locally relatively compact sets was introduced recently by Fonf, Pallares, Troyanski and the author, and were found to be a useful topological tool in the theory of isomorphic smoothness and polyhedrality in Banach spaces. We develop the topological theory of these sets and present some Banach space applications.

  5. Sub-polyhedral scheduling using (unit-)two-variable-per-inequality polyhedra

    OpenAIRE

    Upadrasta , Ramakrishna; Cohen , Albert

    2013-01-01

    International audience; Polyhedral compilation has been successful in the design and implementation of complex loop nest optimizers and parallelizing compilers. The algorithmic complexity and scalability limitations remain one important weakness. We address it using sub-polyhedral under-aproximations of the systems of constraints resulting from affine scheduling problems. We propose a sub-polyhedral scheduling technique using (Unit-)Two-Variable-Per-Inequality or (U)TVPI Polyhedra. This techn...

  6. Polyhedral Boranes: A Versatile Building Block for Nanoporous Materials

    Science.gov (United States)

    Clingerman, Daniel Jon

    The studies described in this dissertation examine several new concepts related to polyhedral boranes and their applications towards the synthesis of novel nanoporous materials. The unique thermal and chemical robustness, rigidity, quasi-spherical geometry, and high boron content of polyhedral boranes are explored to generate materials not possible with typical organic synthons. Aside from the fundamental synthetic work, this work was also aimed at solving larger global issues such as energy storage and new routes to therapeutics. Chapter 2 highlights the discovery of the first highly porous carborane-based metal-organic framework, where the spherical nature of the carborane increases volumetric surface area without reducing pore volume. Chapter 3 examines the first tritopic carborane-based ligand and the stabilizing effect the rigid, sterically bulky carboranyl groups have on highly porous topologies not stable with typical organic ligands. Chapters 4 and 5 describe the use of polyhedral borane-based ligands as a means to influence and generate unexpected topologies. Lastly, chapter 6 explores using a simple carborane-based ligand that harnesses the power of coordination-driven assembly to rapidly generate a high boron-containing supramolecular cuboctahedron.

  7. Toward Increasing Micropore Volume between Hybrid Layered Perovskites with Silsesquioxane Interlayers.

    Science.gov (United States)

    Kataoka, Sho; Kamimura, Yoshihiro; Endo, Akira

    2018-04-10

    Hybrid organic-inorganic layered perovskites are typically nonporous solids. However, the incorporation of silsesquioxanes with a cubic cage structure as interlayer materials creates micropores between the perovskite layers. In this study, we increase in the micropore volume in layered perovskites by replacing a portion of the silsesquioxane interlayers with organic amines. In the proposed method, approximately 20% of the silsesquioxane interlayers can be replaced without changing the layer distance owing to the size of the silsesquioxane. When small amines (e.g., ethylamine) are used in this manner, the micropore volume of the obtained hybrid layered perovskites increases by as much as 44%; when large amines (e.g., phenethylamine) are used, their micropore volume decreases by as much as 43%. Through the variation of amine fraction, the micropore volume can be adjusted in the range. Finally, the magnetic moment measurements reveal that the layered perovskites with mixed interlayers exhibit ferromagnetic ordering at temperature below 20 K, thus indicating that the obtained perovskites maintain their functions as layered perovskites.

  8. An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15

    NARCIS (Netherlands)

    Santen, van R.A.; Zhang, Lei; Abbenhuis, H.C.L.; Gerritsen, G.; Ní Bhriain, N.M.; Magusin, P.C.M.M.; Mezari, B.; Han, W.; Yang, Q.; Li, Can

    2007-01-01

    A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active

  9. Electron transport nonlocality in monolayer graphene modified with hydrogen silsesquioxane polymerization

    NARCIS (Netherlands)

    Kaverzin, A. A.; van Wees, B. J.

    2015-01-01

    A number of practical and fundamental applications of graphene requires modification of some of its properties. In this paper we study the effect of polymerization of a hydrogen silsesquioxane film on top of monolayer graphene with the intent to increase the strength of the spin-orbit interaction.

  10. Enzymatically Degradable Hybrid Organic-Inorganic Bridged Silsesquioxane Nanoparticles for In-Vitro Imaging

    KAUST Repository

    Fatieiev, Yevhen

    2015-06-30

    Non-aggregated dense bridged silsesquioxane (BS) nanoparticles based on nature-inspired oxamide bridges are shown to degrade in simulated biological media upon cleavage with endopeptidase. Fluorescent BS nanoprobes with incorporated fluorescein dyes were applied for in-vitro imaging in cancer cells.

  11. Low Temperature Curing of Hydrogen Silsesquioxane Surface Coatings for Corrosion Protection of Aluminum

    DEFF Research Database (Denmark)

    Lampert, Felix; Jensen, Annemette Hindhede; Møller, Per

    2016-01-01

    Hydrogen Silsesquioxane (HSQ) has shown to be a promising precursor for corrosion protective glass coatings for metallic substrates due to the excellent barrier properties of the films, especially in the application of protective coatings for aluminum in the automotive industry where high chemica...

  12. Organo-bridged silsesquioxane titanates for heterogeneous catalytic epoxidation with aqueous hydrogen peroxide

    NARCIS (Netherlands)

    Wang, Y.M.; Magusin, P.C.M.M.; Santen, van R.A.; Abbenhuis, H.C.L.

    2007-01-01

    Organo-bridged silsesquioxane titanates for heterogeneous catalytic epoxidation with aqueous hydrogen peroxide were synthesized through the acid-catalyzed hydrolysis and co-condensation of organotrialkoxysilane monomers and a,¿-bis(trialkoxysilyl) alkane cross-linkers in ethanol–water solution, with

  13. Polyhedral meshing in numerical analysis of conjugate heat transfer

    Science.gov (United States)

    Sosnowski, Marcin; Krzywanski, Jaroslaw; Grabowska, Karolina; Gnatowska, Renata

    2018-06-01

    Computational methods have been widely applied in conjugate heat transfer analysis. The very first and crucial step in such research is the meshing process which consists in dividing the analysed geometry into numerous small control volumes (cells). In Computational Fluid Dynamics (CFD) applications it is desirable to use the hexahedral cells as the resulting mesh is characterized by low numerical diffusion. Unfortunately generating such mesh can be a very time-consuming task and in case of complicated geometry - it may not be possible to generate cells of good quality. Therefore tetrahedral cells have been implemented into commercial pre-processors. Their advantage is the ease of its generation even in case of very complex geometry. On the other hand tetrahedrons cannot be stretched excessively without decreasing the mesh quality factor, so significantly larger number of cells has to be used in comparison to hexahedral mesh in order to achieve a reasonable accuracy. Moreover the numerical diffusion of tetrahedral elements is significantly higher. Therefore the polyhedral cells are proposed within the paper in order to combine the advantages of hexahedrons (low numerical diffusion resulting in accurate solution) and tetrahedrons (rapid semi-automatic generation) as well as to overcome the disadvantages of both the above mentioned mesh types. The major benefit of polyhedral mesh is that each individual cell has many neighbours, so gradients can be well approximated. Polyhedrons are also less sensitive to stretching than tetrahedrons which results in better mesh quality leading to improved numerical stability of the model. In addition, numerical diffusion is reduced due to mass exchange over numerous faces. This leads to a more accurate solution achieved with a lower cell count. Therefore detailed comparison of numerical modelling results concerning conjugate heat transfer using tetrahedral and polyhedral meshes is presented in the paper.

  14. Form-finding with polyhedral meshes made simple

    KAUST Repository

    Tang, Chengcheng; Sun, Xiang; Gomes, Alexandra; Wallner, Johannes; Pottmann, Helmut

    2015-01-01

    We solve the form-finding problem for polyhedral meshes in a way which combines form, function and fabrication; taking care of user-specified constraints like boundary interpolation, planarity of faces, statics, panel size and shape, enclosed volume, and cost. Our main application is the interactive modeling of meshes for architectural and industrial design. Our approach can be described as guided exploration of the constraint space whose algebraic structure is simplified by introducing auxiliary variables and ensuring that constraints are at most quadratic.

  15. Form-finding with polyhedral meshes made simple

    KAUST Repository

    Tang, Chengcheng

    2015-08-09

    We solve the form-finding problem for polyhedral meshes in a way which combines form, function and fabrication; taking care of user-specified constraints like boundary interpolation, planarity of faces, statics, panel size and shape, enclosed volume, and cost. Our main application is the interactive modeling of meshes for architectural and industrial design. Our approach can be described as guided exploration of the constraint space whose algebraic structure is simplified by introducing auxiliary variables and ensuring that constraints are at most quadratic.

  16. Polyhedral and semidefinite programming methods in combinatorial optimization

    CERN Document Server

    Tunçel, Levent

    2010-01-01

    Since the early 1960s, polyhedral methods have played a central role in both the theory and practice of combinatorial optimization. Since the early 1990s, a new technique, semidefinite programming, has been increasingly applied to some combinatorial optimization problems. The semidefinite programming problem is the problem of optimizing a linear function of matrix variables, subject to finitely many linear inequalities and the positive semidefiniteness condition on some of the matrix variables. On certain problems, such as maximum cut, maximum satisfiability, maximum stable set and geometric r

  17. Bending-active reciprocal structures based on equilateral polyhedral geometries

    DEFF Research Database (Denmark)

    Popovic Larsen, Olga; BRANCART, Stijn; DE TEMMERMAN, Niels

    2017-01-01

    As mutually supported beam structures, reciprocal frames limit the number of components that are joined at each connection to two. However, this system of intermediate connections introduces undesirable bending moments in the beam elements. By utilising elastic deformation to create curved...... of parts of reciprocal bending-active components based on a selection of polyhedral dome types. To simplify the assembly of the structures and avoid the manual bending of the components on site, we introduce the concept of a double-layered, pre-bent component. Finally, this paper presents the development...

  18. Oligoaniline-containing electrochromic polymers with tunable properties

    Directory of Open Access Journals (Sweden)

    Y. Li

    2018-07-01

    Full Text Available Electrochromic polymers have attracted much attention due to their potential applications in displays, smart windows, intelligent mirrors, and wearable devices. Here, a novel polyamic acid containing aniline pentamer with improved electrochromic properties and new functionalities was synthesized via oxidative coupling polymerization, followed by postpolymerization of tetraaniline, polyhedral oligomeric silsesquioxane, and fluorene, respectively. With the introduction of tetraaniline pendants, the resultant polymer exhibits improved electrochromic performance with high optical contrast value and rapid switching rate, because of the high content of electrochromic units in the polymeric structure. The polyamic acid functionalized with polyhedral oligomeric silsesquioxane, demonstrates a great enhancement of switching rate in the electrochromism, due to the rapid electrolyte migration through polymer film under electrochemical potentials. In addition, a new electrofluorochromic feature is easily achieved through the introduction of fluorescent fluorene groups into the polymeric architecture.

  19. SALOME PLATFORM and TetGen for Polyhedral Mesh Generation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang Yong; Park, Chan Eok; Kim, Shin Whan [KEPCO E and C Company, Inc., Daejeon (Korea, Republic of)

    2014-05-15

    SPACE and CUPID use the unstructured mesh and they also require reliable mesh generation system. The combination of CAD system and mesh generation system is necessary to cope with a large number of cells and the complex fluid system with structural materials inside. In the past, a CAD system Pro/Engineer and mesh generator Pointwise were evaluated for this application. But, the cost of those commercial CAD and mesh generator is sometimes a great burden. Therefore, efforts have been made to set up a mesh generation system with open source programs. The evaluation of the TetGen has been made in focusing the application for the polyhedral mesh generation. In this paper, SALOME will be evaluated for the efforts in conjunction with TetGen. In section 2, review will be made on the CAD and mesh generation capability of SALOME. SALOME and TetGen codes are being integrated to construct robust polyhedral mesh generator. Edge removal on the flat surface and vertex reattachment to the solid are two challenging tasks. It is worthwhile to point out that the Python script capability of the SALOME should be fully utilized for the future investigation.

  20. Approximation of scalar and vector transport problems on polyhedral meshes

    International Nuclear Information System (INIS)

    Cantin, Pierre

    2016-01-01

    This thesis analyzes, at the continuous and at the discrete level on polyhedral meshes, the scalar and the vector transport problems in three-dimensional domains. These problems are composed of a diffusive term, an advective term, and a reactive term. In the context of Friedrichs systems, the continuous problems are analyzed in Lebesgue graph spaces. The classical positivity assumption on the Friedrichs tensor is generalized so as to consider the case of practical interest where this tensor takes null or slightly negative values. A new scheme converging at the order 3/2 is devised for the scalar advection-reaction problem using scalar degrees of freedom attached to mesh vertices. Two new schemes considering as well scalar degrees of freedom attached to mesh vertices are devised for the scalar transport problem and are robust with respect to the dominant regime. The first scheme converges at the order 1/2 when advection effects are dominant and at the order 1 when diffusion effects are dominant. The second scheme improves the accuracy by converging at the order 3/2 when advection effects are dominant. Finally, a new scheme converging at the order 1/2 is devised for the vector advection-reaction problem considering only one scalar degree of freedom per mesh edge. The accuracy and the efficiency of all these schemes are assessed on various test cases using three-dimensional polyhedral meshes. (author)

  1. Molecular Modeling of Interfacial Behaviors of Nanomaterials

    Science.gov (United States)

    2007-05-01

    potential was originally designed for the modeling of mixed covalent- ionic bonding and was successfully used to describe oxides in crystalline, glassy, and...is separates from the bulk liquid polymer, i.e., the structure of this layer, as influenced by that of the meatal surface, is significantly more...Striolo, J. Kieffer, and P. Cummings, ’Evaluation of Force- fields for molecular simulation of polyhedral oligomeric silsesquioxanes,’ J. Phys. Chem

  2. POSS Ionic Liquid.

    Science.gov (United States)

    Tanaka, Kazuo; Ishiguro, Fumiyasu; Chujo, Yoshiki

    2010-12-22

    We report the synthesis of a stable room-temperature ionic liquid consisting of an octacarboxy polyhedral oligomeric silsesquioxane (POSS) anion and an imidazolium cation. The introduction of the POSS moiety enhances the thermal stability and reduces the melting temperature. From an evaluation of the thermodynamic parameters during the melting, it was found that the rigidity and cubic structure of POSS can contribute to the enhancement of these thermal properties.

  3. Symmetry and Algorithmic Complexity of Polyominoes and Polyhedral Graphs

    KAUST Repository

    Zenil, Hector

    2018-02-24

    We introduce a definition of algorithmic symmetry able to capture essential aspects of geometric symmetry. We review, study and apply a method for approximating the algorithmic complexity (also known as Kolmogorov-Chaitin complexity) of graphs and networks based on the concept of Algorithmic Probability (AP). AP is a concept (and method) capable of recursively enumeration all properties of computable (causal) nature beyond statistical regularities. We explore the connections of algorithmic complexity---both theoretical and numerical---with geometric properties mainly symmetry and topology from an (algorithmic) information-theoretic perspective. We show that approximations to algorithmic complexity by lossless compression and an Algorithmic Probability-based method can characterize properties of polyominoes, polytopes, regular and quasi-regular polyhedra as well as polyhedral networks, thereby demonstrating its profiling capabilities.

  4. Symmetry and Algorithmic Complexity of Polyominoes and Polyhedral Graphs

    KAUST Repository

    Zenil, Hector; Kiani, Narsis A.; Tegner, Jesper

    2018-01-01

    We introduce a definition of algorithmic symmetry able to capture essential aspects of geometric symmetry. We review, study and apply a method for approximating the algorithmic complexity (also known as Kolmogorov-Chaitin complexity) of graphs and networks based on the concept of Algorithmic Probability (AP). AP is a concept (and method) capable of recursively enumeration all properties of computable (causal) nature beyond statistical regularities. We explore the connections of algorithmic complexity---both theoretical and numerical---with geometric properties mainly symmetry and topology from an (algorithmic) information-theoretic perspective. We show that approximations to algorithmic complexity by lossless compression and an Algorithmic Probability-based method can characterize properties of polyominoes, polytopes, regular and quasi-regular polyhedra as well as polyhedral networks, thereby demonstrating its profiling capabilities.

  5. A Minimum Path Algorithm Among 3D-Polyhedral Objects

    Science.gov (United States)

    Yeltekin, Aysin

    1989-03-01

    In this work we introduce a minimum path theorem for 3D case. We also develop an algorithm based on the theorem we prove. The algorithm will be implemented on the software package we develop using C language. The theorem we introduce states that; "Given the initial point I, final point F and S be the set of finite number of static obstacles then an optimal path P from I to F, such that PA S = 0 is composed of straight line segments which are perpendicular to the edge segments of the objects." We prove the theorem as well as we develop the following algorithm depending on the theorem to find the minimum path among 3D-polyhedral objects. The algorithm generates the point Qi on edge ei such that at Qi one can find the line which is perpendicular to the edge and the IF line. The algorithm iteratively provides a new set of initial points from Qi and exploits all possible paths. Then the algorithm chooses the minimum path among the possible ones. The flowchart of the program as well as the examination of its numerical properties are included.

  6. Endocytic pathways mediating oligomeric Aβ42 neurotoxicity

    Directory of Open Access Journals (Sweden)

    Laxton Kevin

    2010-05-01

    Full Text Available Abstract Background One pathological hallmark of Alzheimer's disease (AD is amyloid plaques, composed primarily of amyloid-β peptide (Aβ. Over-production or diminished clearance of the 42 amino acid form of Aβ (Aβ42 in the brain leads to accumulation of soluble Aβ and plaque formation. Soluble oligomeric Aβ (oAβ has recently emerged to be as a likely proximal cause of AD. Results Here we demonstrate that endocytosis is critical in mediating oAβ42-induced neurotoxicity and intraneuronal accumulation of Aβ. Inhibition of clathrin function either with a pharmacological inhibitor, knock-down of clathrin heavy chain expression, or expression of the dominant-negative mutant of clathrin-assembly protein AP180 did not block oAβ42-induced neurotoxicity or intraneuronal accumulation of Aβ. However, inhibition of dynamin and RhoA by expression of dominant negative mutants reduced neurotoxicity and intraneuronal Aβ accumulation. Pharmacologic inhibition of the dynamin-mediated endocytic pathway by genistein also reduced neurotoxicity. Conclusions These data suggest that dynamin-mediated and RhoA-regulated endocytosis are integral steps for oligomeric Aβ42-induced neurotoxicity and intraneuronal Aβ accumulation.

  7. Synthesis and characterization of a new composite based on copper (II) and octa (aminopropil)silsesquioxane

    International Nuclear Information System (INIS)

    Magossi, M.S. de; Carmo, D.R. do

    2014-01-01

    In this work, a new compound based silsesquioxane and nitroprusside of copper was prepared starting from octa (aminopropyl)silsesquioxane following a new route of synthesis. The composite prepared as described ACCuN was preliminarily characterized by spectroscopic techniques, such as Infrared Spectroscopy in the Region of the Fourier transform (FTIR), Energy Dispersive X-ray (EDX), Scanning Electron Microscopy (SEM) and cyclic voltammetry (VC). The FTIR spectra showed absorption bands at 1106 cm"-"1 due to stretching Si-O-Si_(_ν_S_i_-_O_-_S_i_) characteristic of the structure of octa(aminopropylsilsesquioxane and absorption bands at 2063 cm"-"1 ascribed to the stretching NO_(_ν_N_-_O) and 2192 cm"-"1 attributed to the stretching C≡N_(_ν_≡N_). SEM and EDX observed cluster of cubic particles with an average size of approximately 241 nm, containing Si, O, N, Cu and Fe. Cyclic voltammogram of the material (ACCuN) showed a redox couple with average potential Eθ '= 0.73 V. (author)

  8. Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles

    KAUST Repository

    Croissant, Jonas G.

    2017-01-13

    The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous silica nanoparticles (MSNs) have been an ongoing discussion in research circles. The reason for such a concern is that approved pharmaceutical products must not accumulate in the human body, to prevent severe and unpredictable side-effects. Here, the biorelated degradability and clearance of silicon and silica nanoparticles (NPs) are comprehensively summarized. The influence of the size, morphology, surface area, pore size, and surface functional groups, to name a few, on the degradability of silicon and silica NPs is described. The noncovalent organic doping of silica and the covalent incorporation of either hydrolytically stable or redox- and enzymatically cleavable silsesquioxanes is then described for organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica (PMO) NPs. Inorganically doped silica particles such as calcium-, iron-, manganese-, and zirconium-doped NPs, also have radically different hydrolytic stabilities. To conclude, the degradability and clearance timelines of various siliceous nanomaterials are compared and it is highlighted that researchers can select a specific nanomaterial in this large family according to the targeted applications and the required clearance kinetics.

  9. Naming polyhedra by general face-spirals - theory and applications to fullerenes and other polyhedral molecules

    DEFF Research Database (Denmark)

    Wirz, Lukas; Schwerdtfeger, Peter; Avery, James Emil

    2018-01-01

    We present a general face-spiral algorithm for cubic polyhedral graphs (including fullerenes and fulleroids), and extend it to the full class of all polyhedral graphs by way of the leapfrog transform. This yields compact canonical representations of polyhedra with a simple and intuitive geometrical...... polyhedral molecules, and an especially compact form for the special class of fullerenes. A unique numbering of vertices is obtained as a byproduct of the spiral algorithm. This is required to denote modifications of the parent cage in IUPAC naming schemes. Similarly, the symmetry group of the molecule can...... be found together with the canonical general spiral at negligible cost. The algorithm is fully compatible with the classical spiral algorithm developed by Manolopoulos for fullerenes, i. e., classical spirals are accepted as input, and spiralable graphs lead to identical output. We prove that the algorithm...

  10. Topology and Oligomerization of Mono- and Oligomeric Proteins Regulate Their Half-Lives in the Cell.

    Science.gov (United States)

    Mallik, Saurav; Kundu, Sudip

    2018-06-05

    To find additional structural constraints (besides disordered segments) that regulate protein half-life in the cell, we herein assess the influence of native topology of monomeric and sequestration of oligomeric proteins into multimeric complexes in yeast, human, and mouse. Native topology acts as a molecular marker of globular protein's mechanical resistance and consequently captures their half-life variations on genome scale. Sequestration into multimeric complexes elongates oligomeric protein half-life in the cell, presumably by burying ubiquitinoylation sites and disordered segments required for proteasomal recognition. The latter effect is stronger for proteins associated with multiple complexes and for those binding early during complex self-assembly, including proteins that oligomerize with large proportions of surface buried. After gene duplication, diversification of topology and sequestration into non-identical sets of complexes alter half-lives of paralogous proteins during the course of evolution. Thus, native topology and sequestration into multimeric complexes reflect designing principles of proteins to regulate their half-lives. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. Polymorphism and mesomorphism of oligomeric surfactants: effect of the degree of oligomerization.

    Science.gov (United States)

    Jurašin, D; Pustak, A; Habuš, I; Šmit, I; Filipović-Vinceković, N

    2011-12-06

    A series of cationic oligomeric surfactants (quaternary dodecyldimethylammonium ions with two, three, or four chains connected by an ethylene spacer at the headgroup level, abbreviated as dimer, trimer, and tetramer) were synthesized and characterized. The influence of the degree of oligomerization on their polymorphic and mesomorphic properties was investigated by means of X-ray diffraction, polarizing optical microscopy, thermogravimetry, and differential scanning calorimetry. All compounds display layered arrangements with interdigitated dodecyl chains. The increase in the degree of oligomerization increases the interlayer distance and decreases the ordering in the solid phase; whereas the dimer sample is fully crystalline with well-developed 3D ordering and the trimer and tetramer crystallize as highly ordered crystal smectic phases. The number of thermal phase transitions and sequence of phases are markedly affected by the number of dodecyl chains. Anhydrous samples exhibit polymorphism and thermotropic mesomorphism of the smectic type, with the exception of the tetramer that displays only transitions at higher temperature associated with decomposition and melting. All hydrated compounds form lyotropic mesophases showing reversible phase transitions upon heating and cooling. The sequence of liquid-crystalline phases for the dimer, typical of concentrated ionic surfactant systems, comprises a hexagonal phase at lower temperatures and a smectic phase at higher temperatures. In contrast, the trimer and tetramer reveal textures of the hexagonal phase. © 2011 American Chemical Society

  12. Genetic noise control via protein oligomerization

    Energy Technology Data Exchange (ETDEWEB)

    Ghim, C; Almaas, E

    2008-06-12

    Gene expression in a cell entails random reaction events occurring over disparate time scales. Thus, molecular noise that often results in phenotypic and population-dynamic consequences sets a fundamental limit to biochemical signaling. While there have been numerous studies correlating the architecture of cellular reaction networks with noise tolerance, only a limited effort has been made to understand the dynamical role of protein-protein associations. We have developed a fully stochastic model for the positive feedback control of a single gene, as well as a pair of genes (toggle switch), integrating quantitative results from previous in vivo and in vitro studies. In particular, we explicitly account for the fast protein binding-unbinding kinetics, RNA polymerases, and the promoter/operator sequences of DNA. We find that the overall noise-level is reduced and the frequency content of the noise is dramatically shifted to the physiologically irrelevant high-frequency regime in the presence of protein dimerization. This is independent of the choice of monomer or dimer as transcription factor and persists throughout the multiple model topologies considered. For the toggle switch, we additionally find that the presence of a protein dimer, either homodimer or heterodimer, may significantly reduce its intrinsic switching rate. Hence, the dimer promotes the robust function of bistable switches by preventing the uninduced (induced) state from randomly being induced (uninduced). The specific binding between regulatory proteins provides a buffer that may prevent the propagation of fluctuations in genetic activity. The capacity of the buffer is a non-monotonic function of association-dissociation rates. Since the protein oligomerization per se does not require extra protein components to be expressed, it provides a basis for the rapid control of intrinsic or extrinsic noise. The stabilization of phenotypically important toggle switches, and nested positive feedback loops in

  13. Different domains are critical for oligomerization compatibility of different connexins

    Science.gov (United States)

    MARTÍNEZ, Agustín D.; MARIPILLÁN, Jaime; ACUÑA, Rodrigo; MINOGUE, Peter J.; BERTHOUD, Viviana M.; BEYER, Eric C.

    2011-01-01

    Oligomerization of connexins is a critical step in gap junction channel formation. Some members of the connexin family can oligomerize with other members and form functional heteromeric hemichannels [e.g. Cx43 (connexin 43) and Cx45], but others are incompatible (e.g. Cx43 and Cx26). To find connexin domains important for oligomerization, we constructed chimaeras between Cx43 and Cx26 and studied their ability to oligomerize with wild-type Cx43, Cx45 or Cx26. HeLa cells co-expressing Cx43, Cx45 or Cx26 and individual chimaeric constructs were analysed for interactions between the chimaeras and the wild-type connexins using cell biological (subcellular localization by immunofluorescence), functional (intercellular diffusion of microinjected Lucifer yellow) and biochemical (sedimentation velocity through sucrose gradients) assays. All of the chimaeras containing the third transmembrane domain of Cx43 interacted with wild-type Cx43 on the basis of co-localization, dominant-negative inhibition of intercellular communication, and altered sedimentation velocity. The same chimaeras also interacted with co-expressed Cx45. In contrast, immunofluorescence and intracellular diffusion of tracer suggested that other domains influenced oligomerization compatibility when chimaeras were co-expressed with Cx26. Taken together, these results suggest that amino acids in the third transmembrane domain are critical for oligomerization with Cx43 and Cx45. However, motifs in different domains may determine oligomerization compatibility in members of different connexin subfamilies. PMID:21348854

  14. Molecular basis of coiled-coil oligomerization-state specificity.

    Science.gov (United States)

    Ciani, Barbara; Bjelic, Saša; Honnappa, Srinivas; Jawhari, Hatim; Jaussi, Rolf; Payapilly, Aishwarya; Jowitt, Thomas; Steinmetz, Michel O; Kammerer, Richard A

    2010-11-16

    Coiled coils are extensively and successfully used nowadays to rationally design multistranded structures for applications, including basic research, biotechnology, nanotechnology, materials science, and medicine. The wide range of applications as well as the important functions these structures play in almost all biological processes highlight the need for a detailed understanding of the factors that control coiled-coil folding and oligomerization. Here, we address the important and unresolved question why the presence of particular oligomerization-state determinants within a coiled coil does frequently not correlate with its topology. We found an unexpected, general link between coiled-coil oligomerization-state specificity and trigger sequences, elements that are indispensable for coiled-coil formation. By using the archetype coiled-coil domain of the yeast transcriptional activator GCN4 as a model system, we show that well-established trimer-specific oligomerization-state determinants switch the peptide's topology from a dimer to a trimer only when inserted into the trigger sequence. We successfully confirmed our results in two other, unrelated coiled-coil dimers, ATF1 and cortexillin-1. We furthermore show that multiple topology determinants can coexist in the same trigger sequence, revealing a delicate balance of the resulting oligomerization state by position-dependent forces. Our experimental results should significantly improve the prediction of the oligomerization state of coiled coils. They therefore should have major implications for the rational design of coiled coils and consequently many applications using these popular oligomerization domains.

  15. Synthesis and characterization of polyhedral and quasi-sphere non-polyhedral Pt nanoparticles: effects of their various surface morphologies and sizes on electrocatalytic activity for fuel cell applications

    International Nuclear Information System (INIS)

    Long, Nguyen Viet; Ohtaki, Michitaka; Hien, Tong Duy; Jalem, Randy; Nogami, Masayuki

    2011-01-01

    In this article, polyhedral and non-polyhedral Pt nanoparticles were prepared by modified polyol method using AgNO 3 as a good structure-modifying agent. Their TEM and HRTEM images showed the particle size in the range of 8–16 nm for both the above cases. The structures and properties of the surfaces of Pt nanoparticles were investigated through cyclic voltammetry in dilute perchloric acid (HClO 4 ) electrolyte solution. A comparison of the electrocatalytic property in methanol electrooxidation was made. Here, the effects of polyhedral and non-polyhedral morphologies on their catalytic properties were studied. The results revealed that the special catalytic activity of quasi-sphere non-polyhedral Pt nanoparticles is higher than that of polyhedral Pt nanoparticles. In addition, Pt nanoparticles of un-sharp and quasi-sphere morphologies exhibit the tolerance to poisoning species better than that of Pt nanoparticles of sharp and polyhedral morphologies due to the various morphologies of the catalyst surfaces in the chronoamperometric plots. Therefore, these experimental evidences showed the morphology-dependent catalytic property according to the various morphologies and complexity of their catalyst surfaces.

  16. Cartilage oligomeric matrix protein in patients with juvenile idiopathic arthritis

    DEFF Research Database (Denmark)

    Bjørnhart, Birgitte; Juul, Anders; Nielsen, Susan

    2009-01-01

    Cartilage oligomeric matrix protein (COMP) has been identified as a prognostic marker of progressive joint destruction in rheumatoid arthritis. In this population based study we evaluated associations between plasma concentrations of COMP, disease activity, and growth velocity in patients...

  17. Protic Cationic Oligomeric Ionic Liquids of the Urethane Type

    DEFF Research Database (Denmark)

    Shevchenko, V. V.; Stryutsky, A. V.; Klymenko, N. S.

    2014-01-01

    Protic oligomeric cationic ionic liquids of the oligo(ether urethane) type are synthesized via the reaction of an isocyanate prepolymer based on oligo(oxy ethylene)glycol with M = 1000 with hexamethylene-diisocyanate followed by blocking of the terminal isocyanate groups with the use of amine...... derivatives of imidazole, pyridine, and 3-methylpyridine and neutralization of heterocycles with ethanesulfonic acid and p-toluenesulfonic acid. The structures and properties of the synthesized oligomeric ionic liquids substantially depend on the structures of the ionic groups. They are amorphous at room...... temperature, but ethanesulfonate imidazolium and pyridinium oligomeric ionic liquids form a low melting crystalline phase. The proton conductivities of the oligomeric ionic liquids are determined by the type of cation in the temperature range 80-120 degrees C under anhydrous conditions and vary within five...

  18. Modeling IrisCode and its variants as convex polyhedral cones and its security implications.

    Science.gov (United States)

    Kong, Adams Wai-Kin

    2013-03-01

    IrisCode, developed by Daugman, in 1993, is the most influential iris recognition algorithm. A thorough understanding of IrisCode is essential, because over 100 million persons have been enrolled by this algorithm and many biometric personal identification and template protection methods have been developed based on IrisCode. This paper indicates that a template produced by IrisCode or its variants is a convex polyhedral cone in a hyperspace. Its central ray, being a rough representation of the original biometric signal, can be computed by a simple algorithm, which can often be implemented in one Matlab command line. The central ray is an expected ray and also an optimal ray of an objective function on a group of distributions. This algorithm is derived from geometric properties of a convex polyhedral cone but does not rely on any prior knowledge (e.g., iris images). The experimental results show that biometric templates, including iris and palmprint templates, produced by different recognition methods can be matched through the central rays in their convex polyhedral cones and that templates protected by a method extended from IrisCode can be broken into. These experimental results indicate that, without a thorough security analysis, convex polyhedral cone templates cannot be assumed secure. Additionally, the simplicity of the algorithm implies that even junior hackers without knowledge of advanced image processing and biometric databases can still break into protected templates and reveal relationships among templates produced by different recognition methods.

  19. Polybenzimidazole and sulfonated polyhedral oligosilsesquioxane composite membranes for high temperature polymer electrolyte membrane fuel cells

    DEFF Research Database (Denmark)

    Aili, David; Allward, Todd; Alfaro, Silvia Martinez

    2014-01-01

    Composite membranes based on poly(2,2′(m-phenylene)-5,5́bibenzimidazole) (PBI) and sulfonated polyhedral oligosilsesquioxane (S-POSS) with S-POSS contents of 5 and 10wt.% were prepared by solution casting as base materials for high temperature polymer electrolyte membrane fuel cells. With membranes...

  20. Rheological Behavior of Entangled Polystyrene-Polyhedral Oligosilsesquioxane (POSS) Copolymer (Postprint)

    National Research Council Canada - National Science Library

    Wu, Jian; Mather, Patrick T; Haddad, Timothy S; Kim, Gyeong-Man

    2006-01-01

    ...: random copolymers of polystyrene (PS) and styryl-based polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(C6H4CH=CH2), with R = isobutyl (iBu). A series of styrene-styryl POSS random copolymers with 0, 6, 15, 30, 50 wt...

  1. Robust Hinf control of uncertain switched systems defined on polyhedral sets with Filippov solutions

    DEFF Research Database (Denmark)

    Ahmadi, Mohamadreza; Mojallali, Hamed; Wisniewski, Rafal

    2012-01-01

    This paper considers the control problem of a class of uncertain switched systems defined on polyhedral sets known as piecewise linear systems where, instead of the conventional Carathe ́odory solutions, Filippov solutions are studied. In other words, in contrast to the previous studies, solutions...

  2. Robust superhydrophobic bridged silsesquioxane aerogels with tunable performances and their applications.

    Science.gov (United States)

    Wang, Zhen; Wang, Dong; Qian, Zhenchao; Guo, Jing; Dong, Haixia; Zhao, Ning; Xu, Jian

    2015-01-28

    Aerogels are a family of highly porous materials whose applications are commonly restricted by poor mechanical properties. Herein, thiol-ene chemistry is employed to synthesize a series of novel bridged silsesquioxane (BSQ) precursors with various alkoxy groups. On the basis of the different hydrolyzing rates of the methoxy and ethoxy groups, robust superhydrophobic BSQ aerogels with tailorable morphology and mechanical performances have been prepared. The flexible thioether bridge contributes to the robustness of the as-formed aerogels, and the property can be tuned on the basis of the distinct combinations of alkoxy groups with the density of the aerogels almost unchanged. To the best of our knowledge, the lowest density among the ambient pressure dried aerogels is obtained. Further, potential application of the aerogels for oil/water separation and acoustic materials has also been presented.

  3. Interfacial enhancement of polypropylene composites modified with sorbitol derivatives and siloxane-silsesquioxane resin

    Science.gov (United States)

    Dobrzyńska-Mizera, Monika; Dutkiewicz, Michał; Sterzyński, Tomasz; Di Lorenzo, Maria Laura

    2015-12-01

    Composites based on polypropylene (iPP) modified with a sorbitol derivative (NX8000) and siloxane-silsesquioxane resin (SiOPh) containing maleated polypropylene (MAPP) as compatibilizer were prepared by melt extrusion. Calorimetric investigations were carried out using differential scanning calorimetry (DSC), whereas the morphological and mechanical properties were investigated by scanning electron microscopy (SEM) and static tensile tests. DSC measurements revealed no influence of SiOPh and a slight effect of MAPP addition on the crystallization kinetics of polypropylene. Additionally, the introduction of MAPP into the iPP+NX8000+SiOPh composites increased plastic properties of the samples. All the above was attributed to the compatibilizing effect of MAPP which improved interfacial adhesion between iPP, NX8000 and SiOPh. This phenomenon was also confirmed by the SEM images illustrating more homogenous distribution of the filler in the compatibilized samples.

  4. Hydrogen Silsesquioxane based silica glass coatings for the corrosion protection of austenitic stainless steel

    DEFF Research Database (Denmark)

    Lampert, Felix; Jensen, Annemette Hindhede; Din, Rameez Ud

    2016-01-01

    -film barrier coatings were deposited on AISI 316L grade austenitic stainless steel with 2B surface finish from Hydrogen Silsesquioxane (HSQ) spin-on-glass precursor and thermally cured to tailor the film properties. Results showed that curing at 500 °C resulted in a film-structure with a polymerized siloxane...... backbone and a reduced amount of Si-H moieties. The coatings showed good substrate coverage and the average thickness was between 200 and 400 nm on the rough substrate surface, however, film thicknesses of > 1400 nm were observed at substrate defects. Deposition of these films significantly improved...... the barrier-properties by showing a 1000 times higher modulus while an ionic transport over the coating was also observed....

  5. Polyhedral oligomeric butyl stannoxane cages (Sn-POSS) as oxidation-activated linear repairing units or crosslinking nano-building blocks, depending on structure of the polymer matrix

    Czech Academy of Sciences Publication Activity Database

    Rodzen, Krzysztof; Strachota, Adam; Raus, Vladimír; Pavlova, Ewa

    2017-01-01

    Roč. 142, August (2017), s. 1-20 ISSN 0141-3910 R&D Projects: GA ČR(CZ) GA17-05007S Institutional support: RVO:61389013 Keywords : POSS * stannoxane * nanocomposite Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.386, year: 2016

  6. Preparation of highly hydrophobic cotton fabrics by modification with bifunctional silsesquioxanes in the sol-gel process

    Energy Technology Data Exchange (ETDEWEB)

    Przybylak, Marcin, E-mail: marcin.przybylak@ppnt.poznan.pl [Poznań Science and Technology Park, Adam Mickiewicz University Foundation, Rubież 46, 61-612 Poznań (Poland); Maciejewski, Hieronim, E-mail: maciejm@amu.edu.pl [Poznań Science and Technology Park, Adam Mickiewicz University Foundation, Rubież 46, 61-612 Poznań (Poland); Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań (Poland); Dutkiewicz, Agnieszka, E-mail: agdut@interia.pl [Poznań Science and Technology Park, Adam Mickiewicz University Foundation, Rubież 46, 61-612 Poznań (Poland)

    2016-11-30

    Highlights: • Fabric hydrophobization process using bifunctional silsesquioxanes was studied. • Superhydrophobic fabric was produced using fluorofunctional silsesquioxanes. • Surface of modified fabrics was analyzed using different techniques. - Abstract: The surface modification of cotton fabrics was carried out using two types of bifunctional fluorinated silsesquioxanes with different ratios of functional groups. The modification was performed either by one- or two-step process. Two methods, the sol-gel and the dip coating method were used in different configurations. The heat treatment and the washing process were applied after modification. The wettability of cotton fabric was evaluated by measuring water contact angles (WCA). Changes in the surface morphology were examined by scanning electron microscopy (SEM, SEM-LFD) and atomic force microscopy (AFM). Moreover, the modified fabrics were subjected to analysis of elemental composition of the applied coatings using SEM-EDS techniques. Highly hydrophobic textiles were obtained in all cases studied and one of the modifications resulted in imparting superhydrophobic properties. Most of impregnated textiles remained hydrophobic even after multiple washing process which shows that the studied modification is durable.

  7. Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hawthorne, M. Frederick; Jalisatgi, Satish S.; Safronov, Alexander V.; Lee, Han Beak; Wu, Jianguo

    2010-10-01

    Phase 1. Hydrolysis of borohydride compounds offer the potential for significant hydrogen storage capacity, but most work to date has focused on one particular anion, BH4-, which requires high pH for stability. Other borohydride compounds, in particular polyhedral borane anions offer comparable hydrogen storage capacity without requiring high pH media and their long term thermal and hydrolytic stability coupled with non-toxic nature make them a very attractive alternative to NaBH4. The University of Missouri project provided the overall program focal point for the investigation of catalytic hydrolysis of polyhedral borane anions for hydrogen release. Due to their inherent stability, a transition metal catalyst was necessary for the hydrolysis of polyhedral borane anions. Transition metal ions such as cobalt, nickel, palladium and rhodium were investigated for their catalytic activity in the hydrolysis of nido-KB11H14, closo-K2B10H10, and closo-K2B12H12. The rate of hydrolysis follows first-order kinetics with respect to the concentration of the polyhedral borane anion and surface area of the rhodium catalyst. The rate of hydrolysis depends upon a) choice of polyhedral borane anion, c) concentration of polyhedral borane anion, d) surface area of the rhodium catalyst and e) temperature of the reaction. In all cases the yield of hydrogen was 100% which corresponds to ~7 wt% of hydrogen (based on material wt%). Phase 2. The phase 2 of program at the University of Missouri was focused upon developing aluminum ammonia-boranes (Al-AB) as chemical hydrogen storage materials, specifically their synthesis and studies of their dehydrogenation. The ammonia borane molecule (AB) is a demonstrated source of chemically stored hydrogen (19.6 wt%) which meets DOE performance parameters except for its regeneration from spent AB and elemental hydrogen. The presence of an aluminum center bonded to multiple AB residues might combine the efficiency of AB dehydrogenation with an aluminum

  8. Large-scale, rapid synthesis and application in surface-enhanced Raman spectroscopy of sub-micrometer polyhedral gold nanocrystals

    International Nuclear Information System (INIS)

    Guo Shaojun; Wang Yuling; Wang Erkang

    2007-01-01

    Macromolecule-protected sub-micrometer polyhedral gold nanocrystals have been facilely prepared by heating an aqueous solution containing poly (N-vinyl-2-pyrrolidone) (PVP) and HAuCl 4 without adding other reducing agents. Scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX), ultraviolet-visible-near-infrared spectroscopy (UV-vis-NIR), and x-ray diffraction (XRD) were employed to characterize the obtained polyhedral gold nanocrystals. It is found that the 10:1 molar ratio of PVP to gold is a key factor for obtaining quasi-monodisperse polyhedral gold nanocrystals. Furthermore, the application of polyhedral gold nanocrystals in surface-enhanced Raman scattering (SERS) was investigated by using 4-aminothiophenol (4-ATP) as a probe molecule. The results indicated that the sub-micrometer polyhedral gold nanocrystals modified on the ITO substrate exhibited higher SERS activity compared to the traditional gold nanoparticle modified film. The enhancement factor (EF) on polyhedral gold nanocrystals was about six times larger than that obtained on aggregated gold nanoparticles (∼25 nm)

  9. Cartilage oligomeric matrix protein enhances the vascularization of acellular nerves

    Directory of Open Access Journals (Sweden)

    Wei-ling Cui

    2016-01-01

    Full Text Available Vascularization of acellular nerves has been shown to contribute to nerve bridging. In this study, we used a 10-mm sciatic nerve defect model in rats to determine whether cartilage oligomeric matrix protein enhances the vascularization of injured acellular nerves. The rat nerve defects were treated with acellular nerve grafting (control group alone or acellular nerve grafting combined with intraperitoneal injection of cartilage oligomeric matrix protein (experimental group. As shown through two-dimensional imaging, the vessels began to invade into the acellular nerve graft from both anastomotic ends at day 7 post-operation, and gradually covered the entire graft at day 21. The vascular density, vascular area, and the velocity of revascularization in the experimental group were all higher than those in the control group. These results indicate that cartilage oligomeric matrix protein enhances the vascularization of acellular nerves.

  10. An engineered allosteric switch in leucine-zipper oligomerization.

    Science.gov (United States)

    Gonzalez, L; Plecs, J J; Alber, T

    1996-06-01

    Controversy remains about the role of core side-chain packing in specifying protein structure. To investigate the influence of core packing on the oligomeric structure of a coiled coil, we engineered a GCN4 leucine zipper mutant that switches from two to three strands upon binding the hydrophobic ligands cyclohexane and benzene. In solution these ligands increased the apparent thermal stability and the oligomerization order of the mutant leucine zipper. The crystal structure of the peptide-benzene complex shows a single benzene molecule bound at the engineered site in the core of the trimer. These results indicate that coiled coils are well-suited to function as molecular switches and emphasize that core packing is an important determinant of oligomerization specificity.

  11. Genetic noise control via protein oligomerization

    Directory of Open Access Journals (Sweden)

    Almaas Eivind

    2008-11-01

    Full Text Available Abstract Background Gene expression in a cell entails random reaction events occurring over disparate time scales. Thus, molecular noise that often results in phenotypic and population-dynamic consequences sets a fundamental limit to biochemical signaling. While there have been numerous studies correlating the architecture of cellular reaction networks with noise tolerance, only a limited effort has been made to understand the dynamic role of protein-protein interactions. Results We have developed a fully stochastic model for the positive feedback control of a single gene, as well as a pair of genes (toggle switch, integrating quantitative results from previous in vivo and in vitro studies. In particular, we explicitly account for the fast binding-unbinding kinetics among proteins, RNA polymerases, and the promoter/operator sequences of DNA. We find that the overall noise-level is reduced and the frequency content of the noise is dramatically shifted to the physiologically irrelevant high-frequency regime in the presence of protein dimerization. This is independent of the choice of monomer or dimer as transcription factor and persists throughout the multiple model topologies considered. For the toggle switch, we additionally find that the presence of a protein dimer, either homodimer or heterodimer, may significantly reduce its random switching rate. Hence, the dimer promotes the robust function of bistable switches by preventing the uninduced (induced state from randomly being induced (uninduced. Conclusion The specific binding between regulatory proteins provides a buffer that may prevent the propagation of fluctuations in genetic activity. The capacity of the buffer is a non-monotonic function of association-dissociation rates. Since the protein oligomerization per se does not require extra protein components to be expressed, it provides a basis for the rapid control of intrinsic or extrinsic noise. The stabilization of regulatory circuits

  12. Convex polyhedral abstractions, specialisation and property-based predicate splitting in Horn clause verification

    DEFF Research Database (Denmark)

    Kafle, Bishoksan; Gallagher, John Patrick

    2014-01-01

    We present an approach to constrained Horn clause (CHC) verification combining three techniques: abstract interpretation over a domain of convex polyhedra, specialisation of the constraints in CHCs using abstract interpretation of query-answer transformed clauses, and refinement by splitting...... in conjunction with specialisation for propagating constraints it can frequently solve challenging verification problems. This is a contribution in itself, but refinement is needed when it fails, and the question of how to refine convex polyhedral analyses has not been studied much. We present a refinement...... technique based on interpolants derived from a counterexample trace; these are used to drive a property-based specialisation that splits predicates, leading in turn to more precise convex polyhedral analyses. The process of specialisation, analysis and splitting can be repeated, in a manner similar...

  13. Decompositions of the polyhedral product functor with applications to moment-angle complexes and related spaces.

    Science.gov (United States)

    Bahri, A; Bendersky, M; Cohen, F R; Gitler, S

    2009-07-28

    This article gives a natural decomposition of the suspension of a generalized moment-angle complex or partial product space which arises as the polyhedral product functor described below. The introduction and application of the smash product moment-angle complex provides a precise identification of the stable homotopy type of the values of the polyhedral product functor. One direct consequence is an analysis of the associated cohomology. For the special case of the complements of certain subspace arrangements, the geometrical decomposition implies the homological decomposition in earlier work of others as described below. Because the splitting is geometric, an analogous homological decomposition for a generalized moment-angle complex applies for any homology theory. Implied, therefore, is a decomposition for the Stanley-Reisner ring of a finite simplicial complex, and natural generalizations.

  14. hp-version discontinuous Galerkin methods on polygonal and polyhedral meshes

    CERN Document Server

    Cangiani, Andrea; Georgoulis, Emmanuil H; Houston, Paul

    2017-01-01

    Over the last few decades discontinuous Galerkin finite element methods (DGFEMs) have been witnessed tremendous interest as a computational framework for the numerical solution of partial differential equations. Their success is due to their extreme versatility in the design of the underlying meshes and local basis functions, while retaining key features of both (classical) finite element and finite volume methods. Somewhat surprisingly, DGFEMs on general tessellations consisting of polygonal (in 2D) or polyhedral (in 3D) element shapes have received little attention within the literature, despite the potential computational advantages. This volume introduces the basic principles of hp-version (i.e., locally varying mesh-size and polynomial order) DGFEMs over meshes consisting of polygonal or polyhedral element shapes, presents their error analysis, and includes an extensive collection of numerical experiments. The extreme flexibility provided by the locally variable elemen t-shapes, element-sizes, and elemen...

  15. Status of the Polyhedral Mesh Generator using SALOME PLATFORM and TetGen

    International Nuclear Information System (INIS)

    Lee, Sang Yong; Park, Chan Eok; Kim, Shin Whan

    2014-01-01

    Recently developed porous body approach codes such as SPACE and CUPID require a CAD system to estimate the porosity. Since they use the unstructured mesh and they also require reliable mesh generation system. The combination of CAD system and mesh generation system is necessary to cope with a large number of cells and the complex fluid system with structural materials inside. In the past, a CAD system Pro/Engineer and mesh generator Pointwise were evaluated for this application. But, the cost of those commercial CAD and mesh generator is sometimes a great burden. Therefore, efforts have been made to set up a mesh generation system with open source programs. The evaluation of the TetGen has been made in focusing the application for the polyhedral mesh generation. In this paper, SALOME will be described for the efforts to combine TetGen with it. In section 2, brief introduction will be made on the CAD and mesh generation capability of SALOME and Tetgen. SALOME and TetGen codes are being integrated to construct robust polyhedral mesh generator. Procedures to merge boundary faces and to cut concave cells are developed to remove concave cells to get final convex polyhedral mesh. Treating the internal boundary face, i.e. non-manifold face will be the next task in the future investigation

  16. Computer-Aided Panoramic Images Enriched by Shadow Construction on a Prism and Pyramid Polyhedral Surface

    Directory of Open Access Journals (Sweden)

    Jolanta Dzwierzynska

    2017-10-01

    Full Text Available The aim of this study is to develop an efficient and practical method of a direct mapping of a panoramic projection on an unfolded prism and pyramid polyhedral projection surface with the aid of a computer. Due to the fact that straight lines very often appear in any architectural form we formulate algorithms which utilize data about lines and draw panoramas as plots of functions in Mathcad software. The ability to draw panoramic images of lines enables drawing a wireframe image of an architectural object. The application of the multicenter projection, as well as the idea of shadow construction in the panoramic representation, aims at achieving a panoramic image close to human perception. The algorithms are universal as the application of changeable base elements of panoramic projection—horizon height, station point location, number of polyhedral walls—enables drawing panoramic images from various viewing positions. However, for more efficient and easier drawing, the algorithms should be implemented in some graphical package. The representation presented in the paper and the method of its direct mapping on a flat unfolded projection surface can find application in the presentation of architectural spaces in advertising and art when drawings are displayed on polyhedral surfaces and can be observed from multiple viewing positions.

  17. Logical and Geometrical Distance in Polyhedral Aristotelian Diagrams in Knowledge Representation

    Directory of Open Access Journals (Sweden)

    Lorenz Demey

    2017-09-01

    Full Text Available Aristotelian diagrams visualize the logical relations among a finite set of objects. These diagrams originated in philosophy, but recently, they have also been used extensively in artificial intelligence, in order to study (connections between various knowledge representation formalisms. In this paper, we develop the idea that Aristotelian diagrams can be fruitfully studied as geometrical entities. In particular, we focus on four polyhedral Aristotelian diagrams for the Boolean algebra B 4 , viz. the rhombic dodecahedron, the tetrakis hexahedron, the tetraicosahedron and the nested tetrahedron. After an in-depth investigation of the geometrical properties and interrelationships of these polyhedral diagrams, we analyze the correlation (or lack thereof between logical (Hamming and geometrical (Euclidean distance in each of these diagrams. The outcome of this analysis is that the Aristotelian rhombic dodecahedron and tetrakis hexahedron exhibit the strongest degree of correlation between logical and geometrical distance; the tetraicosahedron performs worse; and the nested tetrahedron has the lowest degree of correlation. Finally, these results are used to shed new light on the relative strengths and weaknesses of these polyhedral Aristotelian diagrams, by appealing to the congruence principle from cognitive research on diagram design.

  18. Polygonal Prism Mesh in the Viscous Layers for the Polyhedral Mesh Generator, PolyGen

    International Nuclear Information System (INIS)

    Lee, Sang Yong; Park, Chan Eok; Kim, Shin Whan

    2015-01-01

    Polyhedral mesh has been known to have some benefits over the tetrahedral mesh. Efforts have been made to set up a polyhedral mesh generation system with open source programs SALOME and TetGen. The evaluation has shown that the polyhedral mesh generation system is promising. But it is necessary to extend the capability of the system to handle the viscous layers to be a generalized mesh generator. A brief review to the previous works on the mesh generation for the viscous layers will be made in section 2. Several challenging issues for the polygonal prism mesh generation will be discussed as well. The procedure to generate a polygonal prism mesh will be discussed in detail in section 3. Conclusion will be followed in section 4. A procedure to generate meshes in the viscous layers with PolyGen has been successfully designed. But more efforts have to be exercised to find the best way for the generating meshes for viscous layers. Using the extrusion direction of the STL data will the first of the trials in the near future

  19. ORGANIC/INORGANIC HYBRID EPOXY NANOCOMPOSITES BASED ON OCTA(AMINOPHENYL)SILSESQUIOXANE

    Institute of Scientific and Technical Information of China (English)

    Hai-bo Fan; Rong-jie Yang; Xiang-mei Li

    2013-01-01

    Octa(aminophenyl)silsesquioxane (OAPS) was used as the curing agent of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin.A study on comparison of DGEBA/OAPS with DGEBA/4,4'-diaminodiphenyl sulfone (DDS) epoxy resins was achieved.Differential scanning calorimetry was used to investigate the curing reaction and its kinetics,and the glass transition of DGEBA/OAPS.Thermogravimetric analysis was used to investigate thermal decomposition of the two kinds of epoxy resins.The reactions between amino groups and epoxy groups were investigated using Fourier transform infrared spectroscopy.Scanning electron microscopy was used to observe morphology of the two epoxy resins.The results indicated that OAPS had very good compatibility with DGEBA in molecular level,and could form a transparent DGEBA/OAPS resin.The curing reaction of the DGEBA/OAPS prepolymer could occur under low temperatures compared with DGEBA/DDS.The DGEBA/OAPS resin didn't exhibit glass transition,but the DGEBA/DDS did,which meant that the large cage structure of OAPS limited the motion of chains between the cross-linking points.Measurements of the contact angle indicated that the DGEBA/OAPS showed larger angles with water than the DGEBA/DDS resin.Thermogravimetric analysis indicated that the incorporation of OAPS into epoxy system resulted in low mass loss rate and high char yield,but its initial decomposition temperature seemed to be lowered.

  20. Development of ceramic composites from mixture of alumina and ceramic precursor polymer poly (silsesquioxane))

    International Nuclear Information System (INIS)

    Machado, Glauson Aparecido Ferreira

    2009-01-01

    Processing of ceramics materials, by polymer precursors pyrolysis, has been intensively researched over the past decades, due to advantages that this path provides, such as: lower temperature process compared to conventional techniques; structure control at molecular level; synthesis possibility of a wide range of ceramic compounds; obtaining parts with dimensions of the final product etc. The active filler controlled polymer pyrolysis (AFCOP) process, enables the synthesis of ceramic composites, by reaction between added filler (oxides, metals, intermetallic etc.) and solid and gaseous products, from polymer decomposition. In this study, based on this process, samples of alumina, with addition of 10 and 20 mass% of poly silsesquioxane polymer precursor, were manufactured. These samples were pyrolyzed at 900 degree C and thermal treated at temperatures of 1100, 1300 and 1500 degree C. The samples were characterized for bulk density, porosity and hardness, after each stage of thermal treatment. Structural transformations were analyzed by X-ray diffraction, scanning electron microscopy and infrared spectroscopy. Samples treated until 1300 degree C resulted in composites of alumina and silicon oxycarbide, while those treated at 1500 degree C, formed composites of mullite and alumina. The samples with 20% of polymer added started to density around 800 degree C and high retraction rate was observed at 1400 degree C. (author)

  1. Relationships between nanostructure and dynamic-mechanical properties of epoxy network containing PMMA-modified silsesquioxane

    Directory of Open Access Journals (Sweden)

    2009-06-01

    Full Text Available A new class of organic-inorganic hybrid nanocomposites was obtained by blending PMMA-modified silsesquioxane hybrid materials with epoxy matrix followed by curing with methyl tetrahydrophthalic anhydride. The hybrid materials were obtained by sol-gel method through the hydrolysis and polycondensation of the silicon species of the hybrid precursor, 3-methacryloxypropyltrimethoxysilane (MPTS, simultaneously to the polymerization of the methacrylate (MMA groups covalently bonded to the silicon atoms. The nanostructure of these materials was investigated by small angle X-ray scattering (SAXS and correlated to their dynamic mechanical properties. The SAXS results revealed a hierarchical nanostructure consisting on two structural levels. The first level is related to the siloxane nanoparticles spatially correlated in the epoxy matrix, forming larger hybrid secondary aggregates. The dispersion of siloxane nanoparticles in epoxy matrix was favored by increasing the MMA content in the hybrid material. The presence of small amount of hybrid material affected significantly the dynamic mechanical properties of the epoxy networks.

  2. Tetrahedral silsesquioxane-C2H2Ti complex for hydrogen storage

    Science.gov (United States)

    Konda, Ravinder; Tavhare, Priyanka; Ingale, Nilesh; Chaudhari, Ajay

    2018-04-01

    The interaction of molecular hydrogen with tetrahedral silsesquioxane (T4)-C2H2Ti complex has been studied using Density Functional Theory with M06-2X functional and MP2 method with 6-311++G** basis set. T4-C2H2Ti complex can absorb maximum five hydrogen molecules with the gravimetric hydrogen storage capacity of 3.4 wt %. Adsorption energy calculations show that H2 adsorption on T4-C2H2Ti complex is favorable at room temperature by both the methods. We have studied the effect of temperature and pressure on Gibbs free energy corrected adsorption energies. Molecular dynamics simulations for H2 adsorbed T4-C2H2Ti complex have also been performed at 300K and show that loosely bonded H2 molecule flies away within 1fs. Various interaction energies within the complex are studied. Stability of a complex is predicted by means of a gap between Highest Occupied Molecular Orbital (HUMO) and Lowest Unoccupied Molecular Orbital (LUMO). The H2 desorption temperature for T4-C2H2Ti complex is calculated with Van't Hoff equation and it is found to be 229K.

  3. High Content Analysis of Compositional Heterogeneities to Study GPCR Oligomerization

    DEFF Research Database (Denmark)

    Walsh, Samuel McEwen

    In this thesis I demonstrate how the natural compositional heterogeneities of synthetic and living cell model systems can be used to quantitate the mechanics of G-protein coupled receptor (GPCR) oligomerization with Förster resonance energy transfer (FRET). The thesis is structured around three a...

  4. Facile synthesis of octahedral Pt-Pd nanoparticles stabilized by silsesquioxane for the electrooxidation of formic acid

    International Nuclear Information System (INIS)

    Li, Yusong; Hao, Furui; Wang, Yihong; Zhang, Yihong; Ge, Cunwang; Lu, Tianhong

    2014-01-01

    Graphical abstract: The octahedral Pt-Pd alloy nanoparticles (octahedral Pt-Pd NPs) with dominant {111} facets were successfully synthesized through a facile route in the presence of octa(3-aminopropyl) silsesquioxane as the capping agent and complexing agent, methanol as the reductant and solvent. The octahedral Pt-Pd NPs display the significantly enhanced electrocatalytic activity, increased CO tolerance and favourable stability for the electrooxidation of formic acid. - Highlights: • Octa Pt-Pd nanoparticles were synthesized with silsesquioxane as capping agent. • Octa Pt-Pd nanoparticles display uniform morphology and favorable dispersibility. • Octa Pt-Pd nanoparticles have high catalytic activity for formic acid by direct process. - Abstract: The octahedral Pt-Pd alloy nanoparticles (octahedral Pt-Pd NPs) with dominant {111} facets were successfully synthesized through a facile route in the presence of octa(3-aminopropyl) silsesquioxane as the capping agent and complexing agent, methanol as the reductant and solvent. Their morphology, composition and structure were charactered by transmission electron microscopy (TEM), energy dispersive spectrum (EDS) and X-ray diffraction (XRD). The electrocatalytic activity, CO tolerance and stability of the octahedral Pt-Pd NPs for the electrooxidation of formic acid were investigated by cyclic voltammetry, CO stripping voltammetry and chronoamperometry, respectively. Compared with the Pt nanoparticles and commercial Pt black, the octahedral Pt-Pd NPs display a significantly enhanced electrocatalytic activity, increased CO tolerance and favourable stability for the electrooxidation of formic acid. Therefore, the octahedral Pt-Pd NPs might be an alternative candidate for the anode catalyst for the electrooxidation of formic acid in future

  5. Crystal Structure of the Marburg Virus VP35 Oligomerization Domain

    Energy Technology Data Exchange (ETDEWEB)

    Bruhn, Jessica F.; Kirchdoerfer, Robert N.; Urata, Sarah M.; Li, Sheng; Tickle, Ian J.; Bricogne, Gérard; Saphire, Erica Ollmann (Scripps); (Globel Phasing); (UCSD)

    2016-11-09

    ABSTRACT

    Marburg virus (MARV) is a highly pathogenic filovirus that is classified in a genus distinct from that of Ebola virus (EBOV) (generaMarburgvirusandEbolavirus, respectively). Both viruses produce a multifunctional protein termed VP35, which acts as a polymerase cofactor, a viral protein chaperone, and an antagonist of the innate immune response. VP35 contains a central oligomerization domain with a predicted coiled-coil motif. This domain has been shown to be essential for RNA polymerase function. Here we present crystal structures of the MARV VP35 oligomerization domain. These structures and accompanying biophysical characterization suggest that MARV VP35 is a trimer. In contrast, EBOV VP35 is likely a tetramer in solution. Differences in the oligomeric state of this protein may explain mechanistic differences in replication and immune evasion observed for MARV and EBOV.

    IMPORTANCEMarburg virus can cause severe disease, with up to 90% human lethality. Its genome is concise, only producing seven proteins. One of the proteins, VP35, is essential for replication of the viral genome and for evasion of host immune responses. VP35 oligomerizes (self-assembles) in order to function, yet the structure by which it assembles has not been visualized. Here we present two crystal structures of this oligomerization domain. In both structures, three copies of VP35 twist about each other to form a coiled coil. This trimeric assembly is in contrast to tetrameric predictions for VP35 of Ebola virus and to known structures of homologous proteins in the measles, mumps, and Nipah viruses. Distinct oligomeric states of the Marburg and Ebola virus VP35 proteins may explain differences between them in polymerase function and immune evasion. These findings may provide a more accurate understanding of the

  6. Hydrophobic Coatings by Thiol-Ene Click Functionalization of Silsesquioxanes with Tunable Architecture.

    Science.gov (United States)

    Dirè, Sandra; Bottone, Davide; Callone, Emanuela; Maniglio, Devid; Génois, Isabelle; Ribot, François

    2017-08-08

    The hydrolysis-condensation of trialkoxysilanes under strictly controlled conditions allows the production of silsesquioxanes (SSQs) with tunable size and architecture ranging from ladder to cage-like structures. These nano-objects can serve as building blocks for the preparation of hybrid organic/inorganic materials with selected properties. The SSQs growth can be tuned by simply controlling the reaction duration in the in situ water production route (ISWP), where the kinetics of the esterification reaction between carboxylic acids and alcohols rules out the extent of organosilane hydrolysis-condensation. Tunable SSQs with thiol functionalities (SH-NBBs) are suitable for further modification by exploiting the simple thiol-ene click reaction, thus allowing for modifying the wettability properties of derived coatings. In this paper, coatings were prepared from SH-NBBs with different architecture onto cotton fabrics and paper, and further functionalized with long alkyl chains by means of initiator-free UV-induced thiol-ene coupling with 1-decene (C10) and 1-tetradecene (C14). The coatings appeared to homogeneously cover the natural fibers and imparted a multi-scale roughness that was not affected by the click functionalization step. The two-step functionalization of cotton and paper warrants a stable highly hydrophobic character to the surface of natural materials that, in perspective, suggests a possible application in filtration devices for oil-water separation. Furthermore, the purification of SH-NBBs from ISWP by-products was possible during the coating process, and this step allowed for the fast, initiator-free, click-coupling of purified NBBs with C10 and C14 in solution with a nearly quantitative yield. Therefore, this approach is an alternative route to get sol-gel-derived, ladder-like, and cage-like SSQs functionalized with long alkyl chains.

  7. Fabrication of two-dimensional visible wavelength nanoscale plasmonic structures using hydrogen silsesquioxane based resist

    Science.gov (United States)

    Smith, Kyle Z.; Gadde, Akshitha; Kadiyala, Anand; Dawson, Jeremy M.

    2016-03-01

    In recent years, the global market for biosensors has continued to increase in combination with their expanding use in areas such as biodefense/detection, home diagnostics, biometric identification, etc. A constant necessity for inexpensive, portable bio-sensing methods, while still remaining simple to understand and operate, is the motivation behind novel concepts and designs. Labeled visible spectrum bio-sensing systems provide instant feedback that is both simple and easy to work with, but are limited by the light intensity thresholds required by the imaging systems. In comparison, label-free bio-sensing systems and other detection modalities like electrochemical, frequency resonance, thermal change, etc., can require additional technical processing steps to convey the final result, increasing the system's complexity and possibly the time required for analysis. Further decrease in the detection limit can be achieved through the addition of plasmonic structures into labeled bio-sensing systems. Nano-structures that operate in the visible spectrum have feature sizes typically in the order of the operating wavelength, calling for high aspect ratio nanoscale fabrication capabilities. In order to achieve these dimensions, electron beam lithography (EBL) is used due to its accurate feature production. Hydrogen silsesquioxane (HSQ) based electron beam resist is chosen for one of its benefits, which is after exposure to oxygen plasma, the patterned resist cures into silicon dioxide (SiO2). These cured features in conjunction with nanoscale gold particles help in producing a high electric field through dipole generation. In this work, a detailed process flow of the fabrication of square lattice of plasmonic structures comprising of gold coated silicon dioxide pillars designed to operate at 560 nm wavelength and produce an intensity increase of roughly 100 percent will be presented.

  8. A piecewise linear finite element discretization of the diffusion equation for arbitrary polyhedral grids

    Energy Technology Data Exchange (ETDEWEB)

    Bailey, T S; Adams, M L [Texas A M Univ., Dept. of Nuclear Engineering, College Station, TX (United States); Yang, B; Zika, M R [Lawrence Livermore National Lab., Livermore, CA (United States)

    2005-07-01

    We develop a piecewise linear (PWL) Galerkin finite element spatial discretization for the multi-dimensional radiation diffusion equation. It uses piecewise linear weight and basis functions in the finite element approximation, and it can be applied on arbitrary polygonal (2-dimensional) or polyhedral (3-dimensional) grids. We show that this new PWL method gives solutions comparable to those from Palmer's finite-volume method. However, since the PWL method produces a symmetric positive definite coefficient matrix, it should be substantially more computationally efficient than Palmer's method, which produces an asymmetric matrix. We conclude that the Galerkin PWL method is an attractive option for solving diffusion equations on unstructured grids. (authors)

  9. Asymmetrical Polyhedral Configuration of Giant Vesicles Induced by Orderly Array of Encapsulated Colloidal Particles.

    Science.gov (United States)

    Natsume, Yuno; Toyota, Taro

    2016-01-01

    Giant vesicles (GVs) encapsulating colloidal particles by a specific volume fraction show a characteristic configuration under a hypertonic condition. Several flat faces were formed in GV membrane with orderly array of inner particles. GV shape changed from the spherical to the asymmetrical polyhedral configuration. This shape deformation was derived by entropic interaction between inner particles and GV membrane. Because a part of inner particles became to form an ordered phase in the region neighboring the GV membrane, free volume for the other part of particles increased. Giant vesicles encapsulating colloidal particles were useful for the model of "crowding effect" which is the entropic interaction in the cell.

  10. Synthesis, characterization and thermal properties of the silsesquioxane organically modified with 4,5-diphenyl-2-Imidazoltiol

    International Nuclear Information System (INIS)

    Silvestrini, D.R.; Carmo, D.R. do

    2014-01-01

    The present paper describes the preparation of a nanostructured silsesquioxane, the octa-(3-chloropropyl)-octasilsesquioxane (S) that was organofunctionalised with the 4,5-Diphenyl-2-imidazolethiol (DIT). The modification of silsesquioxane with DIT proposed in this paper follows two steps. The composite prepared after functionalization was ascribed as SDIT. The composite SDIT and precursors were characterized by infrared (FTIR), "1"3C and "2"9Si Nuclear Resonance Magnetic (NMR) in solid state, Scanning Electron microscopy (SEM); X-Ray Diffraction (XRD); Energy-Dispersive X-ray spectroscopy (EDS) and Thermogravimetry. By spectroscopic analysis using above techniques, we conclude with that the SDIT synthesis was conducted with success. It was observed a cluster of particles containing cavities in an orderly fashion. The thermogravimetry analyzes performed in two different atmospheres, concluding that the materials (S, DIT and SDIT) when in air atmosphere has a slower degradation process in relation to nitrogen atmosphere. The thermogravimetry of SDIT indicate a greater thermal stability in nitrogen atmosphere. (author)

  11. Induced oligomerization targets Golgi proteins for degradation in lysosomes.

    Science.gov (United States)

    Tewari, Ritika; Bachert, Collin; Linstedt, Adam D

    2015-12-01

    Manganese protects cells against forms of Shiga toxin by down-regulating the cycling Golgi protein GPP130. Down-regulation occurs when Mn binding causes GPP130 to oligomerize and traffic to lysosomes. To determine how GPP130 is redirected to lysosomes, we tested the role of GGA1 and clathrin, which mediate sorting in the canonical Golgi-to-lysosome pathway. GPP130 oligomerization was induced using either Mn or a self-interacting version of the FKBP domain. Inhibition of GGA1 or clathrin specifically blocked GPP130 redistribution, suggesting recognition of the aggregated GPP130 by the GGA1/clathrin-sorting complex. Unexpectedly, however, GPP130's cytoplasmic domain was not required, and redistribution also occurred after removal of GPP130 sequences needed for its normal cycling. Therefore, to test whether aggregate recognition might be a general phenomenon rather than one involving a specific GPP130 determinant, we induced homo-oligomerization of two unrelated Golgi-targeted constructs using the FKBP strategy. These were targeted to the cis- and trans-Golgi, respectively, using domains from mannosidase-1 and galactosyltransferase. Significantly, upon oligomerization, each redistributed to peripheral punctae and was degraded. This occurred in the absence of detectable UPR activation. These findings suggest the unexpected presence of quality control in the Golgi that recognizes aggregated Golgi proteins and targets them for degradation in lysosomes. © 2015 Tewari et al. This article is distributed by The American Society for Cell Biology under license from the author(s). Two months after publication it is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

  12. Oxygen Plasma Modification of Poss-Coated Kapton(Registered TradeMark) HN Films

    Science.gov (United States)

    Wohl, C. J.; Belcher, M. A.; Ghose, S.; Connell, J. W.

    2008-01-01

    The surface energy of a material depends on both surface composition and topographic features. In an effort to modify the surface topography of Kapton(Registered TradeMark) HN film, organic solutions of a polyhedral oligomeric silsesquioxane, octakis(dimethylsilyloxy)silsesquioxane (POSS), were spray-coated onto the Kapton(Registered TradeMark) HN surface. Prior to POSS application, the Kapton(Registered TradeMark) HN film was activated by exposure to radio frequency (RF)-generated oxygen plasma. After POSS deposition and solvent evaporation, the films were exposed to various durations of RF-generated oxygen plasma to create a topographically rich surface. The modified films were characterized using optical microscopy, attenuated total reflection infrared (ATR-IR) spectroscopy, and high-resolution scanning electron microscopy (HRSEM). The physical properties of the modified films will be presented.

  13. Towards reproducible experimental studies for non-convex polyhedral shaped particles

    Science.gov (United States)

    Wilke, Daniel N.; Pizette, Patrick; Govender, Nicolin; Abriak, Nor-Edine

    2017-06-01

    The packing density and flat bottomed hopper discharge of non-convex polyhedral particles are investigated in a systematic experimental study. The motivation for this study is two-fold. Firstly, to establish an approach to deliver quality experimental particle packing data for non-convex polyhedral particles that can be used for characterization and validation purposes of discrete element codes. Secondly, to make the reproducibility of experimental setups as convenient and readily available as possible using affordable and accessible technology. The primary technology for this study is fused deposition modeling used to 3D print polylactic acid (PLA) particles using readily available 3D printer technology. A total of 8000 biodegradable particles were printed, 1000 white particles and 1000 black particles for each of the four particle types considered in this study. Reproducibility is one benefit of using fused deposition modeling to print particles, but an extremely important additional benefit is that specific particle properties can be explicitly controlled. As an example in this study the volume fraction of each particle can be controlled i.e. the effective particle density can be adjusted. In this study the particle volumes reduces drastically as the non-convexity is increased, however all printed white particles in this study have the same mass within 2% of each other.

  14. Towards reproducible experimental studies for non-convex polyhedral shaped particles

    Directory of Open Access Journals (Sweden)

    Wilke Daniel N.

    2017-01-01

    Full Text Available The packing density and flat bottomed hopper discharge of non-convex polyhedral particles are investigated in a systematic experimental study. The motivation for this study is two-fold. Firstly, to establish an approach to deliver quality experimental particle packing data for non-convex polyhedral particles that can be used for characterization and validation purposes of discrete element codes. Secondly, to make the reproducibility of experimental setups as convenient and readily available as possible using affordable and accessible technology. The primary technology for this study is fused deposition modeling used to 3D print polylactic acid (PLA particles using readily available 3D printer technology. A total of 8000 biodegradable particles were printed, 1000 white particles and 1000 black particles for each of the four particle types considered in this study. Reproducibility is one benefit of using fused deposition modeling to print particles, but an extremely important additional benefit is that specific particle properties can be explicitly controlled. As an example in this study the volume fraction of each particle can be controlled i.e. the effective particle density can be adjusted. In this study the particle volumes reduces drastically as the non-convexity is increased, however all printed white particles in this study have the same mass within 2% of each other.

  15. Fourth class of convex equilateral polyhedron with polyhedral symmetry related to fullerenes and viruses.

    Science.gov (United States)

    Schein, Stan; Gayed, James Maurice

    2014-02-25

    The three known classes of convex polyhedron with equal edge lengths and polyhedral symmetry--tetrahedral, octahedral, and icosahedral--are the 5 Platonic polyhedra, the 13 Archimedean polyhedra--including the truncated icosahedron or soccer ball--and the 2 rhombic polyhedra reported by Johannes Kepler in 1611. (Some carbon fullerenes, inorganic cages, icosahedral viruses, geodesic structures, and protein complexes resemble these fundamental shapes.) Here we add a fourth class, "Goldberg polyhedra," which are also convex and equilateral. We begin by decorating each of the triangular facets of a tetrahedron, an octahedron, or an icosahedron with the T vertices and connecting edges of a "Goldberg triangle." We obtain the unique set of internal angles in each planar face of each polyhedron by solving a system of n equations and n variables, where the equations set the dihedral angle discrepancy about different types of edge to zero, and the variables are a subset of the internal angles in 6gons. Like the faces in Kepler's rhombic polyhedra, the 6gon faces in Goldberg polyhedra are equilateral and planar but not equiangular. We show that there is just a single tetrahedral Goldberg polyhedron, a single octahedral one, and a systematic, countable infinity of icosahedral ones, one for each Goldberg triangle. Unlike carbon fullerenes and faceted viruses, the icosahedral Goldberg polyhedra are nearly spherical. The reasoning and techniques presented here will enable discovery of still more classes of convex equilateral polyhedra with polyhedral symmetry.

  16. Polyhedral Lyapunov functions structurally ensure global asymptotic stability of dynamical networks iff the Jacobian is non-singular

    NARCIS (Netherlands)

    Blanchini, Franco; Giordano, G.

    2017-01-01

    For a vast class of dynamical networks, including chemical reaction networks (CRNs) with monotonic reaction rates, the existence of a polyhedral Lyapunov function (PLF) implies structural (i.e., parameter-free) local stability. Global structural stability is ensured under the additional

  17. Preparation and characterization of a new hybrid material formed by reaction of cobalt (II) nitroprusside and octa(aminopropyl)silsesquioxane

    International Nuclear Information System (INIS)

    Magossi, Mariana de Souza; Carmo, Devaney Ribeiro do

    2016-01-01

    Full text: The term silsesquioxane etymologically refers to the nanostructured compounds that has structures that feature the empirical formula (RSiO 1,5 ) n , where R is a hydrogen atom or an organic group. Each silicon atom is connected on an average of 1.5 oxygen atoms and a group R (hydrocarbon, or an organic group) [1]. In this work, a new hybrid material (ACCoN) based on octa(aminopropyl)silsesquioxane (AC) and cobalt (II) nitroprusside have been prepared following a new synthesis route. Within this context, the objective of this work was to prepare and characterize this new material for electro analytical purposes. The ACCoN was characterized by several techniques such as: spectroscopy in the region of infrared (FTIR), Energy-Dispersive X-ray spectroscopy (EDS), Scanning Electron microscopy (SEM) and X-Ray Diffraction (XRD). The FTIR spectra showed absorption bands in 1106 cm -1 refer to the stretching vibration ν s (Si-O-Si) characteristics of the structure of silsesquioxane. An important vibration can be observed which is related to the stretching vibrations of the type νN-O which occurs near 1945 cm -1 , characteristic of the sodium nitroprusside, where in the ACCoN the νN-O is shifted for more high frequency (about 117 cm -1 ) relative to sodium nitroprusside. Additionally a drastic reduction of stretching vibrations intensity νC≡N was observed in the ACCoN. This fact is an indicative of the formation of the intervalence complex, where the CN- and metal centers are bound. Through SEM and EDS spectroscopies was observed clusters of cubic particles with an average size of 325 nm. The ACCoN presents the elements Si, O, N, Co and Fe in its structure. Therefore through the aforementioned spectroscopic analysis, we conclude that the preparation of ACCoN was successfully conducted. [1] Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Chemical Reviews, vol. 110, p. 2081-2173 (2010). (author)

  18. Preparation and characterization of a new hybrid material formed by reaction of cobalt (II) nitroprusside and octa(aminopropyl)silsesquioxane

    Energy Technology Data Exchange (ETDEWEB)

    Magossi, Mariana de Souza; Carmo, Devaney Ribeiro do, E-mail: marymagossi@gmail.com [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Ilha Solteira, SP (Brazil). Faculdade de Engenharia

    2016-07-01

    Full text: The term silsesquioxane etymologically refers to the nanostructured compounds that has structures that feature the empirical formula (RSiO{sub 1,5}){sub n}, where R is a hydrogen atom or an organic group. Each silicon atom is connected on an average of 1.5 oxygen atoms and a group R (hydrocarbon, or an organic group) [1]. In this work, a new hybrid material (ACCoN) based on octa(aminopropyl)silsesquioxane (AC) and cobalt (II) nitroprusside have been prepared following a new synthesis route. Within this context, the objective of this work was to prepare and characterize this new material for electro analytical purposes. The ACCoN was characterized by several techniques such as: spectroscopy in the region of infrared (FTIR), Energy-Dispersive X-ray spectroscopy (EDS), Scanning Electron microscopy (SEM) and X-Ray Diffraction (XRD). The FTIR spectra showed absorption bands in 1106 cm{sup -1} refer to the stretching vibration ν{sub s}(Si-O-Si) characteristics of the structure of silsesquioxane. An important vibration can be observed which is related to the stretching vibrations of the type νN-O which occurs near 1945 cm{sup -1}, characteristic of the sodium nitroprusside, where in the ACCoN the νN-O is shifted for more high frequency (about 117 cm{sup -1}) relative to sodium nitroprusside. Additionally a drastic reduction of stretching vibrations intensity νC≡N was observed in the ACCoN. This fact is an indicative of the formation of the intervalence complex, where the CN- and metal centers are bound. Through SEM and EDS spectroscopies was observed clusters of cubic particles with an average size of 325 nm. The ACCoN presents the elements Si, O, N, Co and Fe in its structure. Therefore through the aforementioned spectroscopic analysis, we conclude that the preparation of ACCoN was successfully conducted. [1] Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Chemical Reviews, vol. 110, p. 2081-2173 (2010). (author)

  19. Oligomerization of G protein-coupled receptors: computational methods.

    Science.gov (United States)

    Selent, J; Kaczor, A A

    2011-01-01

    Recent research has unveiled the complexity of mechanisms involved in G protein-coupled receptor (GPCR) functioning in which receptor dimerization/oligomerization may play an important role. Although the first high-resolution X-ray structure for a likely functional chemokine receptor dimer has been deposited in the Protein Data Bank, the interactions and mechanisms of dimer formation are not yet fully understood. In this respect, computational methods play a key role for predicting accurate GPCR complexes. This review outlines computational approaches focusing on sequence- and structure-based methodologies as well as discusses their advantages and limitations. Sequence-based approaches that search for possible protein-protein interfaces in GPCR complexes have been applied with success in several studies, but did not yield always consistent results. Structure-based methodologies are a potent complement to sequence-based approaches. For instance, protein-protein docking is a valuable method especially when guided by experimental constraints. Some disadvantages like limited receptor flexibility and non-consideration of the membrane environment have to be taken into account. Molecular dynamics simulation can overcome these drawbacks giving a detailed description of conformational changes in a native-like membrane. Successful prediction of GPCR complexes using computational approaches combined with experimental efforts may help to understand the role of dimeric/oligomeric GPCR complexes for fine-tuning receptor signaling. Moreover, since such GPCR complexes have attracted interest as potential drug target for diverse diseases, unveiling molecular determinants of dimerization/oligomerization can provide important implications for drug discovery.

  20. Mechanism of the electrochemical oligomerization of thionaphteneindole: a spectroscopic study

    Science.gov (United States)

    Poggi, Gabriella; Casalbore Miceli, Giuseppe; Beggiato, Giancarlo; Emmi, Salvatore S.

    1997-10-01

    The UV, visible and NIR spectra recorded during electrolysis of TNI in CH 2Cl 2 have been studied as a function of electrolysis time and of the quantity of charge exchanged. Among the oligomeric species that might be responsible for the behaviour observed, particular attention has been devoted to dimers of TNI characterized by different charges, presence of unpaired electrons, and deprotonation of the amino hydrogens. A sample of these species has been described theoretically by means of the PM3 semiempirical hamiltonian and their spectra have been computed giving results in reasonable agreement with the observed transitions.

  1. Cartilage oligomeric matrix protein specific antibodies are pathogenic

    DEFF Research Database (Denmark)

    Geng, Hui; Nandakumar, Kutty Selva; Pramhed, Anna

    2012-01-01

    -specific monoclonal antibodies (mAbs). METHODS: B cell immunodominant regions on the COMP molecule were measured with a novel enzyme-linked immunosorbent assay using mammalian expressed full-length mouse COMP as well as a panel of recombinant mouse COMP fragments. 18 mAbs specific to COMP were generated......ABSTRACT: INTRODUCTION: Cartilage oligomeric matrix protein (COMP) is a major non-collagenous component of cartilage. Earlier, we developed a new mouse model for rheumatoid arthritis using COMP. This study was undertaken to investigate the epitope specificity and immunopathogenicity of COMP...

  2. Receptor Oligomerization as a Process Modulating Cellular Semiotics

    DEFF Research Database (Denmark)

    Giorgi, Franco; Bruni, Luis Emilio; Maggio, Roberto

    2010-01-01

    be another level of quality control that may help maintaining GPCRs rather stable throughout evolution. We propose here receptor oligomerization to be a basic molecular mechanism controlling GPCRs redundancy in many different cell types, and the plasma membrane as the first hierarchical cell structure...... at which selective categorical sensing may occur. Categorical sensing can be seen as the cellular capacity for identifying and ordering complex patterns of mixed signals out of a contextual matrix, i.e., the recognition of meaningful patterns out of ubiquitous signals. In this context, redundancy...

  3. Synthesis, characterization and metal adsorption properties of the new ion exchanger polymer 3-n-propyl(4-methylpyridinium) silsesquioxane chloride.

    Science.gov (United States)

    Magosso, H A; Panteleimonov, A V; Kholin, Y V; Gushikem, Y

    2006-11-01

    The preparation and anion exchange properties of 3-n-propyl(4-methylpyridinium) silsesquioxane chloride polymer are described. This new polymer was prepared by the sol-gel processing method and is designated as SiPic+Cl-. It is insoluble in water and showed an anion exchange capacity of 1.46x10(-3) mol g-1. The adsorption isotherms of ZnCl2, CdCl2 and HgCl2 were determined from aqueous solutions and the adsorption equilibria simulations fit the model of fixed bidentate centers with the absence of lateral interactions and energetic heterogeneity between them. The metal ions diffuse into the solid solution interface and are dominantly present as MCl2-(4) species for Zn(II), MCl(2-)4 and MCl-3 species for Cd(II) and MCl-3 species for Hg(II).

  4. A piecewise linear finite element discretization of the diffusion equation for arbitrary polyhedral grids

    Energy Technology Data Exchange (ETDEWEB)

    Bailey, Teresa S. [Texas A and M University, Department of Nuclear Engineering, College Station, TX 77843-3133 (United States)], E-mail: baileyte@tamu.edu; Adams, Marvin L. [Texas A and M University, Department of Nuclear Engineering, College Station, TX 77843-3133 (United States)], E-mail: mladams@tamu.edu; Yang, Brian [Lawrence Livermore National Laboratory, Livermore, CA 94551 (United States); Zika, Michael R. [Lawrence Livermore National Laboratory, Livermore, CA 94551 (United States)], E-mail: zika@llnl.gov

    2008-04-01

    We develop a piecewise linear (PWL) Galerkin finite element spatial discretization for the multi-dimensional radiation diffusion equation. It uses recently introduced piecewise linear weight and basis functions in the finite element approximation and it can be applied on arbitrary polygonal (2D) or polyhedral (3D) grids. We first demonstrate some analytical properties of the PWL method and perform a simple mode analysis to compare the PWL method with Palmer's vertex-centered finite-volume method and with a bilinear continuous finite element method. We then show that this new PWL method gives solutions comparable to those from Palmer's. However, since the PWL method produces a symmetric positive-definite coefficient matrix, it should be substantially more computationally efficient than Palmer's method, which produces an asymmetric matrix. We conclude that the Galerkin PWL method is an attractive option for solving diffusion equations on unstructured grids.

  5. A piecewise linear finite element discretization of the diffusion equation for arbitrary polyhedral grids

    Energy Technology Data Exchange (ETDEWEB)

    Bailey, T.S.; Adams, M.L. [Texas A M Univ., Dept. of Nuclear Engineering, College Station, TX (United States); Yang, B.; Zika, M.R. [Lawrence Livermore National Lab., Livermore, CA (United States)

    2005-07-01

    We develop a piecewise linear (PWL) Galerkin finite element spatial discretization for the multi-dimensional radiation diffusion equation. It uses piecewise linear weight and basis functions in the finite element approximation, and it can be applied on arbitrary polygonal (2-dimensional) or polyhedral (3-dimensional) grids. We show that this new PWL method gives solutions comparable to those from Palmer's finite-volume method. However, since the PWL method produces a symmetric positive definite coefficient matrix, it should be substantially more computationally efficient than Palmer's method, which produces an asymmetric matrix. We conclude that the Galerkin PWL method is an attractive option for solving diffusion equations on unstructured grids. (authors)

  6. A piecewise linear finite element discretization of the diffusion equation for arbitrary polyhedral grids

    International Nuclear Information System (INIS)

    Bailey, Teresa S.; Adams, Marvin L.; Yang, Brian; Zika, Michael R.

    2008-01-01

    We develop a piecewise linear (PWL) Galerkin finite element spatial discretization for the multi-dimensional radiation diffusion equation. It uses recently introduced piecewise linear weight and basis functions in the finite element approximation and it can be applied on arbitrary polygonal (2D) or polyhedral (3D) grids. We first demonstrate some analytical properties of the PWL method and perform a simple mode analysis to compare the PWL method with Palmer's vertex-centered finite-volume method and with a bilinear continuous finite element method. We then show that this new PWL method gives solutions comparable to those from Palmer's. However, since the PWL method produces a symmetric positive-definite coefficient matrix, it should be substantially more computationally efficient than Palmer's method, which produces an asymmetric matrix. We conclude that the Galerkin PWL method is an attractive option for solving diffusion equations on unstructured grids

  7. Spontaneous growth of the polyhedral fullerene crystals in the supersaturated Ni-C(60) composite

    Czech Academy of Sciences Publication Activity Database

    Vacík, Jiří; Lavrentiev, Vasyl; Michalcová, A.; Abe, H.; Horák, Pavel

    2011-01-01

    Roč. 509, č. 1 (2011), S380-S383 ISSN 0925-8388. [17th International Symposium on Metastable, Amorphous and Nanostructured Materials (ISMANAM 2010). Zurich, 04.09.2010-09.06.2010] R&D Projects: GA ČR GAP107/11/1856; GA AV ČR(CZ) KAN400480701; GA AV ČR(CZ) IAA400320901; GA AV ČR IAA200480702; GA ČR GA106/09/1264; GA MŠk(CZ) LC06041 Institutional research plan: CEZ:AV0Z10480505; CEZ:AV0Z40320502 Keywords : Nickel * Fullerene s * Phase separation * Polyhedral particles Subject RIV: JJ - Other Materials Impact factor: 2.289, year: 2011

  8. Development of highly open polyhedral networks from vitreous carbon for orthopaedic applications

    Science.gov (United States)

    Güiza-Argüello, V.; Bayona-Becerra, M.; Cruz-Orellana, S.; Córdoba-Tuta, E.

    2017-01-01

    Highly open polyhedral networks were fabricated using an economical and environmentally friendly template route. Recycled cellulose foams were impregnated with a sucrose resin and then pyrolyzed in order to produce reticulated vitreous carbon foams with morphological features that closely resemble trabecular bone. Also, cell sizes ~1mm were achieved, a trait that will allow the mechanical reinforcement of such scaffolds using a biomaterial coating without compromising the pore size that favors osteoblast cell infiltration and growth (200-500µm). Moreover, initial studies showed that carbonization conditions have an effect on the mechanical properties of the synthesized foams and, therefore, such process parameters could be further evaluated towards the enhancement of the mechanical resistance of the scaffolds. The materials developed here are visualized as the porous component of a synthetic bone graft with features that could help overcome the current limitations associated with the medical treatments used for bone defect repair.

  9. Descriptive and Computer Aided Drawing Perspective on an Unfolded Polyhedral Projection Surface

    Science.gov (United States)

    Dzwierzynska, Jolanta

    2017-10-01

    The aim of the herby study is to develop a method of direct and practical mapping of perspective on an unfolded prism polyhedral projection surface. The considered perspective representation is a rectilinear central projection onto a surface composed of several flat elements. In the paper two descriptive methods of drawing perspective are presented: direct and indirect. The graphical mapping of the effects of the representation is realized directly on the unfolded flat projection surface. That is due to the projective and graphical connection between points displayed on the polyhedral background and their counterparts received on the unfolded flat surface. For a significant improvement of the construction of line, analytical algorithms are formulated. They draw a perspective image of a segment of line passing through two different points determined by their coordinates in a spatial coordinate system of axis x, y, z. Compared to other perspective construction methods that use information about points, for computer vision and the computer aided design, our algorithms utilize data about lines, which are applied very often in architectural forms. Possibility of drawing lines in the considered perspective enables drawing an edge perspective image of an architectural object. The application of the changeable base elements of perspective as a horizon height and a station point location enable drawing perspective image from different viewing positions. The analytical algorithms for drawing perspective images are formulated in Mathcad software, however, they can be implemented in the majority of computer graphical packages, which can make drawing perspective more efficient and easier. The representation presented in the paper and the way of its direct mapping on the flat unfolded projection surface can find application in presentation of architectural space in advertisement and art.

  10. Compatible discrete operator schemes on polyhedral meshes for elliptic and Stokes equations

    International Nuclear Information System (INIS)

    Bonelle, Jerome

    2014-01-01

    This thesis presents a new class of spatial discretization schemes on polyhedral meshes, called Compatible Discrete Operator (CDO) schemes and their application to elliptic and Stokes equations In CDO schemes, preserving the structural properties of the continuous equations is the leading principle to design the discrete operators. De Rham maps define the degrees of freedom according to the physical nature of fields to discretize. CDO schemes operate a clear separation between topological relations (balance equations) and constitutive relations (closure laws). Topological relations are related to discrete differential operators, and constitutive relations to discrete Hodge operators. A feature of CDO schemes is the explicit use of a second mesh, called dual mesh, to build the discrete Hodge operator. Two families of CDO schemes are considered: vertex-based schemes where the potential is located at (primal) mesh vertices, and cell-based schemes where the potential is located at dual mesh vertices (dual vertices being in one-to-one correspondence with primal cells). The CDO schemes related to these two families are presented and their convergence is analyzed. A first analysis hinges on an algebraic definition of the discrete Hodge operator and allows one to identify three key properties: symmetry, stability, and P0-consistency. A second analysis hinges on a definition of the discrete Hodge operator using reconstruction operators, and the requirements on these reconstruction operators are identified. In addition, CDO schemes provide a unified vision on a broad class of schemes proposed in the literature (finite element, finite element, mimetic schemes... ). Finally, the reliability and the efficiency of CDO schemes are assessed on various test cases and several polyhedral meshes. (author)

  11. Oligomerization and polymerization of the filovirus matrix protein VP40

    International Nuclear Information System (INIS)

    Timmins, Joanna; Schoehn, Guy; Kohlhaas, Christine; Klenk, Hans-Dieter; Ruigrok, Rob W.H.; Weissenhorn, Winfried

    2003-01-01

    The matrix protein VP40 from Ebola virus plays an important role in the assembly process of virus particles by interacting with cellular factors, cellular membranes, and the ribonuclearprotein particle complex. Here we show that the N-terminal domain of VP40 folds into a mixture of two different oligomeric states in vitro, namely hexameric and octameric ringlike structures, as detected by gel filtration chromatography, chemical cross-linking, and electron microscopy. Octamer formation depends largely on the interaction with nucleic acids, which in turn confers in vitro SDS resistance. Refolding experiments with a nucleic acid free N-terminal domain preparation reveal a mostly dimeric form of VP40, which is transformed into an SDS resistant octamer upon incubation with E. coli nucleic acids. In addition, we demonstrate that the N-terminal domain of Marburg virus VP40 also folds into ringlike structures, similar to Ebola virus VP40. Interestingly, Marburg virus VP40 rings reveal a high tendency to polymerize into rods composed of stacked rings. These results may suggest distinct roles for different oligomeric forms of VP40 in the filovirus life cycle

  12. Bacterial flagellar capping proteins adopt diverse oligomeric states

    Energy Technology Data Exchange (ETDEWEB)

    Postel, Sandra; Deredge, Daniel; Bonsor, Daniel A.; Yu, Xiong; Diederichs, Kay; Helmsing, Saskia; Vromen, Aviv; Friedler, Assaf; Hust, Michael; Egelman, Edward H.; Beckett, Dorothy; Wintrode, Patrick L.; Sundberg, Eric J. (UV); (Braunschweig); (Maryland-MED); (Konstanz); (Maryland); (Hebrew)

    2016-09-24

    Flagella are crucial for bacterial motility and pathogenesis. The flagellar capping protein (FliD) regulates filament assembly by chaperoning and sorting flagellin (FliC) proteins after they traverse the hollow filament and exit the growing flagellum tip. In the absence of FliD, flagella are not formed, resulting in impaired motility and infectivity. Here, we report the 2.2 Å resolution X-ray crystal structure of FliD fromPseudomonas aeruginosa, the first high-resolution structure of any FliD protein from any bacterium. Using this evidence in combination with a multitude of biophysical and functional analyses, we find thatPseudomonasFliD exhibits unexpected structural similarity to other flagellar proteins at the domain level, adopts a unique hexameric oligomeric state, and depends on flexible determinants for oligomerization. Considering that the flagellin filaments on which FliD oligomers are affixed vary in protofilament number between bacteria, our results suggest that FliD oligomer stoichiometries vary across bacteria to complement their filament assemblies.

  13. Zn(2+) site engineering at the oligomeric interface of the dopamine transporter

    DEFF Research Database (Denmark)

    Norgaard-Nielsen, Kristine; Norregaard, Lene; Hastrup, Hanne

    2002-01-01

    Increasing evidence suggests that Na(+)/Cl(-)-dependent neurotransmitter transporters exist as homo-oligomeric proteins. However, the functional implication of this oligomerization remains unclear. Here we demonstrate the engineering of a Zn(2+) binding site at the predicted dimeric interface...

  14. An exact line integral representation of the physical optics scattered field: the case of a perfectly conducting polyhedral structure illuminated by electric Hertzian dipoles

    DEFF Research Database (Denmark)

    Johansen, Peter M.; Breinbjerg, Olav

    1995-01-01

    An exact line integral representation of the electric physical optics scattered field is presented. This representation applies to scattering configurations with perfectly electrically conducting polyhedral structures illuminated by a finite number of electric Hertzian dipoles. The positions...

  15. Chondrogenic potential of bone marrow–derived mesenchymal stem cells on a novel, auricular-shaped, nanocomposite scaffold

    Directory of Open Access Journals (Sweden)

    Kavi H Patel

    2013-12-01

    Full Text Available Reconstruction of the human auricle remains a challenge to plastic surgeons, and current approaches are not ideal. Tissue engineering provides a promising alternative. This study aims to evaluate the chondrogenic potential of bone marrow–derived mesenchymal stem cells on a novel, auricular-shaped polymer. The proposed polyhedral oligomeric silsesquioxane-modified poly(hexanolactone/carbonateurethane/urea nanocomposite polymer has already been transplanted in patients as the world’s first synthetic trachea, tear duct and vascular bypass graft. The nanocomposite scaffold was fabricated via a coagulation/salt-leaching method and shaped into an auricle. Adult bone marrow–derived mesenchymal stem cells were isolated, cultured and seeded onto the scaffold. On day 21, samples were sent for scanning electron microscopy, histology and immunofluorescence to assess for neocartilage formation. Cell viability assay confirmed cytocompatability and normal patterns of cellular growth at 7, 14 and 21 days after culture. This study demonstrates the potential of a novel polyhedral oligomeric silsesquioxane-modified poly(hexanolactone/carbonateurethane/urea scaffold for culturing bone marrow–derived mesenchymal stem cells in chondrogenic medium to produce an auricular-shaped construct. This is supported by scanning electron microscopy, histological and immunofluorescence analysis revealing markers of chondrogenesis including collagen type II, SOX-9, glycosaminoglycan and elastin. To the best of our knowledge, this is the first report of stem cell application on an auricular-shaped scaffold for tissue engineering purposes. Although many obstacles remain in producing a functional auricle, this is a promising step forward.

  16. Oligomerization interface of RAGE receptor revealed by MS-monitored hydrogen deuterium exchange.

    Directory of Open Access Journals (Sweden)

    Ewa Sitkiewicz

    Full Text Available Activation of the receptor for advanced glycation end products (RAGE leads to a chronic proinflammatory signal, affecting patients with a variety of diseases. Potentially beneficial modification of RAGE activity requires understanding the signal transduction mechanism at the molecular level. The ligand binding domain is structurally uncoupled from the cytoplasmic domain, suggesting receptor oligomerization is a requirement for receptor activation. In this study, we used hydrogen-deuterium exchange and mass spectrometry to map structural differences between the monomeric and oligomeric forms of RAGE. Our results indicated the presence of a region shielded from exchange in the oligomeric form of RAGE and led to the identification of a new oligomerization interface localized at the linker region between domains C1 and C2. Based on this finding, a model of a RAGE dimer and higher oligomeric state was constructed.

  17. Synaptic transmission block by presynaptic injection of oligomeric amyloid beta

    Science.gov (United States)

    Moreno, Herman; Yu, Eunah; Pigino, Gustavo; Hernandez, Alejandro I.; Kim, Natalia; Moreira, Jorge E.; Sugimori, Mutsuyuki; Llinás, Rodolfo R.

    2009-01-01

    Early Alzheimer's disease (AD) pathophysiology is characterized by synaptic changes induced by degradation products of amyloid precursor protein (APP). The exact mechanisms of such modulation are unknown. Here, we report that nanomolar concentrations of intraaxonal oligomeric (o)Aβ42, but not oAβ40 or extracellular oAβ42, acutely inhibited synaptic transmission at the squid giant synapse. Further characterization of this phenotype demonstrated that presynaptic calcium currents were unaffected. However, electron microscopy experiments revealed diminished docked synaptic vesicles in oAβ42-microinjected terminals, without affecting clathrin-coated vesicles. The molecular events of this modulation involved casein kinase 2 and the synaptic vesicle rapid endocytosis pathway. These findings open the possibility of a new therapeutic target aimed at ameliorating synaptic dysfunction in AD. PMID:19304802

  18. Fluorescence reporters for Hfq oligomerization and RNA annealing

    Science.gov (United States)

    Panja, Subrata; Woodson, Sarah A.

    2015-01-01

    Fluorescence spectroscopy is a sensitive technique for detecting protein-protein, protein-RNA and RNA-RNA interactions, requiring only nanomolar concentrations of labeled components. Fluorescence anisotropy provides information about the assembly of multi-subunit proteins, while molecular beacons provide a sensitive and quantitative reporter for base pairing between complementary RNAs. Here we present a detailed protocol for labeling Hfq protein with cyanine 3-maleimide and dansyl chloride to study the protein oligomerization and RNA binding by semi-native polyacrylamide gel electrophoresis (PAGE) and fluorescence anisotropy. We also present a detailed protocol for measuring the rate of annealing between a molecular beacon and a target RNA in the presence of Hfq using a stopped-flow spectrometer. PMID:25579597

  19. Electron Microscopy Structural Insights into CPAP Oligomeric Behavior

    DEFF Research Database (Denmark)

    Alvarez-Cabrera, Ana L; Delgado, Sandra; Gil-Carton, David

    2017-01-01

    Centrosomal P4.1-associated protein (CPAP) is a cell cycle regulated protein fundamental for centrosome assembly and centriole elongation. In humans, the region between residues 897-1338 of CPAP mediates interactions with other proteins and includes a homodimerization domain. CPAP mutations cause...... into clearly different regular 3D maps (putatively corresponding to dimers and tetramers) and direct observation of individual images representing other complexes of HsCPAP(897-1338) (i.e., putative flexible monomers and higher-order multimers), we report a dynamic oligomeric behavior of this protein, where...... of different oligomers of CPAP, suggesting further insights to understand how this protein works, contributing to the elucidation of control mechanisms for centriole biogenesis....

  20. Effects of Glycine, Water, Ammonia, and Ammonium Bicarbonate on the Oligomerization of Methionine

    Science.gov (United States)

    Huang, Rui; Furukawa, Yoshihiro; Otake, Tsubasa; Kakegawa, Takeshi

    2017-06-01

    The abiotic oligomerization of amino acids may have created primordial, protein-like biological catalysts on the early Earth. Previous studies have proposed and evaluated the potential of diagenesis for the amino acid oligomerization, simulating the formation of peptides that include glycine, alanine, and valine, separately. However, whether such conditions can promote the formation of peptides composed of multiple amino acids remains unclear. Furthermore, the chemistry of pore water in sediments should affect the oligomerization and degradation of amino acids and oligomers, but these effects have not been studied extensively. In this study, we investigated the effects of water, ammonia, ammonium bicarbonate, pH, and glycine on the oligomerization and degradation of methionine under high pressure (150 MPa) and high temperature conditions (175 °C) for 96 h. Methionine is more difficult to oligomerize than glycine and methionine dimer was formed in the incubation of dry powder of methionine. Methionine oligomers as long as trimers, as well as methionylglycine and glycylmethionine, were formed under every condition with these additional compounds. Among the compounds tested, the oligomerization reaction rate was accelerated by the presence of water and by an increase in pH. Ammonia also increased the oligomerization rate but consumed methionine by side reactions and resulted in the rapid degradation of methionine and its peptides. Similarly, glycine accelerated the oligomerization rate of methionine and the degradation of methionine, producing water, ammonia, and bicarbonate through its decomposition. With Gly, heterogeneous dimers (methionylglycine and glycylmethionine) were formed in greater amounts than with other additional compounds although smaller amount of these heterogeneous dimers were formed with other additional compounds. These results suggest that accelerated reaction rates induced by water and co-existing reactive compounds promote the oligomerization

  1. Self-assembled amphiphilic polyhedral oligosilsesquioxane (POSS) grafted poly(vinyl alcohol) (PVA) nanoparticles

    International Nuclear Information System (INIS)

    Sheikh, Faheem A.; Barakat, Nasser A.M.; Kim, Byoung-Suhk; Aryal, Santosh; Khil, Myung-Seob; Kim, Hak-Yong

    2009-01-01

    In the present study, spherical nanoparticles (NPs) containing polyhedral oligosilsesquioxane (POSS) as an inner hydrophobic core and poly(vinyl alcohol) PVA as a hydrophilic outer shell were prepared by dialysis approach. Preparation of amphiphilic POSS-grafted-PVA co-polymer was characterized by 1 H NMR and FT-IR. The results indicated urethane linkage between monoisocyanate group of POSS macromer and the hydroxyl groups of PVA. The dynamic light scattering (DLS) and electrophoretic light scattering (ELS) of the NPs revealed that they have an average hydrodynamic diameter and negative zeta (ζ)-potential of 215 nm and - 161 mV, respectively. Atomic force microscopy (AFM) and bio-transmission electron microscope (BIO-TEM) have shown unagglomerated NPs within a diameter range of 60-90 nm. The prepared NPs were investigated to improve the control release of anticancer drug; paclitaxel as a model drug. Due to drug loading, the hydrodynamic diameter and negative zeta (ζ)-potential have changed to 325 nm and - 14 mV, respectively. In addition, in-vitro drug release experiments were conducted; the obtained results explicated continuous release for over 40 days. However, in case of using pure drug only, the drug completely released within 1 h.

  2. Synthesis of Zirconium-Containing Polyhedral Oligometallasilsesquioxane as an Efficient Thermal Stabilizer for Silicone Rubber

    Directory of Open Access Journals (Sweden)

    Jiedong Qiu

    2018-05-01

    Full Text Available Free radicals play a negative role during the thermal degradation of silicone rubber (SR. Quenching free radicals is proposed to be an efficient way to improve the thermal-oxidative stability of SR. In this work, a novel zirconium-containing polyhedral oligometallasilsesquioxane (Zr-POSS with free-radical quenching capability was synthesized and characterized. The incorporation of Zr-POSS effectively improved the thermal-oxidative stability of SR. The T5 (temperature at 5% weight loss of SR/Zr-POSS significantly increased by 31.7 °C when compared to the unmodified SR. Notably, after aging 12 h at 280 °C, SR/Zr-POSS was still retaining about 65%, 60%, 75%, and 100% of the tensile strength, tear strength, elongation at break, and hardness before aging, respectively, while the mechanical properties of the unmodified SR were significantly decreased. The possible mechanism of Zr-POSS for improving the thermal-oxidative stability of SR was intensively studied and it was revealed that the POSS structure could act as a limiting point to suppress the random scission reaction of backbone. Furthermore, Zr could quench the free radicals by its empty orbital and transformation of valence states. Therefore, it effectively suppressed the thermal-oxidative degradation and crosslinking reaction of the side chains.

  3. A new equi-dimensional fracture model using polyhedral cells for microseismic data sets

    KAUST Repository

    Al-Hinai, Omar

    2017-04-09

    We present a method for modeling flow in porous media in the presence of complex fracture networks. The approach utilizes the Mimetic Finite Difference (MFD) method. We employ a novel equi-dimensional approach for meshing fractures. By using polyhedral cells we avoid the common challenge in equi-dimensional fracture modeling of creating small cells at the intersection point. We also demonstrate how polyhedra can mesh complex fractures without introducing a large number of cells. We use polyhedra and the MFD method a second time for embedding fracture boundaries in the matrix domain using a “cut-cell” paradigm. The embedding approach has the advantage of being simple and localizes irregular cells to the area around the fractures. It also circumvents the need for conventional mesh generation, which can be challenging when applied to complex fracture geometries. We present numerical results confirming the validity of our approach for complex fracture networks and for different flow models. In our first example, we compare our method to the popular dual-porosity technique. Our second example compares our method with directly meshed fractures (single-porosity) for two-phase flow. The third example demonstrates two-phase flow for the case of intersecting ellipsoid fractures in three-dimensions, which are typical in microseismic analysis of fractures. Finally, we demonstrate our method on a two-dimensional fracture network produced from microseismic field data.

  4. Quantifying the thermodynamic interactions of polyhedral boranes in solution to guide nanocomposite fabrication

    International Nuclear Information System (INIS)

    Mutz, M.; Eastwood, Eric; Lee, Mark E.; Bowen, Daniel E.; Dadmun, M. D.

    2012-01-01

    The solubility of boron containing nanoparticles in a variety of solvents is quantified using static light scattering in conjunction with refractometry. Four polyhedral boranes were tested in this work, using refractometry to obtain dn/dc, while static light scattering quantifies A 2 . A 2 obtained from these measurements was then used to calculate χ, the solute–solvent interaction parameter, and the Hildebrand solubility parameter, δ, which provides a quantifiable method to identify good solvents. Of the nanoparticles studied, 1,3-di-o-carboranylpropane is thermodynamically stable in toluene, with a χ less than 0.5, a solubility limit of 2.47 mg/mL, and all solutions remaining clear with no visible particle settling. For all of the particles tested, there was good correlation between the physical observations of the solutions, χ, and δ. For instance, lower values of χ correspond to a smaller radius of gyration (R g ). A list of suitable solvents based on δ is also presented.

  5. Quantifying the thermodynamic interactions of polyhedral boranes in solution to guide nanocomposite fabrication

    Energy Technology Data Exchange (ETDEWEB)

    Mutz, M. [University of Tennessee, Department of Chemistry (United States); Eastwood, Eric [Honeywell Kansas City Plant (United States); Lee, Mark E. [University of Missouri (United States); Bowen, Daniel E. [Honeywell Kansas City Plant (United States); Dadmun, M. D., E-mail: dad@utk.edu [University of Tennessee, Department of Chemistry (United States)

    2012-11-15

    The solubility of boron containing nanoparticles in a variety of solvents is quantified using static light scattering in conjunction with refractometry. Four polyhedral boranes were tested in this work, using refractometry to obtain dn/dc, while static light scattering quantifies A{sub 2}. A{sub 2} obtained from these measurements was then used to calculate {chi}, the solute-solvent interaction parameter, and the Hildebrand solubility parameter, {delta}, which provides a quantifiable method to identify good solvents. Of the nanoparticles studied, 1,3-di-o-carboranylpropane is thermodynamically stable in toluene, with a {chi} less than 0.5, a solubility limit of 2.47 mg/mL, and all solutions remaining clear with no visible particle settling. For all of the particles tested, there was good correlation between the physical observations of the solutions, {chi}, and {delta}. For instance, lower values of {chi} correspond to a smaller radius of gyration (R{sub g}). A list of suitable solvents based on {delta} is also presented.

  6. Polyhedral microcrystals encapsulating bone morphogenetic protein 2 improve healing in the alveolar ridge.

    Science.gov (United States)

    Matsumoto, Goichi; Ueda, Takayo; Sugita, Yoshihiko; Kubo, Katsutoshi; Mizoguchi, Megumi; Kotani, Eiji; Oda, Naoki; Kawamata, Shin; Segami, Natsuki; Mori, Hajime

    2015-08-01

    Atelocollagen sponges incorporating polyhedra encapsulating bone morphogenetic protein 2 (BMP-2) were implanted into lateral bone defects in the mandible. Half of the bone defects on the left side were treated with atelocollagen sponges containing 1.8 × 10(7) BMP-2 polyhedra, and half were treated with sponges containing 3.6 × 10(6) BMP-2 polyhedra. As controls, we treated the right-side bone defects in each animal with an atelocollagen sponge containing 5 µg of recombinant human BMP-2 (rhBMP-2) or 1.8 × 10(7) empty polyhedral. After a healing period of six months, whole mandibles were removed for micro-computed tomography (CT) and histological analyses. Micro-CT images showed that more bone had formed at all experimental sites than at control sites. However, the density of the new bone was not significantly higher at sites with an atelocollagen sponge containing BMP-2 polyhedra than at sites with an atelocollagen sponge containing rhBMP-2 or empty polyhedra. Histological examination confirmed that the BMP-2 polyhedra almost entirely replaced the atelocollagen sponges and connected the original bone with the regenerated bone. These results show that the BMP-2 delivery system facilitates the regeneration of new bone in the mandibular alveolar bone ridge and has an advance in the technology of bone regeneration for implant site development. © The Author(s) 2015.

  7. Recurring polyhedral motifs in the amorphous indium gallium zinc oxide network

    International Nuclear Information System (INIS)

    Divya; Deepak; Prasad, Rajendra

    2017-01-01

    The coordination polyhedra around the cations are the building blocks of ionic solids. For amorphous InGaZn oxide (a-IGZO), these coordination polyhedra are identified to investigate properties that depend on short range interactions. Therefore, in this first principles based study, a large number (10) of samples of a-IGZO were prepared by ab initio melt-and-quench molecular dynamics, so that several distinct samples of the amorphous landscape are obtained corresponding to local minima in energy. Based on a method of comparing bond angles between metal and oxygen atoms, the identified polyhedra were matched to the polyhedral motifs present in the related crystalline systems, such as, InGaZnO_4, In_2O_3, Ga_2O_3, and ZnO. Consequently, we find, the a-IGZO primarily consists of the following polyhedra: a tetrahedron from space group 199 and an octahedron from space group 206 of In_2O_3; a tetrahedron from space group 12 and an octahedron from space group 167 of Ga_2O_3; a tetrahedron from space group 186 of ZnO; zinc and gallium trigonal bipyramids from c-IGZO; and one zinc fourfold, one zinc fivefold, and one indium fivefold coordination polyhedra that occur only in the amorphous phase. Thus, we were able to reduce the description of structure from 360 to 10 groups of polyhedra. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. A new equi-dimensional fracture model using polyhedral cells for microseismic data sets

    KAUST Repository

    Al-Hinai, Omar; Dong, Rencheng; Srinivasan, Sanjay; Wheeler, Mary F.

    2017-01-01

    We present a method for modeling flow in porous media in the presence of complex fracture networks. The approach utilizes the Mimetic Finite Difference (MFD) method. We employ a novel equi-dimensional approach for meshing fractures. By using polyhedral cells we avoid the common challenge in equi-dimensional fracture modeling of creating small cells at the intersection point. We also demonstrate how polyhedra can mesh complex fractures without introducing a large number of cells. We use polyhedra and the MFD method a second time for embedding fracture boundaries in the matrix domain using a “cut-cell” paradigm. The embedding approach has the advantage of being simple and localizes irregular cells to the area around the fractures. It also circumvents the need for conventional mesh generation, which can be challenging when applied to complex fracture geometries. We present numerical results confirming the validity of our approach for complex fracture networks and for different flow models. In our first example, we compare our method to the popular dual-porosity technique. Our second example compares our method with directly meshed fractures (single-porosity) for two-phase flow. The third example demonstrates two-phase flow for the case of intersecting ellipsoid fractures in three-dimensions, which are typical in microseismic analysis of fractures. Finally, we demonstrate our method on a two-dimensional fracture network produced from microseismic field data.

  9. Synthesis of poly(aminopropyl/methyl)silsesquioxane particles as effective Cu(II) and Pb(II) adsorbents.

    Science.gov (United States)

    Lu, Xin; Yin, Qiangfeng; Xin, Zhong; Li, Yang; Han, Ting

    2011-11-30

    Poly(aminopropyl/methyl)silsesquioxane (PAMSQ) particles have been synthesized by a one-step hydrolytic co-condensation process using 3-aminopropyltriethoxysilane (APTES) and methyltrimethoxysilane (MTMS) as precursors in the presence of base catalyst in aqueous medium. The amino functionalities of the particles could be controlled by adjusting the organosilanes feed ratio. The compositions of the amino-functionalized polysilsesquioxanes were confirmed by FT-IR spectroscopy, solid-state (29)Si NMR spectroscopy, and elemental analysis. The strong adsorbability of Cu(II) and Pb(II) ions onto PAMSQ particles was systematically examined. The effect of adsorption time, initial metal ions concentration and pH of solutions was studied to optimize the metal ions adsorbability of PAMSQ particles. The kinetic studies indicated that the adsorption process well fits the pseudo-second-order kinetics. Adsorption phenomena appeared to follow Langmuir isotherm. The PAMSQ particles demonstrate the highest Cu(II) and Pb(II) adsorption capacity of 2.29 mmol/g and 1.31 mmol/g at an initial metal ions concentration of 20mM, respectively. The PAMSQ particles demonstrate a promising application in the removal of Cu(II) and Pb(II) ions from aqueous solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. Hybrid Films Based on a Bridged Silsesquioxane Doped with Goethite and Montmorillonite Nanoparticles as Sorbents of Wastewater Contaminants

    Directory of Open Access Journals (Sweden)

    Carolina V. Waiman

    2016-01-01

    Full Text Available The synthesis and characterization of silsesquioxane (SSO films with pendant dodecyl groups and doped with goethite (Gt or montmorillonite (MMT nanoparticles were carried out and the new materials tested as sorbents of diverse contaminants. The synthetic method used yielded SSO films with the inorganic substrates homogeneously distributed within the polymeric matrices. The new materials were characterized by SEM, FTIR, XRD, and DSC and tested to evaluate their capability for adsorbing metallic cations, organic dyes, and phosphate, frequent contaminants of industrial effluents. All films were found suitable for removing metallic cations. Results also showed that the SSO films undoped and doped with Gt are primarily apt for anionic compounds removal. Although the SSO films doped with MMT are capable of removing cationic contaminants from aqueous samples, the stiffness of the SSO matrix hinders MMT properties as an adsorbent. The possibility of dispersing nanoparticulate systems in the stable and chemically inert SSO matrices simplifies their application for contaminant removal, particularly because it makes the separation process of the absorbed pollutant from the treated medium easier.

  11. Electron beam exposure mechanisms in hydrogen silsesquioxane investigated by vibrational spectroscopy and in-situ electron beam induced desorption

    Energy Technology Data Exchange (ETDEWEB)

    Olynick, D.L.; Cord, B.; Schipotinin, A.; Ogletree, D.F.; Schuck, P.J.

    2009-11-13

    Hydrogen Silsesquioxane (HSQ) is used as a high-resolution resist with resolution down below 10nm half-pitch. This material or materials with related functionalities could have widespread impact in nanolithography and nanoscience applications if the exposure mechanism was understood and instabilities controlled. Here we have directly investigated the exposure mechanism using vibrational spectroscopy (both Raman and Fourier transform Infrared) and electron beam desorption spectrocscopy (EBDS). In the non-networked HSQ system, silicon atoms sit at the corners of a cubic structure. Each silicon is bonded to a hydrogen atom and bridges 3 oxygen atoms (formula: HSiO3/2). For the first time, we have shown, via changes in the Si-H2 peak at ~;;2200 cm -1 in the Raman spectra and the release of SiHx products in EBID, that electron-bam exposed materials crosslinks via a redistribution reaction. In addition, we observe the release of significantly more H2 than SiH2 during EBID, which is indicative of additional reaction mechanisms. Additionally, we compare the behavior of HSQ in response to both thermal and electron-beam induced reactions.

  12. Interaction of SF6 and O2 plasma with porous poly phenyl methyl silsesquioxane low-κ films

    International Nuclear Information System (INIS)

    Cherunilam, J F; Rajani, K V; Daniels, S; Byrne, C; Heise, A; McNally, P J

    2015-01-01

    A reduction in the κ-value of dielectric materials is of great interest today as it leads to the reduction of resistance–capacitance delays and parasitic capacitances within integrated circuits, thereby improving device performance. We have recently reported our studies on the great potential of the Poly phenyl methyl silsesquioxane (PMSQ) low-κ films (κ = 2.7  ±  0.2) for interlayer dielectric applications. Here we report on the deposition and characterisation of porous PMSQ thin films using Heptakis (2,3,6-tri-O-methyl)-β-cyclodextrin as the porogen. A reduction in the κ-value of the films was achieved as a function of the increase in porogen loading in the film. The removal of the thermally liable porogen material from the hybrid films was studied using thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). The change in density as a function of the porosity was studied using x-ray reflectivity techniques. The interaction of the films with pure SF 6 and O 2 plasmas was studied and the surface modification that occurs in the films as a result of the interaction was studied using FTIR and x-ray photoelectron spectroscopy. A change in the κ-value of the films was observed after plasma treatment which is attributed to the chemical modification of the film surface due to plasma interaction. (paper)

  13. Photophysical Behavior of Modified Xanthenic Dyes Embedded into Silsesquioxane Hybrid Films: Application in Photooxidation of Organic Molecules

    Directory of Open Access Journals (Sweden)

    Carolina V. Waiman

    2017-01-01

    Full Text Available Polymeric materials based on a bridged silsesquioxane with pendant dodecyl chains were synthesized and modified with different xanthenic dyes with the aim of developing a material with potential application in photooxidation of organic compounds. The employed dyes constitute a family of novel xanthenic chromophores with outstanding properties as singlet oxygen photosensitizers. The hybrid matrix was chosen for its enhanced properties such as flexibility and chemical resistance. The employed dyes were easily incorporated into the hybrid polymer obtaining homogeneous, transparent, and low-refractive-index materials. The polymeric films were characterized using UV-Vis absorption, fluorescence, and laser flash photolysis techniques. The ability of these materials to produce singlet oxygen was tested following the photooxidation of 9,10-dimethylanthracene which is a well-known chemical trap for singlet oxygen. High photooxidation efficiencies were observed for these materials, which present the advantage of being easily removed/collected from the solution where photooxidation takes place. While photobleaching of the incorporated dyes is commonly observed in the solution, it takes place very slowly when dyes are embedded in the hybrid matrix. These properties bode well for the potential use of these materials in novel wastewater purification strategies.

  14. Solution processeable organic-inorganic hybrids based on pyrene functionalized mixed cubic silsesquioxanes as emitters in OLEDs

    KAUST Repository

    Yang, Xiaohui

    2012-01-01

    Traditional materials for application in organic light emitting diodes (OLEDs) are primarily based on small molecules and polymers, with much fewer examples of intermediate molecular weight materials. Our interest lies in this intermediate molecular weight range, specifically in hybrids based on 3-dimensional silsesquioxane (SSQ) cores that represents a new class of versatile materials for application in solution processable OLEDs. We report here various SSQ based hybrids that are easily prepared in one high-yield step from the Heck coupling of commercially available 1-bromopyrene, and 1-bromo-4-heptylbenzene with octavinyl-T8-SSQ, and a mixture of octavinyl-T8-, decavinyl-T10- and dodecavinyl-T12-SSQ. The resulting materials offer numerous advantages for OLEDs including amorphous properties, high-glass-transition temperatures (T g), low polydispersity, solubility in common solvents, and high purity via column chromatography. Solution processed OLEDs prepared from the SSQ hybrids provide sky-blue emission with external quantum efficiencies and current efficiencies of 3.64% and 9.56 cd A -1 respectively. © 2012 The Royal Society of Chemistry.

  15. Oligomeric protein structure networks: insights into protein-protein interactions

    Directory of Open Access Journals (Sweden)

    Brinda KV

    2005-12-01

    Full Text Available Abstract Background Protein-protein association is essential for a variety of cellular processes and hence a large number of investigations are being carried out to understand the principles of protein-protein interactions. In this study, oligomeric protein structures are viewed from a network perspective to obtain new insights into protein association. Structure graphs of proteins have been constructed from a non-redundant set of protein oligomer crystal structures by considering amino acid residues as nodes and the edges are based on the strength of the non-covalent interactions between the residues. The analysis of such networks has been carried out in terms of amino acid clusters and hubs (highly connected residues with special emphasis to protein interfaces. Results A variety of interactions such as hydrogen bond, salt bridges, aromatic and hydrophobic interactions, which occur at the interfaces are identified in a consolidated manner as amino acid clusters at the interface, from this study. Moreover, the characterization of the highly connected hub-forming residues at the interfaces and their comparison with the hubs from the non-interface regions and the non-hubs in the interface regions show that there is a predominance of charged interactions at the interfaces. Further, strong and weak interfaces are identified on the basis of the interaction strength between amino acid residues and the sizes of the interface clusters, which also show that many protein interfaces are stronger than their monomeric protein cores. The interface strengths evaluated based on the interface clusters and hubs also correlate well with experimentally determined dissociation constants for known complexes. Finally, the interface hubs identified using the present method correlate very well with experimentally determined hotspots in the interfaces of protein complexes obtained from the Alanine Scanning Energetics database (ASEdb. A few predictions of interface hot

  16. Diverse oligomeric states of CEACAM IgV domains.

    Science.gov (United States)

    Bonsor, Daniel A; Günther, Sebastian; Beadenkopf, Robert; Beckett, Dorothy; Sundberg, Eric J

    2015-11-03

    Carcinoembryonic antigen-related cell adhesion molecules (CEACAMs) comprise a large family of cell surface adhesion molecules that bind to themselves and other family members to carry out numerous cellular functions, including proliferation, signaling, differentiation, tumor suppression, and survival. They also play diverse and significant roles in immunity and infection. The formation of CEACAM oligomers is caused predominantly by interactions between their N-terminal IgV domains. Although X-ray crystal structures of CEACAM IgV domain homodimers have been described, how CEACAMs form heterodimers or remain monomers is poorly understood. To address this key aspect of CEACAM function, we determined the crystal structures of IgV domains that form a homodimeric CEACAM6 complex, monomeric CEACAM8, and a heterodimeric CEACAM6-CEACAM8 complex. To confirm and quantify these interactions in solution, we used analytical ultracentrifugation to measure the dimerization constants of CEACAM homodimers and isothermal titration calorimetry to determine the thermodynamic parameters and binding affinities of CEACAM heterodimers. We found the CEACAM6-CEACAM8 heterodimeric state to be substantially favored energetically relative to the CEACAM6 homodimer. Our data provide a molecular basis for the adoption of the diverse oligomeric states known to exist for CEACAMs and suggest ways in which CEACAM6 and CEACAM8 regulate the biological functions of one another, as well as of additional CEACAMs with which they interact, both in cis and in trans.

  17. Free-energy landscape of protein oligomerization from atomistic simulations

    Science.gov (United States)

    Barducci, Alessandro; Bonomi, Massimiliano; Prakash, Meher K.; Parrinello, Michele

    2013-01-01

    In the realm of protein–protein interactions, the assembly process of homooligomers plays a fundamental role because the majority of proteins fall into this category. A comprehensive understanding of this multistep process requires the characterization of the driving molecular interactions and the transient intermediate species. The latter are often short-lived and thus remain elusive to most experimental investigations. Molecular simulations provide a unique tool to shed light onto these complex processes complementing experimental data. Here we combine advanced sampling techniques, such as metadynamics and parallel tempering, to characterize the oligomerization landscape of fibritin foldon domain. This system is an evolutionarily optimized trimerization motif that represents an ideal model for experimental and computational mechanistic studies. Our results are fully consistent with previous experimental nuclear magnetic resonance and kinetic data, but they provide a unique insight into fibritin foldon assembly. In particular, our simulations unveil the role of nonspecific interactions and suggest that an interplay between thermodynamic bias toward native structure and residual conformational disorder may provide a kinetic advantage. PMID:24248370

  18. Exceptionally High Electric Double Layer Capacitances of Oligomeric Ionic Liquids.

    Science.gov (United States)

    Matsumoto, Michio; Shimizu, Sunao; Sotoike, Rina; Watanabe, Masayoshi; Iwasa, Yoshihiro; Itoh, Yoshimitsu; Aida, Takuzo

    2017-11-15

    Electric double layer (EDL) capacitors are promising as next-generation energy accumulators if their capacitances and operation voltages are both high. However, only few electrolytes can simultaneously fulfill these two requisites. Here we report that an oligomeric ionic liquid such as IL4 TFSI with four imidazolium ion units in its structure provides a wide electrochemical window of ∼5.0 V, similar to monomeric ionic liquids. Furthermore, electrochemical impedance measurements using Au working electrodes demonstrated that IL4 TFSI exhibits an exceptionally high EDL capacitance of ∼66 μF/cm 2 , which is ∼6 times as high as those of monomeric ionic liquids so far reported. We also found that an EDL-based field effect transistor (FET) using IL4 TFSI as a gate dielectric material and SrTiO 3 as a channel material displays a very sharp transfer curve with an enhanced carrier accumulation capability of ∼64 μF/cm 2 , as determined by Hall-effect measurements.

  19. Assessing heterogeneity in oligomeric AAA+ machines.

    Science.gov (United States)

    Sysoeva, Tatyana A

    2017-03-01

    ATPases Associated with various cellular Activities (AAA+ ATPases) are molecular motors that use the energy of ATP binding and hydrolysis to remodel their target macromolecules. The majority of these ATPases form ring-shaped hexamers in which the active sites are located at the interfaces between neighboring subunits. Structural changes initiate in an active site and propagate to distant motor parts that interface and reshape the target macromolecules, thereby performing mechanical work. During the functioning cycle, the AAA+ motor transits through multiple distinct states. Ring architecture and placement of the catalytic sites at the intersubunit interfaces allow for a unique level of coordination among subunits of the motor. This in turn results in conformational differences among subunits and overall asymmetry of the motor ring as it functions. To date, a large amount of structural information has been gathered for different AAA+ motors, but even for the most characterized of them only a few structural states are known and the full mechanistic cycle cannot be yet reconstructed. Therefore, the first part of this work will provide a broad overview of what arrangements of AAA+ subunits have been structurally observed focusing on diversity of ATPase oligomeric ensembles and heterogeneity within the ensembles. The second part of this review will concentrate on methods that assess structural and functional heterogeneity among subunits of AAA+ motors, thus bringing us closer to understanding the mechanism of these fascinating molecular motors.

  20. Antibodies against alpha-synuclein reduce oligomerization in living cells.

    Directory of Open Access Journals (Sweden)

    Thomas Näsström

    Full Text Available Recent research implicates soluble aggregated forms of α-synuclein as neurotoxic species with a central role in the pathogenesis of Parkinson's disease and related disorders. The pathway by which α-synuclein aggregates is believed to follow a step-wise pattern, in which dimers and smaller oligomers are initially formed. Here, we used H4 neuroglioma cells expressing α-synuclein fused to hemi:GFP constructs to study the effects of α-synuclein monoclonal antibodies on the early stages of aggregation, as quantified by Bimolecular Fluorescence Complementation assay. Widefield and confocal microscopy revealed that cells treated for 48 h with monoclonal antibodies internalized antibodies to various degrees. C-terminal and oligomer-selective α-synuclein antibodies reduced the extent of α-synuclein dimerization/oligomerization, as indicated by decreased GFP fluorescence signal. Furthermore, ELISA measurements on lysates and conditioned media from antibody treated cells displayed lower α-synuclein levels compared to untreated cells, suggesting increased protein turnover. Taken together, our results propose that extracellular administration of monoclonal antibodies can modify or inhibit early steps in the aggregation process of α-synuclein, thus providing further support for passive immunization against diseases with α-synuclein pathology.

  1. Recurring polyhedral motifs in the amorphous indium gallium zinc oxide network

    Energy Technology Data Exchange (ETDEWEB)

    Divya; Deepak [Department of Materials Science and Engineering, Indian Institute of Technology, Kanpur (India); National Center for Flexible Electronics, Indian Institute of Technology, Kanpur (India); Prasad, Rajendra [Department of Physics, Indian Institute of Technology, Kanpur (India)

    2017-02-15

    The coordination polyhedra around the cations are the building blocks of ionic solids. For amorphous InGaZn oxide (a-IGZO), these coordination polyhedra are identified to investigate properties that depend on short range interactions. Therefore, in this first principles based study, a large number (10) of samples of a-IGZO were prepared by ab initio melt-and-quench molecular dynamics, so that several distinct samples of the amorphous landscape are obtained corresponding to local minima in energy. Based on a method of comparing bond angles between metal and oxygen atoms, the identified polyhedra were matched to the polyhedral motifs present in the related crystalline systems, such as, InGaZnO{sub 4}, In{sub 2}O{sub 3}, Ga{sub 2}O{sub 3}, and ZnO. Consequently, we find, the a-IGZO primarily consists of the following polyhedra: a tetrahedron from space group 199 and an octahedron from space group 206 of In{sub 2}O{sub 3}; a tetrahedron from space group 12 and an octahedron from space group 167 of Ga{sub 2}O{sub 3}; a tetrahedron from space group 186 of ZnO; zinc and gallium trigonal bipyramids from c-IGZO; and one zinc fourfold, one zinc fivefold, and one indium fivefold coordination polyhedra that occur only in the amorphous phase. Thus, we were able to reduce the description of structure from 360 to 10 groups of polyhedra. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Investigation of prototypal MOFs consisting of polyhedral cages with accessible Lewis-acid sites for quinoline synthesis.

    Science.gov (United States)

    Gao, Wen-Yang; Leng, Kunyue; Cash, Lindsay; Chrzanowski, Matthew; Stackhouse, Chavis A; Sun, Yinyong; Ma, Shengqian

    2015-03-21

    A series of prototypal metal-organic frameworks (MOFs) consisting of polyhedral cages with accessible Lewis-acid sites, have been systematically investigated for Friedländer annulation reaction, a straightforward approach to synthesizing quinoline and its derivatives. Amongst them MMCF-2 demonstrates significantly enhanced catalytic activity compared with the benchmark MOFs, HKUST-1 and MOF-505, as a result of a high-density of accessible Cu(II) Lewis acid sites and large window size in the cuboctahedral cage-based nanoreactor of MMCF-2.

  3. Oligomerization of optically active N-(4-hydroxyphenylmandelamide in the presence of β-cyclodextrin and the minor role of chirality

    Directory of Open Access Journals (Sweden)

    Helmut Ritter

    2014-10-01

    Full Text Available The oxidative oligomerization of a chiral mandelamide derivative (N-(4-hydroxyphenylmandelamide, 1 was performed in the presence of horseradish peroxidase, laccase and N,N'-bis(salicylideneethylenediamine-iron(II to obtain chiral oligophenols 2. The low enantioselectivity of the enzymatic catalyzed asymmetric enantiomer-differentiating oligomerizations was investigated. In addition, the poor influence of cyclodextrin on the enantioselectivity of enzymatic catalyzed asymmetric enantiomer-differentiating oligomerizations was studied.

  4. Polycarbonate-silsesquioxane and polycarbonate-siloxane nanocomposites: Synthesis, characterization, and application in the fabrication of porous inorganic films

    Science.gov (United States)

    Abdallah, Jassem

    Three types of poly(bicycle[2.2.1]heptane carbonate) or poly(norbornane carbonate) or PNC oligomers were synthesized and characterized via spectroscopic methods and elemental analyses to validate their chemical structures. End-group analyses were used to estimate the degree of polymerization of the oligomers via the use of proton nuclear magnetic resonance (1H NMR) results. Random-coil and rigid-rod models were used to estimate the sizes of individual PNC chains based on the degrees of polymerization calculated from NMR data. Due to the small sizes of the PNC chains, dynamic light scattering (DLS) was incapable of measuring the hydrodynamic radii, RH, of individual chains. Attempts at using gel permeation chromatography (GPC) data to estimate the hydrodynamic radii of individual chains consistently provided values that were an order of magnitude smaller than the estimated sizes of individual chains based on random-coil calculations. The thermal properties of PNCs were determined via differential scanning calorimetry (DSC) and thermogravimetric analyses (TGAs). All three types of PNC structures were both thermally-labile and acidolytically-labile, allowing them to be used as sacrificial materials in both direct-write and thermally-processed template systems. TGA data was used to determine the kinetic parameters for the thermolytic decomposition reactions and evolved-gas analysis via mass spectrometry (TGA-MS) was used to validate the mechanisms for polycarbonate thermolysis reactions that have been previously proposed in literature. PNC oligomers were freely-mixed with hydrogen silsesquioxane (HSQ) to form solutions that were spin-coated to form templated films. Ellipsometry and dielectric measurements were used to track the changes in the optical and dielectric properties of templated films and effective medium approximations were used to estimate the level of porosity incorporated within each porous film. Transmission electron microscopy (TEM) showed that the free

  5. A fluorimetric readout reporting the kinetics of nucleotide-induced human ribonucleotide reductase oligomerization.

    Science.gov (United States)

    Fu, Yuan; Lin, Hongyu; Wisitpitthaya, Somsinee; Blessing, William A; Aye, Yimon

    2014-11-24

    Human ribonucleotide reductase (hRNR) is a target of nucleotide chemotherapeutics in clinical use. The nucleotide-induced oligomeric regulation of hRNR subunit α is increasingly being recognized as an innate and drug-relevant mechanism for enzyme activity modulation. In the presence of negative feedback inhibitor dATP and leukemia drug clofarabine nucleotides, hRNR-α assembles into catalytically inert hexameric complexes, whereas nucleotide effectors that govern substrate specificity typically trigger α-dimerization. Currently, both knowledge of and tools to interrogate the oligomeric assembly pathway of RNR in any species in real time are lacking. We therefore developed a fluorimetric assay that reliably reports on oligomeric state changes of α with high sensitivity. The oligomerization-directed fluorescence quenching of hRNR-α, covalently labeled with two fluorophores, allows for direct readout of hRNR dimeric and hexameric states. We applied the newly developed platform to reveal the timescales of α self-assembly, driven by the feedback regulator dATP. This information is currently unavailable, despite the pharmaceutical relevance of hRNR oligomeric regulation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Membrane-mediated oligomerization of G protein coupled receptors and its implications for GPCR function

    Directory of Open Access Journals (Sweden)

    Stefan Gahbauer

    2016-10-01

    Full Text Available The dimerization or even oligomerization of G protein coupled receptors (GPCRs causes ongoing, controversial debates about its functional role and the coupled biophysical, biochemical or biomedical implications. A continously growing number of studies hints to a relation between oligomerization and function of GPCRs and strengthens the assumption that receptor assembly plays a key role in the regulation of protein function. Additionally, progress in the structural analysis of GPCR-G protein and GPCR-ligand interactions allows to distinguish between actively functional and non-signalling complexes. Recent findings further suggest that the surrounding membrane, i.e. its lipid composition may modulate the preferred dimerization interface and as a result the abundance of distinct dimeric conformations. In this review, the association of GPCRs and the role of the membrane in oligomerization will be discussed. An overview of the different reported oligomeric interfaces is provided and their capability for signaling discussed. The currently available data is summarized with regard to the formation of GPCR oligomers, their structures and dependency on the membrane microenvironment as well as the coupling of oligomerization to receptor function.

  7. Biocatalytically Oligomerized Epicatechin with Potent and Specific Anti-proliferative Activity for Human Breast Cancer Cells

    Directory of Open Access Journals (Sweden)

    Ramaswamy Nagarajan

    2008-11-01

    Full Text Available Catechins, naturally occurring flavonoids derived from wine and green tea, are known to exhibit multiple health benefits. Epigallocatechin gallate (EGCG is one of the most widely investigated catechins, but its efficacy in cancer therapy is still inconsistent and limited. The poor stability of EGCG has contributed to the disparity in the reported anti-cancer activity and other beneficial properties. Here we report an innovative enzymatic strategy for the oligomerization of catechins (specifically epicatechin that yields stable, water-soluble oligomerized epicatechins with enhanced and highly specific anti-proliferative activity for human breast cancer cells. This one-pot oxidative oligomerization is carried out in ambient conditions using Horseradish Peroxidase (HRP as a catalyst yielding water-soluble oligo(epicatechins. The oligomerized epicatechins obtained exhibit excellent growth inhibitory effects against human breast cancer cells with greater specificity towards growth-inhibiting cancer cells as opposed to normal cells, achieving a high therapeutic differential. Our studies indicate that water-soluble oligomeric epicatechins surpass EGCG in stability, selectivity and efficacy at lower doses.

  8. Transient oligomerization of the SARS-CoV N protein--implication for virus ribonucleoprotein packaging.

    Science.gov (United States)

    Chang, Chung-ke; Chen, Chia-Min Michael; Chiang, Ming-hui; Hsu, Yen-lan; Huang, Tai-huang

    2013-01-01

    The nucleocapsid (N) phosphoprotein of the severe acute respiratory syndrome coronavirus (SARS-CoV) packages the viral genome into a helical ribonucleocapsid and plays a fundamental role during viral self-assembly. The N protein consists of two structural domains interspersed between intrinsically disordered regions and dimerizes through the C-terminal structural domain (CTD). A key activity of the protein is the ability to oligomerize during capsid formation by utilizing the dimer as a building block, but the structural and mechanistic bases of this activity are not well understood. By disulfide trapping technique we measured the amount of transient oligomers of N protein mutants with strategically located cysteine residues and showed that CTD acts as a primary transient oligomerization domain in solution. The data is consistent with the helical oligomer packing model of N protein observed in crystal. A systematic study of the oligomerization behavior revealed that altering the intermolecular electrostatic repulsion through changes in solution salt concentration or phosphorylation-mimicking mutations affects oligomerization propensity. We propose a biophysical mechanism where electrostatic repulsion acts as a switch to regulate N protein oligomerization.

  9. Transient oligomerization of the SARS-CoV N protein--implication for virus ribonucleoprotein packaging.

    Directory of Open Access Journals (Sweden)

    Chung-ke Chang

    Full Text Available The nucleocapsid (N phosphoprotein of the severe acute respiratory syndrome coronavirus (SARS-CoV packages the viral genome into a helical ribonucleocapsid and plays a fundamental role during viral self-assembly. The N protein consists of two structural domains interspersed between intrinsically disordered regions and dimerizes through the C-terminal structural domain (CTD. A key activity of the protein is the ability to oligomerize during capsid formation by utilizing the dimer as a building block, but the structural and mechanistic bases of this activity are not well understood. By disulfide trapping technique we measured the amount of transient oligomers of N protein mutants with strategically located cysteine residues and showed that CTD acts as a primary transient oligomerization domain in solution. The data is consistent with the helical oligomer packing model of N protein observed in crystal. A systematic study of the oligomerization behavior revealed that altering the intermolecular electrostatic repulsion through changes in solution salt concentration or phosphorylation-mimicking mutations affects oligomerization propensity. We propose a biophysical mechanism where electrostatic repulsion acts as a switch to regulate N protein oligomerization.

  10. Polyhedral meshing as an innovative approach to computational domain discretization of a cyclone in a fluidized bed CLC unit

    Directory of Open Access Journals (Sweden)

    Sosnowski Marcin

    2017-01-01

    Full Text Available Chemical Looping Combustion (CLC is a technology that allows the separation of CO2, which is generated by the combustion of fossil fuels. The majority of process designs currently under investigation are systems of coupled fluidized beds. Advances in the development of power generation system using CLC cannot be introduced without using numerical modelling as a research tool. The primary and critical activity in numerical modelling is the computational domain discretization. It influences the numerical diffusion as well as convergence of the model and therefore the overall accuracy of the obtained results. Hence an innovative approach of computational domain discretization using polyhedral (POLY mesh is proposed in the paper. This method reduces both the numerical diffusion of the mesh as well as the time cost of preparing the model for subsequent calculation. The major advantage of POLY mesh is that each individual cell has many neighbours, so gradients can be much better approximated in comparison to commonly-used tetrahedral (TET mesh. POLYs are also less sensitive to stretching than TETs which results in better numerical stability of the model. Therefore detailed comparison of numerical modelling results concerning subsection of CLC system using tetrahedral and polyhedral mesh is covered in the paper.

  11. Silsesquioxane organofunctionalized with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole: Preparation and subsequent reaction with silver and potassium hexacyanoferrate(III) for detection of L-cysteine

    International Nuclear Information System (INIS)

    Carmo, Devaney R. do; Silvestrini, Daniela R.; Silveira, Tayla F.S. da; Cumba, Loanda R.; Dias Filho, Newton L.; Soares, Layciane A.

    2015-01-01

    The octakis(3-chloropropyl)octasilsesquioxane (SS) was organofunctionalized with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (Purpald). The functionalized silsesquioxane with Purpald (SP) was characterized by Fourier transform infrared spectroscopy (FT-IR), and nuclear magnetic resonance (NMR). After functionalized, silsesquioxane can interact with silver nitrate and subsequently with potassium hexacyanoferrate (III) (AgHSP). The novel hybrid composite formed (AgHSP) was characterized by Fourier transform infrared spectra, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). AgHSP was electrochemically characterized by cyclic voltammetry (CV) using graphite paste electrode. The AgHSP incorporated into a graphite paste electrode (20% w/w) was tested for detection of L-cysteine. The modified electrode showed a linear response from 9.0 × 10 −5 to 5.0 × 10 −3 mol L −1 with the corresponding equation Y(A) = 0.01315 + 1.865 [L-cysteine], and a correlation coefficient of r 2 = 0.9995. The method showed a detection limit of 1.76 × 10 −4 mol L −1 with a relative standard deviation of ± 2% (n = 3) and amperometric sensitivity of 1.865 A/mol L −1 . - Highlights: • Functionalization of silsesquioxane with Purpald compound • Characterization of silsesquioxane was done with FT-IR, NMR, SEM, EDX and VC. • The modified silsesquioxane was interacted with AgNO 3 and K 3 [Fe(CN) 6 ]. • The composite was tested by cyclic voltammetry for detection of L-cysteine

  12. Silsesquioxane organofunctionalized with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole: Preparation and subsequent reaction with silver and potassium hexacyanoferrate(III) for detection of L-cysteine

    Energy Technology Data Exchange (ETDEWEB)

    Carmo, Devaney R. do, E-mail: docarmo@dfq.feis.unesp.br; Silvestrini, Daniela R.; Silveira, Tayla F.S. da; Cumba, Loanda R.; Dias Filho, Newton L.; Soares, Layciane A.

    2015-12-01

    The octakis(3-chloropropyl)octasilsesquioxane (SS) was organofunctionalized with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (Purpald). The functionalized silsesquioxane with Purpald (SP) was characterized by Fourier transform infrared spectroscopy (FT-IR), and nuclear magnetic resonance (NMR). After functionalized, silsesquioxane can interact with silver nitrate and subsequently with potassium hexacyanoferrate (III) (AgHSP). The novel hybrid composite formed (AgHSP) was characterized by Fourier transform infrared spectra, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). AgHSP was electrochemically characterized by cyclic voltammetry (CV) using graphite paste electrode. The AgHSP incorporated into a graphite paste electrode (20% w/w) was tested for detection of L-cysteine. The modified electrode showed a linear response from 9.0 × 10{sup −5} to 5.0 × 10{sup −3} mol L{sup −1} with the corresponding equation Y(A) = 0.01315 + 1.865 [L-cysteine], and a correlation coefficient of r{sup 2} = 0.9995. The method showed a detection limit of 1.76 × 10{sup −4} mol L{sup −1} with a relative standard deviation of ± 2% (n = 3) and amperometric sensitivity of 1.865 A/mol L{sup −1}. - Highlights: • Functionalization of silsesquioxane with Purpald compound • Characterization of silsesquioxane was done with FT-IR, NMR, SEM, EDX and VC. • The modified silsesquioxane was interacted with AgNO{sub 3} and K{sub 3}[Fe(CN){sub 6}]. • The composite was tested by cyclic voltammetry for detection of L-cysteine.

  13. Transient structural distortion of metal-free Cu/Zn superoxide dismutase triggers aberrant oligomerization

    DEFF Research Database (Denmark)

    Teilum, Kaare; Smith, Melanie H; Schulz, Eike

    2009-01-01

    remained enigmatic, however, as is the case in other protein-misfolding diseases. Here, we target the critical conformational change that defines the earliest step toward aggregation. Using nuclear spin relaxation dispersion experiments, we identified a short-lived (0.4 ms) and weakly populated (0.......7%) conformation of metal-depleted SOD1 that triggers aberrant oligomerization. This excited state emanates from the folded ground state and is suppressed by metal binding, but is present in both the disulfide-oxidized and disulfide-reduced forms of the protein. Our results pinpoint a perturbed region......Amyotrophic lateral sclerosis (ALS) is a neurodegenerative disease linked to the misfolding of Cu/Zn superoxide dismutase (SOD1). ALS-related defects in SOD1 result in a gain of toxic function that coincides with aberrant oligomerization. The structural events triggering oligomerization have...

  14. Controlling amyloid-beta peptide(1-42) oligomerization and toxicity by fluorinated nanoparticles.

    Science.gov (United States)

    Saraiva, Ana M; Cardoso, Isabel; Pereira, M Carmo; Coelho, Manuel A N; Saraiva, Maria João; Möhwald, Helmuth; Brezesinski, Gerald

    2010-09-03

    The amyloid-beta peptide (Abeta) is a major fibrillar component of neuritic plaques in Alzheimer's disease brains and is related to the pathogenesis of the disease. Soluble oligomers that precede fibril formation have been proposed as the main neurotoxic species that contributes to neurodegeneration and dementia. We hypothesize that oligomerization and cytotoxicity can be repressed by nanoparticles (NPs) that induce conformational changes in Abeta42. We show here that fluorinated and hydrogenated NPs with different abilities to change Abeta42 conformation influence oligomerization as assessed by atomic force microscopy, immunoblot and SDS-PAGE. Fluorinated NPs, which promote an increase in alpha-helical content, exert an antioligomeric effect, whereas hydrogenated analogues do not and lead to aggregation. Cytotoxicity assays confirmed our hypothesis by indicating that the conformational conversion of Abeta42 into an alpha-helical-enriched secondary structure also has antiapoptotic activity, thereby increasing the viability of cells treated with oligomeric species.

  15. Catalyst-controlled oligomerization for the collective synthesis of polypyrroloindoline natural products.

    Science.gov (United States)

    Jamison, Christopher R; Badillo, Joseph J; Lipshultz, Jeffrey M; Comito, Robert J; MacMillan, David W C

    2017-12-01

    In nature, many organisms generate large families of natural product metabolites that have related molecular structures as a means to increase functional diversity and gain an evolutionary advantage against competing systems within the same environment. One pathway commonly employed by living systems to generate these large classes of structurally related families is oligomerization, wherein a series of enzymatically catalysed reactions is employed to generate secondary metabolites by iteratively appending monomers to a growing serial oligomer chain. The polypyrroloindolines are an interesting class of oligomeric natural products that consist of multiple cyclotryptamine subunits. Herein we describe an iterative application of asymmetric copper catalysis towards the synthesis of six distinct oligomeric polypyrroloindoline natural products: hodgkinsine, hodgkinsine B, idiospermuline, quadrigemine H and isopsychotridine B and C. Given the customizable nature of the small-molecule catalysts employed, we demonstrate that this strategy is further amenable to the construction of quadrigemine H-type alkaloids not isolated previously from natural sources.

  16. N-(1-Pyrenyl Maleimide Induces Bak Oligomerization and Mitochondrial Dysfunction in Jurkat Cells

    Directory of Open Access Journals (Sweden)

    Pei-Rong Huang

    2015-01-01

    Full Text Available N-(1-pyrenyl maleimide (NPM is a fluorescent reagent that is frequently used as a derivatization agent for the detection of thio-containing compounds. NPM has been shown to display a great differential cytotoxicity against hematopoietic cancer cells. In this study, the molecular mechanism by which NPM induces apoptosis was examined. Here, we show that treatment of Jurkat cells with NPM leads to Bak oligomerization, loss of mitochondrial membrane potential (Δψm, and release of cytochrome C from mitochondria to cytosol. Induction of Bak oligomerization appears to play a critical role in NPM-induced apoptosis, as downregulation of Bak by shRNA significantly prevented NPM-induced apoptosis. Inhibition of caspase 8 by Z-IETD-FMK and/or depletion of Bid did not affect NPM-induced oligomerization of Bak. Taken together, these results suggest that NPM-induced apoptosis is mediated through a pathway that is independent of caspase-8 activation.

  17. Zn(2+) site engineering at the oligomeric interface of the dopamine transporter.

    Science.gov (United States)

    Norgaard-Nielsen, Kristine; Norregaard, Lene; Hastrup, Hanne; Javitch, Jonathan A; Gether, Ulrik

    2002-07-31

    Increasing evidence suggests that Na(+)/Cl(-)-dependent neurotransmitter transporters exist as homo-oligomeric proteins. However, the functional implication of this oligomerization remains unclear. Here we demonstrate the engineering of a Zn(2+) binding site at the predicted dimeric interface of the dopamine transporter (DAT) corresponding to the external end of transmembrane segment 6. Upon binding to this site, which involves a histidine inserted in position 310 (V310H) and the endogenous Cys306 within the same DAT molecule, Zn(2+) potently inhibits [(3)H]dopamine uptake. These data provide indirect evidence that conformational changes critical for the translocation process may occur at the interface between two transporter molecules in the oligomeric structure.

  18. osFP: a web server for predicting the oligomeric states of fluorescent proteins.

    Science.gov (United States)

    Simeon, Saw; Shoombuatong, Watshara; Anuwongcharoen, Nuttapat; Preeyanon, Likit; Prachayasittikul, Virapong; Wikberg, Jarl E S; Nantasenamat, Chanin

    2016-01-01

    Currently, monomeric fluorescent proteins (FP) are ideal markers for protein tagging. The prediction of oligomeric states is helpful for enhancing live biomedical imaging. Computational prediction of FP oligomeric states can accelerate the effort of protein engineering efforts of creating monomeric FPs. To the best of our knowledge, this study represents the first computational model for predicting and analyzing FP oligomerization directly from the amino acid sequence. After data curation, an exhaustive data set consisting of 397 non-redundant FP oligomeric states was compiled from the literature. Results from benchmarking of the protein descriptors revealed that the model built with amino acid composition descriptors was the top performing model with accuracy, sensitivity and specificity in excess of 80% and MCC greater than 0.6 for all three data subsets (e.g. training, tenfold cross-validation and external sets). The model provided insights on the important residues governing the oligomerization of FP. To maximize the benefit of the generated predictive model, it was implemented as a web server under the R programming environment. osFP affords a user-friendly interface that can be used to predict the oligomeric state of FP using the protein sequence. The advantage of osFP is that it is platform-independent meaning that it can be accessed via a web browser on any operating system and device. osFP is freely accessible at http://codes.bio/osfp/ while the source code and data set is provided on GitHub at https://github.com/chaninn/osFP/.Graphical Abstract.

  19. Methyl methacrylate oligomerically-modified clay and its poly(methyl methacrylate) nanocomposites

    International Nuclear Information System (INIS)

    Zheng Xiaoxia; Jiang, David D.; Wilkie, Charles A.

    2005-01-01

    A methyl methacrylate oligomerically-modified clay was used to prepare poly(methyl methacrylate) clay nanocomposites by melt blending and the effect of the clay loading level on the modified clay and corresponding nanocomposite was studied. These nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis and cone calorimetry. The results show a mixed intercalated/delaminated morphology with good nanodispersion. The compatibility between the methylacrylate-subsituted clay and poly(methyl methacrylate) (PMMA) are greatly improved compared to other oligomerically-modified clays

  20. Conformational detection of p53's oligomeric state by FlAsH Fluorescence

    OpenAIRE

    Webber, Tawnya M.; Allen, Andrew C.; Ma, Wai Kit; Molloy, Rhett G.; Kettelkamp, Charisse N.; Dow, Caitlin A.; Gage, Matthew J.

    2009-01-01

    The p53 tumor suppressor protein is a critical checkpoint in prevention of tumor formation, and the function of p53 is dependent on proper formation of the active tetramer. In vitro studies have shown that p53 binds DNA most efficiently as a tetramer, though inactive p53 is predicted to be monomeric in vivo. We demonstrate that FlAsH binding can be used to distinguish between oligomeric states of p53, providing a potential tool to explore p53 oligomerization in vivo. The FlAsH tetra-cysteine ...

  1. 40 CFR 721.3100 - Oligomeric silicic acid ester compound with a hy-droxyl-al-kyla-mine.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Oligomeric silicic acid ester compound with a hy-droxyl-al-kyla-mine. 721.3100 Section 721.3100 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.3100 Oligomeric silicic acid ester compound with a...

  2. On the evaluation of the gravity effects of polyhedral bodies and a consistent treatment of related singularities

    Science.gov (United States)

    D'Urso, M. G.

    2013-03-01

    We show that the singularities which can affect the computation of the gravity effects (potential, gravity and tensor gradient fields) can be systematically addressed by invoking distribution theory and suitable formulas of differential calculus. Thus, differently from previous contributions on the subject, the use of a-posteriori corrections of the formulas derived in absence of singularities can be ruled out. The general approach presented in the paper is further specialized to the case of polyhedral bodies and detailed for a rectangular prism having a constant mass density. With reference to this last case, we derive novel expressions for the related gravitational field, as well as for its first and second derivative, at an observation point coincident with a prism vertex and show that they turn out to be more compact than the ones reported in the specialized literature.

  3. Influence of oligomeric resins on traction and rolling resistance of silica tire treads

    NARCIS (Netherlands)

    Vleugels, N.; Pille-Wolf, W.; Dierkes, Wilma K.; Noordermeer, Jacobus W.M.

    2016-01-01

    This study concerns the silica-reinforcement of synthetic rubber compounds for passenger tire treads with the objective to gain insight into the beneficial effects of oligomeric resins, derived from natural and synthetic monomers, on the major tire performance factors: rolling resistance and (wet)

  4. Understanding the Influence of oligomeric resins on traction and rolling resistance of silica tire treads

    NARCIS (Netherlands)

    Vleugels, N.; Pille-Wolf, W.; Dierkes, Wilma K.; Noordermeer, Jacobus W.M.

    2015-01-01

    This study concerns the silica reinforcement of styrene–butadiene rubber compounds for passenger car tire treads, with the objective of gaining greater insight into the beneficial effects of oligomeric resins. The major tire performance factors predicted are rolling resistance and (wet) skid

  5. Influence of oligomeric resins on traction and rolling resistance of silica tire treads

    NARCIS (Netherlands)

    Vleugels, N.; Pille-Wolf, W.; Dierkes, Wilma K.; Noordermeer, Jacobus W.M.

    2013-01-01

    This study concerns the silica-reinforcement of synthetic rubber compounds for passenger tire treads with the objective to gain insight into the beneficial effects of oligomeric resins, derived from natural and synthetic monomers, on the major tire performance factors: Rolling Resistance and (Wet)

  6. Oligomerization of a Glucagon-like Peptide 1 Analog: Bridging Experiment and Simulations

    DEFF Research Database (Denmark)

    Frederiksen, Tine Maja; Sønderby, Pernille; Ryberg, Line A.

    2015-01-01

    The glucagon-like peptide 1 (GLP-1) analog, liraglutide, is a GLP-1 agonist and is used in the treatment of type-2 diabetes mellitus and obesity. From a pharmaceutical perspective, it is important to know the oligomerization state of liraglutide with respect to stability. Compared to GLP-1...

  7. Cobalt Oxide on N-Doped Carbon for 1-Butene Oligomerization to Produce Linear Octenes

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dongting [Department; Xu, Zhuoran [Department; Chada, Joseph P. [Department; Carrero, Carlos A. [Department; Rosenfeld, Devon C. [The Dow Chemical Company, 2301 N. Brazosport Boulevard, Freeport, Texas 77541-3257, United States; Rogers, Jessica L. [The Dow Chemical Company, 2301 N. Brazosport Boulevard, Freeport, Texas 77541-3257, United States; Hermans, Ive [Department; Huber, George W. [Department

    2017-10-02

    Cobalt oxide supported on N-doped carbon catalysts were investigated for 1-butene oligomerization. The materials were synthesized by treating activated carbon with nitric acid and subsequently with NH3 at 200, 400, 600, and 800 °C, followed by impregnation with cobalt. The 1-butene oligomerization selectivity increased with ammonia treatment temperature of the carbon support. The oligomerization selectivity of cobalt oxide on N-doped carbon synthesized at 800 °C (800A-CoOx/N-C) is 2.6 times higher than previously reported cobalt oxide on N-doped carbon synthesized with NH4OH (2A-CoOx/N-C). Over 70% of the butene dimers were linear C8 olefins for all catalysts. The oligomerization selectivity increased with 1-butene conversion. The catalysts were characterized by elemental analysis, N2 adsorption, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). The nitrogen content of the catalysts increases with ammonia treatment temperature as confirmed by elemental analysis. The surface content of pyridinic nitrogen with a binding energy of 398.4 ± 0.1 eV increased with ammonia treatment temperature as evidenced by deconvolution of N 1s XPS spectra.

  8. Pro-inflammatory delipidizing cytokines reduce adiponectin secretion from human adipocytes without affecting adiponectin oligomerization

    NARCIS (Netherlands)

    Simons, Peter J.; van den Pangaart, Petra S.; Aerts, Johannes M. F. G.; Boon, Louis

    2007-01-01

    Adiponectin and, especially, its oligomeric complex composition have been suggested to be critical in determining insulin sensitivity. Pro-inflammatory cytokines play an important role in the development of insulin resistance in obesity and associated diseases. Therefore, we investigated the effect

  9. Mechanics of the mannitol transporter from Escherichia coli : substrate-probing and oligomeric structure

    NARCIS (Netherlands)

    Veldhuis, Gertjan

    2006-01-01

    Gertjan Veldhuis bestudeerde de mannitoltransporter van Escherichia coli, EnzymeIImtl (EIImtl), om meer inzicht te krijgen in het bindingsmechanisme en de oligomere toestand van dit membraaneiwit. Hij concludeerde onder andere dat dimeer EIImtl één mannitol bindt, de dimeer zeer stabiel is en dat

  10. RIG-I self-oligomerization is either dispensable or very transient for signal transduction.

    Directory of Open Access Journals (Sweden)

    Jade Louber

    Full Text Available Effective host defence against viruses depends on the rapid triggering of innate immunity through the induction of a type I interferon (IFN response. To this end, microbe-associated molecular patterns are detected by dedicated receptors. Among them, the RIG-I-like receptors RIG-I and MDA5 activate IFN gene expression upon sensing viral RNA in the cytoplasm. While MDA5 forms long filaments in vitro upon activation, RIG-I is believed to oligomerize after RNA binding in order to transduce a signal. Here, we show that in vitro binding of synthetic RNA mimicking that of Mononegavirales (Ebola, rabies and measles viruses leader sequences to purified RIG-I does not induce RIG-I oligomerization. Furthermore, in cells devoid of endogenous functional RIG-I-like receptors, after activation of exogenous Flag-RIG-I by a 62-mer-5'ppp-dsRNA or by polyinosinic:polycytidylic acid, a dsRNA analogue, or by measles virus infection, anti-Flag immunoprecipitation and specific elution with Flag peptide indicated a monomeric form of RIG-I. Accordingly, when using the Gaussia Luciferase-Based Protein Complementation Assay (PCA, a more sensitive in cellula assay, no RIG-I oligomerization could be detected upon RNA stimulation. Altogether our data indicate that the need for self-oligomerization of RIG-I for signal transduction is either dispensable or very transient.

  11. A silica-supported double-decker silsesquioxane provides a second skin for the selective generation of bipodal surface organometallic complexes

    KAUST Repository

    Espinas, Jeff

    2012-11-12

    A well-defined silica-based material with a homogeneous nanolayer presenting identical pairs of vicinal silanols has been prepared by reaction of the surface organometallic species [≡SiOZr(CH 2CMe 3) 3], obtained on a silica dehydroxylated at 900 °C, with the double-decker-shaped silsesquioxane (OH) 2DD(OH) 2. The surface structure has been established using extensive NMR characterization ( 1H, 13C, 29Si, HETCOR, double-quantum, triple-quantum). Treatment with Zr(CH 2CMe 3) 4 leads to the first well-defined single-site bipodal grafted bis-neopentyl zirconium complex. © 2012 American Chemical Society.

  12. Silsesquioxane-based hybrid nanocomposites with methacrylate units containing titania and/or silver nanoparticles as antibacterial/antifungal coatings for monumental stones

    Energy Technology Data Exchange (ETDEWEB)

    Aflori, Magdalena [“Petru Poni” Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, 700487 Iasi (Romania); Simionescu, Bogdana [“Petru Poni” Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, 700487 Iasi (Romania); “Costin D. Nenitescu” Centre of Organic Chemistry, 202B Splaiul Independentei, 7114 Bucharest (Romania); Bordianu, Irina-Elena; Sacarescu, Liviu; Varganici, Cristian-Dragos; Doroftei, Florica; Nicolescu, Alina [“Petru Poni” Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, 700487 Iasi (Romania); Olaru, Mihaela, E-mail: olaruma@icmpp.ro [“Petru Poni” Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, 700487 Iasi (Romania)

    2013-11-20

    Highlights: • Synthesis of nanocomposites with noble metals having high antibacterial efficiency. • Silver nanoparticles antibacterial activity for monumental stone conservation. • A high antibacterial activity while assuring good stone protection. -- Abstract: The present paper reports on the evaluation of two silsesquioxane-based hybrid nanocomposites with methacrylate units containing titania and/or silver nanoparticles aimed as antibacterial coatings for monumental stones. Sol–gel reaction of titanium isopropoxide and/or 3-(trimethoxysilyl)propyl methacrylate, in the presence of silver nitrate and a primary amine surfactant, yielded new types of hybrid nanocomposites with high antibacterial/antifungal efficacy. Different polymer behaviours regarding a frequently used monumental stone originating from Romania were evidenced through Fourier-transform infrared (FTIR) spectroscopy and powder X-ray diffraction (PXRD) technique. Conclusions regarding the stones acid-resistant character and lower influence of salt weathering on its durability, as well as a better protective coating containing titania units were revealed.

  13. Silsesquioxane-based hybrid nanocomposites with methacrylate units containing titania and/or silver nanoparticles as antibacterial/antifungal coatings for monumental stones

    International Nuclear Information System (INIS)

    Aflori, Magdalena; Simionescu, Bogdana; Bordianu, Irina-Elena; Sacarescu, Liviu; Varganici, Cristian-Dragos; Doroftei, Florica; Nicolescu, Alina; Olaru, Mihaela

    2013-01-01

    Highlights: • Synthesis of nanocomposites with noble metals having high antibacterial efficiency. • Silver nanoparticles antibacterial activity for monumental stone conservation. • A high antibacterial activity while assuring good stone protection. -- Abstract: The present paper reports on the evaluation of two silsesquioxane-based hybrid nanocomposites with methacrylate units containing titania and/or silver nanoparticles aimed as antibacterial coatings for monumental stones. Sol–gel reaction of titanium isopropoxide and/or 3-(trimethoxysilyl)propyl methacrylate, in the presence of silver nitrate and a primary amine surfactant, yielded new types of hybrid nanocomposites with high antibacterial/antifungal efficacy. Different polymer behaviours regarding a frequently used monumental stone originating from Romania were evidenced through Fourier-transform infrared (FTIR) spectroscopy and powder X-ray diffraction (PXRD) technique. Conclusions regarding the stones acid-resistant character and lower influence of salt weathering on its durability, as well as a better protective coating containing titania units were revealed

  14. A silica-supported double-decker silsesquioxane provides a second skin for the selective generation of bipodal surface organometallic complexes

    KAUST Repository

    Espinas, Jeff; Pelletier, Jeremie; Abou-Hamad, Edy; Emsley, Lyndon; Basset, Jean-Marie

    2012-01-01

    A well-defined silica-based material with a homogeneous nanolayer presenting identical pairs of vicinal silanols has been prepared by reaction of the surface organometallic species [≡SiOZr(CH 2CMe 3) 3], obtained on a silica dehydroxylated at 900 °C, with the double-decker-shaped silsesquioxane (OH) 2DD(OH) 2. The surface structure has been established using extensive NMR characterization ( 1H, 13C, 29Si, HETCOR, double-quantum, triple-quantum). Treatment with Zr(CH 2CMe 3) 4 leads to the first well-defined single-site bipodal grafted bis-neopentyl zirconium complex. © 2012 American Chemical Society.

  15. Concentration-dependent oligomerization of cross-linked complexes between ferredoxin and ferredoxin–NADP+ reductase

    International Nuclear Information System (INIS)

    Kimata-Ariga, Yoko; Kubota-Kawai, Hisako; Lee, Young-Ho; Muraki, Norifumi; Ikegami, Takahisa; Kurisu, Genji; Hase, Toshiharu

    2013-01-01

    Highlights: •Cross-linked complexes of ferredoxin (Fd) and Fd–NADP + reductase form oligomers. •In the crystal structures, Fd- and FNR moieties swap across the molecules. •The complexes exhibit concentration-dependent oligomerization at sub-milimolar order. -- Abstract: Ferredoxin–NADP + reductase (FNR) forms a 1:1 complex with ferredoxin (Fd), and catalyzes the electron transfer between Fd and NADP + . In our previous study, we prepared a series of site-specifically cross-linked complexes of Fd and FNR, which showed diverse electron transfer properties. Here, we show that X-ray crystal structures of the two different Fd–FNR cross-linked complexes form oligomers by swapping Fd and FNR moieties across the molecules; one complex is a dimer from, and the other is a successive multimeric form. In order to verify whether these oligomeric structures are formed only in crystal, we investigated the possibility of the oligomerization of these complexes in solution. The mean values of the particle size of these cross-linked complexes were shown to increase with the rise of protein concentration at sub-milimolar order, whereas the size of dissociable wild-type Fd:FNR complex was unchanged as analyzed by dynamic light scattering measurement. The oligomerization products were detected by SDS–PAGE after chemical cross-linking of these complexes at the sub-milimolar concentrations. The extent and concentration-dependent profile of the oligomerizaion were differentiated between the two cross-linked complexes. These results show that these Fd–FNR cross-linked complexes exhibit concentration-dependent oligomerization, possibly through swapping of Fd and FNR moieties also in solution. These findings lead to the possibility that some native multi-domain proteins may present similar phenomenon in vivo

  16. DNA structure modulates the oligomerization properties of the AAV initiator protein Rep68.

    Directory of Open Access Journals (Sweden)

    Jorge Mansilla-Soto

    2009-07-01

    Full Text Available Rep68 is a multifunctional protein of the adeno-associated virus (AAV, a parvovirus that is mostly known for its promise as a gene therapy vector. In addition to its role as initiator in viral DNA replication, Rep68 is essential for site-specific integration of the AAV genome into human chromosome 19. Rep68 is a member of the superfamily 3 (SF3 helicases, along with the well-studied initiator proteins simian virus 40 large T antigen (SV40-LTag and bovine papillomavirus (BPV E1. Structurally, SF3 helicases share two domains, a DNA origin interaction domain (OID and an AAA(+ motor domain. The AAA(+ motor domain is also a structural feature of cellular initiators and it functions as a platform for initiator oligomerization. Here, we studied Rep68 oligomerization in vitro in the presence of different DNA substrates using a variety of biophysical techniques and cryo-EM. We found that a dsDNA region of the AAV origin promotes the formation of a complex containing five Rep68 subunits. Interestingly, non-specific ssDNA promotes the formation of a double-ring Rep68, a known structure formed by the LTag and E1 initiator proteins. The Rep68 ring symmetry is 8-fold, thus differing from the hexameric rings formed by the other SF3 helicases. However, similiar to LTag and E1, Rep68 rings are oriented head-to-head, suggesting that DNA unwinding by the complex proceeds bidirectionally. This novel Rep68 quaternary structure requires both the DNA binding and AAA(+ domains, indicating cooperativity between these regions during oligomerization in vitro. Our study clearly demonstrates that Rep68 can oligomerize through two distinct oligomerization pathways, which depend on both the DNA structure and cooperativity of Rep68 domains. These findings provide insight into the dynamics and oligomeric adaptability of Rep68 and serve as a step towards understanding the role of this multifunctional protein during AAV DNA replication and site-specific integration.

  17. Aquaporin-Based Biomimetic Polymeric Membranes: Approaches and Challenges

    DEFF Research Database (Denmark)

    Habel, Joachim Erich Otto; Hansen, Michael; Kynde, Søren

    2015-01-01

    In recent years, aquaporin biomimetic membranes (ABMs) for water separation have gained considerable interest. Although the first ABMs are commercially available, there are still many challenges associated with further ABM development. Here, we discuss the interplay of the main components of ABMs...... thin film interfacial polymerization techniques. Finally, we describe some new developments in interfacial polymerization using polyhedral oligomeric silsesquioxane cages for increasing the physical and chemical durability of thin film composite membranes.......In recent years, aquaporin biomimetic membranes (ABMs) for water separation have gained considerable interest. Although the first ABMs are commercially available, there are still many challenges associated with further ABM development. Here, we discuss the interplay of the main components of ABMs...... for investigating AQP incorporation including freeze-fracture transmission electron microscopy, fluorescence correlation spectroscopy, stopped-flow light scattering, and small-angle X-ray scattering. Third, we focus on recent efforts in embedding reconstituted AQPs in membrane designs that are based on conventional...

  18. Synthesis of POSS-based ionic conductors with low glass transition temperatures for efficient solid-state dye-sensitized solar cells.

    Science.gov (United States)

    Zhang, Wei; Wang, Zhong-Sheng

    2014-07-09

    Replacing liquid-state electrolytes with solid-state electrolytes has been proven to be an effective way to improve the durability of dye-sensitized solar cells (DSSCs). We report herein the synthesis of amorphous ionic conductors based on polyhedral oligomeric silsesquioxane (POSS) with low glass transition temperatures for solid-state DSSCs. As the ionic conductor is amorphous and in the elastomeric state at the operating temperature of DSSCs, good pore filling in the TiO2 film and good interfacial contact between the solid-state electrolyte and the TiO2 film can be guaranteed. When the POSS-based ionic conductor containing an allyl group is doped with only iodine as the solid-state electrolyte without any other additives, power conversion efficiency of 6.29% has been achieved with good long-term stability under one-sun soaking for 1000 h.

  19. Anhydrous proton conducting composite membranes containing Nafion and triazole modified POSS

    International Nuclear Information System (INIS)

    Lei, M.; Wang, Y.G.; Zhang, F.F.; Huang, C.; Xu, X.; Zhang, R.; Fan, D.Y.

    2014-01-01

    Development of membrane electrolytes having reasonable proton conductivity and mechanical strength under anhydrous conditions is of great importance for proton exchange membrane fuel cells operated at elevated temperature. With the introduction of triazole modified polyhedral oligomeric silsesquioxanes (Tz-POSS) into Nafion membrane, the formed composite electrolytes exhibit improved mechanical properties compared to pristine Nafion membrane due to the well distribution of Tz-POSS inside the membrane. The anhydrous proton conductivity of the formed composite membranes increases initially with the increase in temperature, reaching about 0.02 Scm −1 at 140 °C. With further increase in temperature to about 150 °C, the composite membrane reaches its glass transition point above which the proton conductivity decreases dramatically. The performance of assembled single cell from composite membrane is slightly dependent on humidification conditions at 95 °C, reaching 0.45 V at 600 mAcm −2 using hydrogen and oxygen as reaction gases

  20. Self-Assembly Behavior and pH-Stimuli-Responsive Property of POSS-Based Amphiphilic Block Copolymers in Solution

    Directory of Open Access Journals (Sweden)

    Yiting Xu

    2018-05-01

    Full Text Available Stimuli-responsive polymeric systems containing special responsive moieties can undergo alteration of chemical structures and physical properties in response to external stimulus. We synthesized a hybrid amphiphilic block copolymer containing methoxy polyethylene glycol (MePEG, methacrylate isobutyl polyhedral oligomeric silsesquioxane (MAPOSS and 2-(diisopropylaminoethyl methacrylate (DPA named MePEG-b-P(MAPOSS-co-DPA via atom transfer radical polymerization (ATRP. Spherical micelles with a core-shell structure were obtained by a self-assembly process based on MePEG-b-P(MAPOSS-co-DPA, which showed a pH-responsive property. The influence of hydrophobic chain length on the self-assembly behavior was also studied. The pyrene release properties of micelles and their ability of antifouling were further studied.

  1. Novel elastomer dye-functionalised POSS nanocomposites: Enhanced colourimetric, thermomechanical and thermal properties

    Directory of Open Access Journals (Sweden)

    R. A. Shanks

    2012-05-01

    Full Text Available Nanocomposites consisting of poly(styrene-b-butadiene-b-styrene (SBS and polyhedral oligomeric silsesquioxanes (POSS were prepared using a solvent dispersion method. POSS molecules were functionalised with two dichlorotriazine reactive dyes (CI Reactive Blue 4, CI Reactive Red 2 prior to compounding. Infrared spectroscopy confirmed functionalisation.Scanning electron microscopy revealed an increase in filler aggregation with concentration, with preferential phase selectivity. Ultraviolet spectroscopy and colourimetry confirmed colour uniformity and suggested that colour intensity could be controlled. Functionalised POSS improved thermal stability by imparting restrictions on SBS chain motions. Tensile stress-strain analysis revealed an increase in modulus with filler concentration, while creep deformation decreased and permanent strain increased with POSS content. Storage modulus, loss modulus and glass transition temperature increased with filler content due to effective SBS-POSS interaction. Nanocomposite properties were influenced by the phase the filler was dispersed throughout and the structure of the dye chromophore.

  2. Aquaporin-Based Biomimetic Polymeric Membranes: Approaches and Challenges

    Science.gov (United States)

    Habel, Joachim; Hansen, Michael; Kynde, Søren; Larsen, Nanna; Midtgaard, Søren Roi; Jensen, Grethe Vestergaard; Bomholt, Julie; Ogbonna, Anayo; Almdal, Kristoffer; Schulz, Alexander; Hélix-Nielsen, Claus

    2015-01-01

    In recent years, aquaporin biomimetic membranes (ABMs) for water separation have gained considerable interest. Although the first ABMs are commercially available, there are still many challenges associated with further ABM development. Here, we discuss the interplay of the main components of ABMs: aquaporin proteins (AQPs), block copolymers for AQP reconstitution, and polymer-based supporting structures. First, we briefly cover challenges and review recent developments in understanding the interplay between AQP and block copolymers. Second, we review some experimental characterization methods for investigating AQP incorporation including freeze-fracture transmission electron microscopy, fluorescence correlation spectroscopy, stopped-flow light scattering, and small-angle X-ray scattering. Third, we focus on recent efforts in embedding reconstituted AQPs in membrane designs that are based on conventional thin film interfacial polymerization techniques. Finally, we describe some new developments in interfacial polymerization using polyhedral oligomeric silsesquioxane cages for increasing the physical and chemical durability of thin film composite membranes. PMID:26264033

  3. Space Environmental Effects on Coated Tether Materials

    Science.gov (United States)

    Gittemeier, Keith A.; Hawk, Clark W.; Finckenor, Miria M.; Watts, Ed

    2005-01-01

    The University of Alabama in Huntsville s Propulsion Research Center has teamed with NASA's Marshall Space Flight Center (MSFC) to research the effects of atomic oxygen (AO) bombardment on coated tether materials. Tethers Unlimited Inc. has provided several candidate tether materials with various coatings for AO exposure in MSFC s Atomic Oxygen Beam Facility. Additional samples were exposed to ultraviolet (UV) radiation at MSFC. AO erodes most organic materials, and ultraviolet radiation embrittles polymers. This test series was performed to determine the effect of AO and UV on the mechanical integrity of tether materials that were treated with AO-protective coatings, such as polyhedral oligomeric silsesquioxane (POSS) or metallization. Both TUI's Multi-Application Survivable Tether (MAST) Experiment and Marshall Space Flight Center s Momentum Exchange Electrodynamic Reboost (MXER) programs will benefit from this research by helping to determine tether materials and coatings that give the longest life with the lowest mass penalty.

  4. PREPARATION AND PROPERTIES OF MMA/1-PROPYLMETHACRYLATE-POSS COPOLYMER WITH ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    He-xin Zhang; Ho-young Lee; Young-jun Shin; Dong-ho Lee; Seok Kyun Noh

    2008-01-01

    The methyl methacrylate(MMA)/1-propylmethacrylate-polyhedral oligomeric silsesquioxane(PM-POSS) copolymers were synthesized via atom transfer radical polymerization with CuBr as catalyst.The unreacted PM-POSS monomer could be removed completely by washing the copolymerization product with n-hexane.The copolymers were characterized with 1H-NMR,X-ray diffraction,difierential scanning calorimetry,thermogravimetric analysis and gel permeatlon chromatography.With increasing PM-POSS feed ratio.the total conversion increased while the glass transition temperatures of copolymer decreased.The thermogravimetric analysis demonstrated that the thermal stability of copolymer improved slightly with PM-POSS addition.The molecular weight of copolymers increased with incorporation of PM-POSS.

  5. Liquid Crystal Microlens Using Nanoparticle-Induced Vertical Alignment

    Directory of Open Access Journals (Sweden)

    Shug-June Hwang

    2015-01-01

    Full Text Available The nanoparticle-induced vertical alignment (NIVA of the nematic liquid crystals (LC is applied to achieve an adaptive flat LC microlens with hybrid-aligned nematic (HAN mode by dropping polyhedral oligomeric silsesquioxane (POSS nanoparticle solution on a homogeneous alignment layer. The vertical alignment induced by the POSS nanoparticles resulted in the formation of a hybrid-aligned LC layer with concentric nonuniform distribution of the refractive index in the planar LC cell, which subsequently played the role of the lens, even in the absence of any applied voltages. The dimensions of the concentric HAN structure significantly depend on the volume of the microdroplet and the POSS concentration. The focus effect of this flat microlens was observed while electrically controlling its focal length using the applied voltages from −50 mm to −90 mm.

  6. Tangible nanocomposites with diverse properties for heart valve application

    Science.gov (United States)

    Vignesh Vellayappan, Muthu; Balaji, Arunpandian; Priyadarshini Subramanian, Aruna; Aruna John, Agnes; Jaganathan, Saravana Kumar; Murugesan, Selvakumar; Mohandas, Hemanth; Supriyanto, Eko; Yusof, Mustafa

    2015-06-01

    Cardiovascular disease claims millions of lives every year throughout the world. Biomaterials are used widely for the treatment of this fatal disease. With the advent of nanotechnology, the use of nanocomposites has become almost inevitable in the field of biomaterials. The versatile properties of nanocomposites, such as improved durability and biocompatibility, make them an ideal choice for various biomedical applications. Among the various nanocomposites, polyhedral oligomeric silsesquioxane-poly(carbonate-urea)urethane, bacterial cellulose with polyvinyl alcohol, carbon nanotubes, graphene oxide and nano-hydroxyapatite nanocomposites have gained popularity as putative choices for biomaterials in cardiovascular applications owing to their superior properties. In this review, various studies performed utilizing these nanocomposites for improving the mechanical strength, anti-calcification potential and hemocompatibility of heart valves are reviewed and summarized. The primary motive of this work is to shed light on the emerging nanocomposites for heart valve applications. Furthermore, we aim to promote the prospects of these nanocomposites in the campaign against cardiovascular diseases.

  7. Screening of drugs inhibiting in vitro oligomerization of Cu/Zn-superoxide dismutase with a mutation causing amyotrophic lateral sclerosis

    Directory of Open Access Journals (Sweden)

    Itsuki Anzai

    2016-08-01

    Full Text Available Dominant mutations in Cu/Zn-superoxide dismutase (SOD1 gene have been shown to cause a familial form of amyotrophic lateral sclerosis (SOD1-ALS. A major pathological hallmark of this disease is abnormal accumulation of mutant SOD1 oligomers in the affected spinal motor neurons. While no effective therapeutics for SOD1-ALS is currently available, SOD1 oligomerization will be a good target for developing cures of this disease. Recently, we have reproduced the formation of SOD1 oligomers abnormally cross-linked via disulfide bonds in a test tube. Using our in vitro model of SOD1 oligomerization, therefore, we screened 640 FDA-approved drugs for inhibiting the oligomerization of SOD1 proteins, and three effective classes of chemical compounds were identified. Those hit compounds will provide valuable information on the chemical structures for developing a novel drug candidate suppressing the abnormal oligomerization of mutant SOD1 and possibly curing the disease.

  8. Hydration effect on the electronic transport properties of oligomeric phenylene ethynylene molecular junctions

    International Nuclear Information System (INIS)

    Zong-Liang, Li; Huai-Zhi, Li; Yong, Ma; Guang-Ping, Zhang; Chuan-Kui, Wang

    2010-01-01

    A first-principles computational method based on the hybrid density functional theory is developed to simulate the electronic transport properties of oligomeric phenylene ethynylene molecular junctions with H 2 O molecules accumulated in the vicinity as recently reported by Na et al. [Nanotechnology 18 424001 (2007)]. The numerical results show that the hydrogen bonds between the oxygen atoms of the oligomeric phenylene ethynylene molecule and H 2 O molecules result in the localisation of the molecular orbitals and lead to the lower transition peaks. The H 2 O molecular chains accumulated in the vicinity of the molecular junction can not only change the electronic structure of the molecular junctions, but also open additional electronic transport pathways. The obvious influence of H 2 O molecules on the electronic structure of the molecular junction and its electronic transport properties is thus demonstrated. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  9. Receptor oligomerization in family B1 of G-protein-coupled receptors

    DEFF Research Database (Denmark)

    Roed, Sarah Norklit; Ørgaard, Anne; Jørgensen, Rasmus

    2012-01-01

    , the glucagon receptor, and the receptors for parathyroid hormone (PTHR1 and PTHR2). The dysregulation of several family B1 receptors is involved in diseases, such as diabetes, chronic inflammation, and osteoporosis which underlines the pathophysiological importance of this GPCR subfamily. In spite of this......, investigation of family B1 receptor oligomerization and especially its pharmacological importance is still at an early stage. Even though GPCR oligomerization is a well-established phenomenon, there is a need for more investigations providing a direct link between these interactions and receptor functionality......The superfamily of the seven transmembrane G-protein-coupled receptors (7TM/GPCRs) is the largest family of membrane-associated receptors. GPCRs are involved in the pathophysiology of numerous human diseases, and they constitute an estimated 30-40% of all drug targets. During the last two decades...

  10. Domain architecture and oligomerization properties of the paramyxovirus PIV 5 hemagglutinin-neuraminidase (HN) protein.

    Science.gov (United States)

    Yuan, Ping; Leser, George P; Demeler, Borries; Lamb, Robert A; Jardetzky, Theodore S

    2008-09-01

    The mechanism by which the paramyxovirus hemagglutinin-neuraminidase (HN) protein couples receptor binding to activation of virus entry remains to be fully understood, but the HN stalk is thought to play an important role in the process. We have characterized ectodomain constructs of the parainfluenza virus 5 HN to understand better the underlying architecture and oligomerization properties that may influence HN functions. The PIV 5 neuraminidase (NA) domain is monomeric whereas the ectodomain forms a well-defined tetramer. The HN stalk also forms tetramers and higher order oligomers with high alpha-helical content. Together, the data indicate that the globular NA domains form weak intersubunit interactions at the end of the HN stalk tetramer, while stabilizing the stalk and overall oligomeric state of the ectodomain. Electron microscopy of the HN ectodomain reveals flexible arrangements of the NA and stalk domains, which may be important for understanding how these two HN domains impact virus entry.

  11. Anesthetic propofol attenuates the isoflurane-induced caspase-3 activation and Aβ oligomerization.

    Directory of Open Access Journals (Sweden)

    Yiying Zhang

    Full Text Available Accumulation and deposition of β-amyloid protein (Aβ are the hallmark features of Alzheimer's disease. The inhalation anesthetic isoflurane has been shown to induce caspase activation and increase Aβ accumulation. In addition, recent studies suggest that isoflurane may directly promote the formation of cytotoxic soluble Aβ oligomers, which are thought to be the key pathological species in AD. In contrast, propofol, the most commonly used intravenous anesthetic, has been reported to have neuroprotective effects. We therefore set out to compare the effects of isoflurane and propofol alone and in combination on caspase-3 activation and Aβ oligomerization in vitro and in vivo. Naïve and stably-transfected H4 human neuroglioma cells that express human amyloid precursor protein, the precursor for Aβ; neonatal mice; and conditioned cell culture media containing secreted human Aβ40 or Aβ42 were treated with isoflurane and/or propofol. Here we show for the first time that propofol can attenuate isoflurane-induced caspase-3 activation in cultured cells and in the brain tissues of neonatal mice. Furthermore, propofol-mediated caspase inhibition occurred when there were elevated levels of Aβ. Finally, isoflurane alone induces Aβ42, but not Aβ40, oligomerization, and propofol can inhibit the isoflurane-mediated oligomerization of Aβ42. These data suggest that propofol may mitigate the caspase-3 activation by attenuating the isoflurane-induced Aβ42 oligomerization. Our findings provide novel insights into the possible mechanisms of isoflurane-induced neurotoxicity that may aid in the development of strategies to minimize potential adverse effects associated with the administration of anesthetics to patients.

  12. Characterization and ageing study of poly(lactic acid) films plasticized with oligomeric lactic acid

    OpenAIRE

    Burgos, Nuria; Martino, Verónica P.; Jiménez, Alfonso

    2013-01-01

    Poly(lactic acid) (PLA) was melt-blended with a bio-based oligomeric lactic acid (OLA) plasticizer at different concentrations between 15 wt% and 25 wt% in order to enhance PLA ductility and to get a fully biodegradable material with potential application in films manufacturing. OLA was an efficient plasticizer for PLA, as it caused a significant decrease on glass transition temperature (Tg) while improving considerably ductile properties. Only one Tg value was observed in all cases and no ap...

  13. An Investigation of Chemical Landscapes in Aqueous Electrosprays by Tracking Oligomerization of Isoprene

    KAUST Repository

    Junior, Adair Gallo

    2017-12-01

    Electrospray ionization mass spectrometry (ESIMS) is widely used to characterize neutral and ionic species in solvents. Typically, electrical, thermal, and pneumatic potentials are applied to create electrosprays from which charged ionic species are ejected for downstream analysis by mass spectrometry. Most recently, ESIMS has been exploited to investigate ambient proton transfer reactions at air-water interfaces in real time. We assessed the validity of these experiments via complementary laboratory experiments. Specifically, we characterized the products of two reaction scenarios via ESIMS and proton nuclear magnetic resonance (1H-NMR): (i) emulsions of pH-adjusted water and isoprene (C5H8) that were mechanically agitated, and (ii) electrosprays of pH-adjusted water that were collided with gas-phase isoprene. Our experiments unambiguously demonstrate that, while isoprene does not oligomerize in emulsions, it does undergo protonation and oligomerization in electrosprays, both with and without pH-adjusted water, confirming that C-C bonds form along myriad high-energy pathways during electrospray ionization. We also compared our experimental results with some quantum mechanics simulations of isoprene molecules interacting with hydronium at different hydration levels (gas versus liquid phase). In agreement with our experiments, the kinetic barriers to protonation and oligomerization of isoprene were inaccessible under ambient conditions. Rather, the gas-phase chemistries during electrospray ionization drove the oligomerization of isoprene. Therefore, we consider that ESIMS could induce artifacts in interfacial reactions. These findings warrant a reassessment of previous reports on tracking chemistries under ambient conditions at liquid-vapor interfaces via ESIMS. Further, we took some high-speed images of electrosprays where it was possible to observe the main characteristics of the phenomena, i.e. Taylor cone, charge separation, and Coulomb fission. Finally, we took

  14. Stability of human interferon-beta 1: oligomeric human interferon-beta 1 is inactive but is reactivated by monomerization.

    Science.gov (United States)

    Utsumi, J; Yamazaki, S; Kawaguchi, K; Kimura, S; Shimizu, H

    1989-10-05

    Human interferon-beta 1 is extremely stable is a low ionic strength solution of pH 2 such as 10 mM HCl at 37 degrees C. However, the presence of 0.15 M NaCl led to a remarkable loss of antiviral activity. The molecular-sieve high-performance liquid chromatography revealed that, whereas completely active human interferon-beta 1 eluted as a 25 kDa species (monomeric form), the inactivated preparation eluted primarily as a 90 kDa species (oligomeric form). The specific activity (units per mg protein) of the oligomeric form was approx. 10% of that of the monomeric form. This observation shows that oligomeric human interferon-beta 1 is apparently in an inactive form. When the oligomeric eluate was resolved by polyacrylamide gel containing sodium dodecyl sulphate (SDS), it appeared to be monomeric under non-reducing conditions. Monomerization of the oligomeric human interferon-beta 1 by treatment with 1% SDS, fully regenerated its antiviral activity. These results suggest that the inactivation of the human interferon-beta 1 preparation was caused by its oligomerization via hydrophobic interactions without the formation of intermolecular disulphide bonds. These oligomers can be dissociated by SDS to restore biological activity.

  15. Effect Of Oligomeric Enteral Nutrition On Symptoms Of Acute Radiation Enteritis

    International Nuclear Information System (INIS)

    Dubinsky, P.

    2008-01-01

    Radiotherapy of abdominal and pelvic tumours is frequently associated with acute radiation enteritis. Predominant symptoms include diarrhea, watery stools, abdominal pain, nausea and vomiting. There are very few effective interventions available for this condition. Enteral oligomeric nutrition has been used in bowel diseases with functional failure similar to radiation enteritis. The aim of presented work was to observe occurrence of symptoms of radiation enteritis in patients undergoing abdominal or pelvic radiotherapy. Apart from diet and pharmacological therapy, oral oligomeric enteral nutrition (Peptisorb Powder Nutricia) at the dose of 1000 - 2000 ml per day was administered for minimum of 4 days. Planned period of administration was 14 days and longer. Symptoms of radiation enteritis were evaluated at the beginning and in the end of administration. Prevalence of all evaluated symptoms of radiation enteritis was decreased and difference was statistically significant for diarrhea, watery stools, abdominal pain, nausea and vomiting. The use of evaluated oligomeric nutritional support might, in conjunction with pharmacotherapy and diet, alleviate symptoms of acute radiation enteritis and maintain nutritional status of patients. (author)

  16. Chemical activation of bituminous coal for hampering oligomerization of organic contaminants.

    Science.gov (United States)

    Yan, Liang; Sorial, George A

    2011-12-15

    Activated carbons prepared by KOH activation of bituminous coal were studied for hampering oligomerization of phenolic compounds on its surface. A total of 24 activated carbons with different microporosity and BET surface area were created. The effect of the different variables of the activation process (KOH/bituminous coal ratio, heating temperature, activation time, and flow rate of nitrogen gas) on critical carbon parameters was analyzed. The impact of activated carbon on oligomerization was examined by conducting isotherm experiments at a neutral pH on Carbon(exp) produced with optimal characteristics and granular activated carbon (GAC) F400 for phenol, 2-methylphenol and 2-ethylphenol. These isotherms were collected under anoxic (absence of molecular oxygen) and oxic (presence of molecular oxygen) conditions. The single solute adsorption of phenol, 2-methylphenol and 2-ethylphenol on Carbon(exp) showed no obvious differences between oxic and anoxic environment, which indicated that the Carbon(exp) sample is very effective in hampering the oligomerization of phenolic compounds under oxic conditions. On the other hand, F400, which have lower micropore percentage and BET surface area, significant increases in the adsorptive capacity had been observed when molecular oxygen was present. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Homologous ELISA for detection of oligomeric human TNF: properties of the assay.

    Science.gov (United States)

    Petyovka, N; Lyach, L; Voitenok, N N

    1995-10-26

    In order to quantify oligomeric human tumor necrosis factor-alpha (TNF), we have developed a sensitive homologous enzyme-linked immunosorbent assay (Hm-ELISA) using the same monoclonal antibody (MoAb) for both solid and liquid phase. Different anti-TNF MoAb have been compared in terms of their efficacy in the Hm-ELISA, affinity, neutralization capacity and epitope specificity. The data suggest, that effectiveness in the Hm-ELISA may represent a novel characteristic of MoAb. Of the MoAbs tested, 5 N was capable of recognizing oligomeric TNF in the Hm-ELISA with a detection limit of 15 pg/ml. Furthermore, using Hm-ELISA against human TNF, interleukin-8 (IL-8) and lymphotoxin, we have demonstrated that these cytokines are oligomeric in physiological solutions, but are converted into monomeric forms in the presence of the non-ionic detergent Tween 20. High salt buffer was employed to abrogate a nonspecific false positive reaction in the Hm-ELISA found in nearly half of the plasma samples obtained from healthy subjects. Finally, a good correlation between the Hm-ELISA and the L929 bioassay was observed for natural and recombinant TNF measured in human plasma.

  18. Catalytic oligomerization of terminal alkynes promoted by organo-f-complexes

    International Nuclear Information System (INIS)

    Straub, T.; Haskel, A.; Eisen, M.S.

    1995-01-01

    Organoactinides of the type Cp* 2 AcMe 2 (Cp*=C 5 Me 5 ; Ac=Th, U) are active catalyst precursors for the oligomerization of terminal alkynes HC triple-bond CR (R=alkyl, aryl, SiMe 3 ). The regioselectivity and the extent of oligomerization strongly depend on the alkyne substituent R, whereas the catalytic reactivity is similar for 1 and 2. In the presence of one of these organoactinides, for example, HCCSiMe 3 regioselectively oligomerizes to the head-to-tail dimer 3 (5%) and the trimer 4 (95%). 1 and 2 react with the terminal alkynes, releasing methane, to the corresponding bisacetylide complexes which are active species and in the catalytic reactions. The bisacetylide complex (η 5 -C 5 Me 5 ) 2 U(CCPh) 2 was identified by proton NMR spectroscopy. Subsequent insertion of alkyne molecules in the actinide-carbon σ-bonds leads to the formation of actinide-alkenyl complexes. The turnover limiting step is the release of the organic oligomer from the actinide-organyl complex. A species of the latter has been spectroscopically characterized in the trimerization reaction of HCCSiMe 3 . In this poster, the catalytic reactivity of the actinide alkyls 1 and 2 with various mono-substituted alkynes as well as the spectroscopic characterization of the key organometallic intermediate complexes in the catalytic cycle and a detailed mechanistic discussion are given

  19. Crystal Structure of the Oligomeric Form of Lassa Virus Matrix Protein Z.

    Science.gov (United States)

    Hastie, Kathryn M; Zandonatti, Michelle; Liu, Tong; Li, Sheng; Woods, Virgil L; Saphire, Erica Ollmann

    2016-05-01

    The arenavirus matrix protein Z is highly multifunctional and occurs in both monomeric and oligomeric forms. The crystal structure of a dodecamer of Z from Lassa virus, presented here, illustrates a ring-like structure with a highly basic center. Mutagenesis demonstrates that the dimeric interface within the dodecamer and a Lys-Trp-Lys triad at the center of the ring are important for oligomerization. This structure provides an additional template to explore the many functions of Z. The arenavirus Lassa virus causes hundreds of thousands of infections each year, many of which develop into fatal hemorrhagic fever. The arenavirus matrix protein Z is multifunctional, with at least four distinct roles. Z exists in both monomeric and oligomeric forms, each of which likely serves a specific function in the viral life cycle. Here we present the dodecameric form of Lassa virus Z and demonstrate that Z forms a "wreath" with a highly basic center. This structure and that of monomeric Z now provide a pair of critical templates by which the multiple roles of Z in the viral life cycle may be interpreted. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  20. The role of oligomerization and cooperative regulation in protein function: the case of tryptophan synthase.

    Directory of Open Access Journals (Sweden)

    M Qaiser Fatmi

    Full Text Available The oligomerization/co-localization of protein complexes and their cooperative regulation in protein function is a key feature in many biological systems. The synergistic regulation in different subunits often enhances the functional properties of the multi-enzyme complex. The present study used molecular dynamics and Brownian dynamics simulations to study the effects of allostery, oligomerization and intermediate channeling on enhancing the protein function of tryptophan synthase (TRPS. TRPS uses a set of α/β-dimeric units to catalyze the last two steps of L-tryptophan biosynthesis, and the rate is remarkably slower in the isolated monomers. Our work shows that without their binding partner, the isolated monomers are stable and more rigid. The substrates can form fairly stable interactions with the protein in both forms when the protein reaches the final ligand-bound conformations. Our simulations also revealed that the α/β-dimeric unit stabilizes the substrate-protein conformation in the ligand binding process, which lowers the conformation transition barrier and helps the protein conformations shift from an open/inactive form to a closed/active form. Brownian dynamics simulations with a coarse-grained model illustrate how protein conformations affect substrate channeling. The results highlight the complex roles of protein oligomerization and the fine balance between rigidity and dynamics in protein function.

  1. Physiological relevance of plant 2-Cys peroxiredoxin overoxidation level and oligomerization status.

    Science.gov (United States)

    Cerveau, Delphine; Ouahrani, Djelloul; Marok, Mohamed Amine; Blanchard, Laurence; Rey, Pascal

    2016-01-01

    Peroxiredoxins are ubiquitous thioredoxin-dependent peroxidases presumed to display, upon environmental constraints, a chaperone function resulting from a redox-dependent conformational switch. In this work, using biochemical and genetic approaches, we aimed to unravel the factors regulating the redox status and the conformation of the plastidial 2-Cys peroxiredoxin (2-Cys PRX) in plants. In Arabidopsis, we show that in optimal growth conditions, the overoxidation level mainly depends on the availability of thioredoxin-related electron donors, but not on sulfiredoxin, the enzyme reducing the 2-Cys PRX overoxidized form. We also observed that upon various physiological temperature, osmotic and light stress conditions, the overoxidation level and oligomerization status of 2-Cys PRX can moderately vary depending on the constraint type. Further, no major change was noticed regarding protein conformation in water-stressed Arabidopsis, barley and potato plants, whereas species-dependent up- and down-variations in overoxidation were observed. In contrast, both 2-Cys PRX overoxidation and oligomerization were strongly induced during a severe oxidative stress generated by methyl viologen. From these data, revealing that the oligomerization status of plant 2-Cys PRX does not exhibit important variation and is not tightly linked to the protein redox status upon physiologically relevant environmental constraints, the possible in planta functions of 2-Cys PRX are discussed. © 2015 John Wiley & Sons Ltd.

  2. Polyhedral-Like NiMn-Layered Double Hydroxide/Porous Carbon as Electrode for Enhanced Electrochemical Performance Supercapacitors.

    Science.gov (United States)

    Yu, Mei; Liu, Ruili; Liu, Jianhua; Li, Songmei; Ma, Yuxiao

    2017-11-01

    Polyhedral-like NiMn-layered double hydroxide/porous carbon (NiMn-LDH/PC-x) composites are successfully synthesized by hydrothermal method (x = 1, 2 means different mass percent of porous carbon (PC) in composites). The NiMn-LDH/PC-1 composites possess specific capacitance 1634 F g -1 at a current density of 1 A g -1 , and it is much better than that of pure LDH (1095 F g -1 at 1 A g -1 ). Besides, the sample can retain 84.58% of original capacitance after 3000 cycles at 15 A g -1 . An asymmetric supercapacitor with NiMn-LDH/PC-1 as anode and activated carbon as cathode is fabricated, and the supercapacitor can achieve an energy density of 18.60 Wh kg -1 at a power density of 225.03 W kg -1 . The enhanced electrochemical performance attributes to the high faradaic pseudocapacitance of NiMn-LDH, the introduction of PC, and the 3D porous structure of LDH/PC-1 composites. The introduction of PC hinders serious agglomeration of LDH and further accelerates ions transport. The encouraging results indicate that these materials are one of the most potential candidates for energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The slice balance approach (SBA): a characteristic-based, multiple balance SN approach on unstructured polyhedral meshes

    International Nuclear Information System (INIS)

    Grove, R.E.

    2005-01-01

    The Slice Balance Approach (SBA) is an approach for solving geometrically-complex, neutral-particle transport problems within a multi-group discrete ordinates (S N ) framework. The salient feature is an angle-dependent spatial decomposition. We approximate general surfaces with arbitrary polygonal faces and mesh the geometry with arbitrarily-shaped polyhedral cells. A cell-local spatial decomposition divides cells into angle-dependent slices for each S N direction. This subdivision follows from a characteristic-based view of the transport problem. Most balance-based characteristic methods use it implicitly; we use it explicitly and exploit its properties. Our mathematical approach is a multiple balance approach using exact spatial moments balance equations on cells and slices along with auxiliary relations on slices. We call this the slice balance approach; it is a characteristic-based multiple balance approach. The SBA is intentionally general and can extend differencing schemes to arbitrary 2-D and 3-D meshes. This work contributes to development of general-geometry deterministic transport capability to complement Monte Carlo capability for large, geometrically-complex transport problems. The purpose of this paper is to describe the SBA. We describe the spatial decomposition and mathematical framework and highlight a few interesting properties. We sketch the derivation of two solution schemes, a step characteristic scheme and a diamond-difference-like scheme, to illustrate the approach and we present interesting results for a 2-D problem. (author)

  4. Sn-doped polyhedral In2O3 particles: Synthesis, characterization, and origins of luminous emission in wide visible range

    International Nuclear Information System (INIS)

    Zhu Yunqing; Chen Yiqing

    2012-01-01

    Sn-doped octahedronal and tetrakaidecahedronal In 2 O 3 particles were successfully synthesized by simple thermal evaporation of indium grains using SnO as dopant. Structural characterization results demonstrated that the Sn-doped tetrakaidecahedronal In 2 O 3 particle had additional six {001} crystal surfaces compared with the octahedronal one. The luminous properties of both samples were characterized by photoluminescence (PL) and cathodoluminescence (CL) spectroscopy. A broad visible luminous emission around 570 nm was observed. Studies revealed that the emission consisted of three peaks of 511 nm, 564 nm, and 622 nm, which were attributed to radioactive recombination centers such as single ionized oxygen vacancy, indium interstitial, and antisite oxygen, respectively. We believe that the Sn donor level plays an important role in the visible luminous emission. - Graphical abstract: With more oxygen vacancies and tin doping. ITO particles can exhibit a better CL performance. Sn donor level near the conduction band edge plays an important role in luminous emission in wide visible range. Highlights: ► Polyhedral ITO particles synthesized by thermal evaporation using SnO as dopant. ► Broad visible luminous emission around 570 nm. ► Sn donor level plays an important role in the visible emission. ► ITO particles with more oxygen vacancies have better CL performance in visible range.

  5. Procedimiento de corte en cuerpos sólidos poliédricos // Section procedure in solid polyhedral bodies.

    Directory of Open Access Journals (Sweden)

    A. Miguel Iznaga Benítez

    2000-10-01

    Full Text Available El conocimiento de la estructura de datos de los modelos geométricos ha posibilitado el desarrollo de algoritmos parasolucionar problemas complejos. Estos algoritmos han facilitado a su vez, la automatización en las oficinas de diseño através de los medios computacionales.Por tal motivo, se presenta el desarrollo de un algoritmo para la obtención de cortes y secciones en cuerpos geométricospoliédricos, se plantean las etapas fundamentales del algoritmo y a través de un ejercicio se ejemplifica el mismo.Este algoritmo puede ser utilizado en la creación de software que ayuden al proceso docente.Palabras claves: enseñanza, gráfica, separación de sólidos, geometría, dibujo, algoritmo, CAD._________________________________________________________________________Abstract:The knowledge of data structure in geometric models has facilitated the development of algorithms to solve complexproblems. These algorithms have facilitated in turn, the automation in the design by computational means. For such reason,is presented the development of an algorithm for the obtaining of sections in polyhedral geometric bodies, the fundamentalstages of the algorithm are stated and illustrated using an example.This algorithm can be use in the software creation that will help to the educational processKey words: section, separation of solids, algorithm, geometric modeling, graphic, CAD. teaching.

  6. Shape-controlled synthesis of Pt-Pd core-shell nanoparticles exhibiting polyhedral morphologies by modified polyol method

    International Nuclear Information System (INIS)

    Long, Nguyen Viet; Asaka, Toru; Matsubara, Takashi; Nogami, Masayuki

    2011-01-01

    Pt-Pd core-shell nanoparticles were synthesized by a simple synthetic method. First, Pt nanoparticles were synthesized in a controlled manner via the reduction of chloroplantinic acid hexahydrate in ethylene glycol (EG) at 160 deg. C in the presence of silver nitrate and the stabilization of polyvinylpyrrolidon. AgNO 3 used acts as a structure-modifying agent to the morphology of the Pt nanoparticles. These Pt nanoparticles function as the seeds for the successive reduction of sodium tetrachloropalladate (II) hydrate in EG under stirring for 15 min at 160 deg. C in order to synthesize Pt-Pd core-shell nanoparticles. To characterize the as-prepared Pt-Pd nanoparticles, transmission electron microscopy (TEM) and high-resolution TEM are used. The high-resolution elemental mappings were carried out using the combination of scanning TEM and X-ray energy-dispersive spectroscopy. The results also demonstrate the homogeneous nucleation and growth of the Pd metal shell on the definite Pt core. The synthesized Pt-Pd core-shell nanoparticles exhibit a sharp and polyhedral morphology. The epitaxial growth of the controlled Pd shells on the Pt cores via a polyol method was observed. It is suggested that Frank-van der Merwe and Stranski-Krastanov growth modes coexisted in the nucleation and growth of Pt-Pd core-shell nanoparticles.

  7. Enhanced Anti-Ultraviolet and Thermal Stability of a Pesticide via Modification of a Volatile Organic Compound (VOC-Free Vinyl-Silsesquioxane in Desert Areas

    Directory of Open Access Journals (Sweden)

    Derong Lin

    2016-08-01

    Full Text Available Due to the effect of severe environmental conditions, such as intense heat, blowing sand, and ultraviolet light, conventional pesticide applications have repeatedly failed to adequately control mosquito and sandfly populations in desert areas. In this study, a vinyl silsesquioxane (VS was added to a pesticide (citral to enhance residual, thermal and anti-ultraviolet properties via three double-bond reactions in the presence of an initiator: (1 the connection of VS and citral, (2 a radical self-polymerization of VS and (3 a radical self-polymerization of citral. VS-citral, the expected and main product of the copolymerization of VS and citral, was characterized using standard spectrum techniques. The molecular consequences of the free radical polymerization were analyzed by MALDITOF spectrometry. Anti-ultraviolet and thermal stability properties of the VS-citral system were tested using scanning spectrophotometry (SSP and thermogravimetric analysis (TGA. The repellency of VS-citral decreased over time, from 97.63% at 0 h to 72.98% at 1 h and 60.0% at 2 h, as did the repellency of citral, from 89.56% at 0 h to 62.73% at 1 h and 50.95% at 2 h.

  8. Enhancement Corrosion Resistance of (γ-Glycidyloxypropyl-Silsesquioxane-Titanium Dioxide Films and Its Validation by Gas Molecule Diffusion Coefficients Using Molecular Dynamics (MD Simulation

    Directory of Open Access Journals (Sweden)

    Haiyan Wang

    2014-01-01

    Full Text Available Based on silsesquioxanes (SSO derived from the hydrolytic condensation of (γ-glycidyloxypropyltrimethoxysilane (GPMS and titanium tetrabutoxide (TTB, hybrid films on aluminum alloy (AA, film-GPMS-SSO (f-GS and f-GS-TTBi% (f-GSTT5%–25%, i = 5, 10, 15, 20 and 25 wt%, were prepared and tested by electrochemical measurements with typical potentiodynamic polarization curves. The Icorr values of the samples were significantly lower, comparing with the Icorr values of the f-GS, AA and f-GS modified tetraethoxysilane (TEOS in the previous study, which implies that the TTB5%–25% (TiO2 additions in the coatings indeed enhance the electrochemical corrosion resistance. Correlations between the film structures and anticorrosion properties were discussed. To validate the corresponding anticorrosion experiment results, different 3D-amorphous cubic unit cells were employed as models to investigate the self-diffusion coefficient (SDC for SO2, NO2 and H2O molecules by molecular dynamics (MD simulation. All of the SDCs calculated for SO2, NO2 and H2O diffusing in f-GSTT5%–25% cells were less than the SDCs in f-GS. These results validated the corresponding anticorrosion experiment results.

  9. Three-dimensional lattice rotation in GaAs nanowire growth on hydrogen-silsesquioxane covered GaAs (001) using molecular beam epitaxy

    Science.gov (United States)

    Tran, Dat Q.; Pham, Huyen T.; Higashimine, Koichi; Oshima, Yoshifumi; Akabori, Masashi

    2018-05-01

    We report on crystallographic behaviors of inclined GaAs nanowires (NWs) self-crystallized on GaAs (001) substrate. The NWs were grown on hydrogen-silsesquioxane (HSQ) covered substrates using molecular beam epitaxy (MBE). Commonly, the epitaxial growth of GaAs B (B-polar) NWs is prominently observed on GaAs (001); however, we yielded a remarkable number of epitaxially grown GaAs A (A-polar) NWs in addition to the majorly obtained B-polar NWs. Such NW orientations are always accompanied by a typical inclined angle of 35° from (001) plane. NWs with another inclined angle of 74° were additionally observed and attributed to be -oriented, not in direct epitaxial relation with the substrate. Such 74° NWs' existence is related to first-order three-dimensional (3D) lattice rotation taking place at the very beginning of the growth. It turns out that spatially 60° lattice rotation around directions at GaAs seeds is essentially in charge of A- and B-polar 74° NWs. Transmission electron microscope observations reveal a high density of twinning in the B-polar NWs and twin-free characteristic in the A-polar NWs.

  10. Modelling the interdependence between the stoichiometry of receptor oligomerization and ligand binding for a coexisting dimer/tetramer receptor system.

    Science.gov (United States)

    Rovira, X; Vivó, M; Serra, J; Roche, D; Strange, P G; Giraldo, J

    2009-01-01

    Many G protein-coupled receptors have been shown to exist as oligomers, but the oligomerization state and the effects of this on receptor function are unclear. For some G protein-coupled receptors, in ligand binding assays, different radioligands provide different maximal binding capacities. Here we have developed mathematical models for co-expressed dimeric and tetrameric species of receptors. We have considered models where the dimers and tetramers are in equilibrium and where they do not interconvert and we have also considered the potential influence of the ligands on the degree of oligomerization. By analogy with agonist efficacy, we have considered ligands that promote, inhibit or have no effect on oligomerization. Cell surface receptor expression and the intrinsic capacity of receptors to oligomerize are quantitative parameters of the equations. The models can account for differences in the maximal binding capacities of radioligands in different preparations of receptors and provide a conceptual framework for simulation and data fitting in complex oligomeric receptor situations.

  11. N-Glycosylation instead of cholesterol mediates oligomerization and apical sorting of GPI-APs in FRT cells.

    Science.gov (United States)

    Imjeti, Naga Salaija; Lebreton, Stéphanie; Paladino, Simona; de la Fuente, Erwin; Gonzalez, Alfonso; Zurzolo, Chiara

    2011-12-01

    Sorting of glycosylphosphatidyl-inositol--anchored proteins (GPI-APs) in polarized epithelial cells is not fully understood. Oligomerization in the Golgi complex has emerged as the crucial event driving apical segregation of GPI-APs in two different kind of epithelial cells, Madin-Darby canine kidney (MDCK) and Fisher rat thyroid (FRT) cells, but whether the mechanism is conserved is unknown. In MDCK cells cholesterol promotes GPI-AP oligomerization, as well as apical sorting of GPI-APs. Here we show that FRT cells lack this cholesterol-driven oligomerization as apical sorting mechanism. In these cells both apical and basolateral GPI-APs display restricted diffusion in the Golgi likely due to a cholesterol-enriched membrane environment. It is striking that N-glycosylation is the critical event for oligomerization and apical sorting of GPI-APs in FRT cells but not in MDCK cells. Our data indicate that at least two mechanisms exist to determine oligomerization in the Golgi leading to apical sorting of GPI-APs. One depends on cholesterol, and the other depends on N-glycosylation and is insensitive to cholesterol addition or depletion.

  12. Polyhedral shape model for terrain correction of gravity and gravity gradient data based on an adaptive mesh

    Science.gov (United States)

    Guo, Zhikui; Chen, Chao; Tao, Chunhui

    2016-04-01

    Since 2007, there are four China Da yang cruises (CDCs), which have been carried out to investigate polymetallic sulfides in the southwest Indian ridge (SWIR) and have acquired both gravity data and bathymetry data on the corresponding survey lines(Tao et al., 2014). Sandwell et al. (2014) published a new global marine gravity model including the free air gravity data and its first order vertical gradient (Vzz). Gravity data and its gradient can be used to extract unknown density structure information(e.g. crust thickness) under surface of the earth, but they contain all the mass effect under the observation point. Therefore, how to get accurate gravity and its gradient effect of the existing density structure (e.g. terrain) has been a key issue. Using the bathymetry data or ETOPO1 (http://www.ngdc.noaa.gov/mgg/global/global.html) model at a full resolution to calculate the terrain effect could spend too much computation time. We expect to develop an effective method that takes less time but can still yield the desired accuracy. In this study, a constant-density polyhedral model is used to calculate the gravity field and its vertical gradient, which is based on the work of Tsoulis (2012). According to gravity field attenuation with distance and variance of bathymetry, we present an adaptive mesh refinement and coarsening strategies to merge both global topography data and multi-beam bathymetry data. The local coarsening or size of mesh depends on user-defined accuracy and terrain variation (Davis et al., 2011). To depict terrain better, triangular surface element and rectangular surface element are used in fine and coarse mesh respectively. This strategy can also be applied to spherical coordinate in large region and global scale. Finally, we applied this method to calculate Bouguer gravity anomaly (BGA), mantle Bouguer anomaly(MBA) and their vertical gradient in SWIR. Further, we compared the result with previous results in the literature. Both synthetic model

  13. Involvement of C-Terminal Histidines in Soybean PM1 Protein Oligomerization and Cu2+ Binding.

    Science.gov (United States)

    Liu, Guobao; Liu, Ke; Gao, Yang; Zheng, Yizhi

    2017-06-01

    Late embryogenesis abundant (LEA) proteins are widely distributed among plant species, where they contribute to abiotic stress tolerance. LEA proteins can be classified into seven groups according to conserved sequence motifs. The PM1 protein from soybean, which belongs to the Pfam LEA_1 group, has been shown previously to be at least partially natively unfolded, to bind metal ions and potentially to stabilize proteins and membranes. Here, we investigated the role of the PM1 C-terminal domain and in particular the multiple histidine residues in this half of the protein. We constructed recombinant plasmids expressing full-length PM1 and two truncated forms, PM1-N and PM1-C, which represent the N- and C-terminal halves of the protein, respectively. Immunoblotting and cross-linking experiments showed that full-length PM1 forms oligomers and high molecular weight (HMW) complexes in vitro and in vivo, while PM1-C, but not PM1-N, also formed oligomers and HMW complexes in vitro. When the histidine residues in PM1 and PM1-C were chemically modified, oligomerization was abolished, suggesting that histidines play a key role in this process. Furthermore, we demonstrated that high Cu2+ concentrations promote oligomerization and induce PM1 and PM1-C to form HMW complexes. Therefore, we speculate that PM1 proteins not only maintain ion homeostasis in the cytoplasm, but also potentially stabilize and protect other proteins during abiotic stress by forming a large, oligomeric molecular shield around biological targets. © The Author 2017. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  14. Elucidation of amyloid beta-protein oligomerization mechanisms: discrete molecular dynamics study.

    Science.gov (United States)

    Urbanc, B; Betnel, M; Cruz, L; Bitan, G; Teplow, D B

    2010-03-31

    Oligomers of amyloid beta-protein (Abeta) play a central role in the pathology of Alzheimer's disease. Of the two predominant Abeta alloforms, Abeta(1-40) and Abeta(1-42), Abeta(1-42) is more strongly implicated in the disease. We elucidated the structural characteristics of oligomers of Abeta(1-40) and Abeta(1-42) and their Arctic mutants, [E22G]Abeta(1-40) and [E22G]Abeta(1-42). We simulated oligomer formation using discrete molecular dynamics (DMD) with a four-bead protein model, backbone hydrogen bonding, and residue-specific interactions due to effective hydropathy and charge. For all four peptides under study, we derived the characteristic oligomer size distributions that were in agreement with prior experimental findings. Unlike Abeta(1-40), Abeta(1-42) had a high propensity to form paranuclei (pentameric or hexameric) structures that could self-associate into higher-order oligomers. Neither of the Arctic mutants formed higher-order oligomers, but [E22G]Abeta(1-40) formed paranuclei with a similar propensity to that of Abeta(1-42). Whereas the best agreement with the experimental data was obtained when the charged residues were modeled as solely hydrophilic, further assembly from spherical oligomers into elongated protofibrils was induced by nonzero electrostatic interactions among the charged residues. Structural analysis revealed that the C-terminal region played a dominant role in Abeta(1-42) oligomer formation whereas Abeta(1-40) oligomerization was primarily driven by intermolecular interactions among the central hydrophobic regions. The N-terminal region A2-F4 played a prominent role in Abeta(1-40) oligomerization but did not contribute to the oligomerization of Abeta(1-42) or the Arctic mutants. The oligomer structure of both Arctic peptides resembled Abeta(1-42) more than Abeta(1-40), consistent with their potentially more toxic nature.

  15. The effects of oligomerization on Saccharomyces cerevisiae Mcm4/6/7 function

    Directory of Open Access Journals (Sweden)

    Davey Megan J

    2010-09-01

    Full Text Available Abstract Background Minichromosome maintenance proteins (Mcm 2, 3, 4, 5, 6 and 7 are related by sequence and form a variety of complexes that unwind DNA, including Mcm4/6/7. A Mcm4/6/7 trimer forms one half of the Mcm2-7 hexameric ring and can be thought of as the catalytic core of Mcm2-7, the replicative helicase in eukaryotic cells. Oligomeric analysis of Mcm4/6/7 suggests that it forms a hexamer containing two Mcm4/6/7 trimers, however, under certain conditions trimeric Mcm4/6/7 has also been observed. The functional significance of the different Mcm4/6/7 oligomeric states has not been assessed. The results of such an assessment would have implications for studies of both Mcm4/6/7 and Mcm2-7. Results Here, we show that Saccharomyces cerevisiae Mcm4/6/7 reconstituted from individual subunits exists in an equilibrium of oligomeric forms in which smaller oligomers predominate in the absence of ATP. In addition, we found that ATP, which is required for Mcm4/6/7 activity, shifts the equilibrium towards larger oligomers, likely hexamers of Mcm4/6/7. ATPγS and to a lesser extent ADP also shift the equilibrium towards hexamers. Study of Mcm4/6/7 complexes containing mutations that interfere with the formation of inter-subunit ATP sites (arginine finger mutants indicates that full activity of Mcm4/6/7 requires all of its ATP sites, which are formed in a hexamer and not a trimer. In keeping with this observation, Mcm4/6/7 binds DNA as a hexamer. Conclusions The minimal functional unit of Mcm4/6/7 is a hexamer. One of the roles of ATP binding by Mcm4/6/7 may be to stabilize formation of hexamers.

  16. Crystal structures from the Plasmodium peroxiredoxins: new insights into oligomerization and product binding.

    Science.gov (United States)

    Qiu, Wei; Dong, Aiping; Pizarro, Juan C; Botchkarsev, Alexei; Min, Jinrong; Wernimont, Amy K; Hills, Tanya; Hui, Raymond; Artz, Jennifer D

    2012-03-19

    Plasmodium falciparum is the protozoan parasite primarily responsible for more than one million malarial deaths, annually, and is developing resistance to current therapies. Throughout its lifespan, the parasite is subjected to oxidative attack, so Plasmodium antioxidant defences are essential for its survival and are targets for disease control. To further understand the molecular aspects of the Plasmodium redox system, we solved 4 structures of Plasmodium peroxiredoxins (Prx). Our study has confirmed PvTrx-Px1 to be a hydrogen peroxide (H2O2)-sensitive peroxiredoxin. We have identified and characterized the novel toroid octameric oligomer of PyTrx-Px1, which may be attributed to the interplay of several factors including: (1) the orientation of the conserved surface/buried arginine of the NNLA(I/L)GRS-loop; and (2) the C-terminal tail positioning (also associated with the aforementioned conserved loop) which facilitates the intermolecular hydrogen bond between dimers (in an A-C fashion). In addition, a notable feature of the disulfide bonds in some of the Prx crystal structures is discussed. Finally, insight into the latter stages of the peroxiredoxin reaction coordinate is gained. Our structure of PyPrx6 is not only in the sulfinic acid (RSO2H) form, but it is also with glycerol bound in a way (not previously observed) indicative of product binding. The structural characterization of Plasmodium peroxiredoxins provided herein provides insight into their oligomerization and product binding which may facilitate the targeting of these antioxidant defences. Although the structural basis for the octameric oligomerization is further understood, the results yield more questions about the biological implications of the peroxiredoxin oligomerization, as multiple toroid configurations are now known. The crystal structure depicting the product bound active site gives insight into the overoxidation of the active site and allows further characterization of the leaving group

  17. Single-molecule diffusometry reveals the nucleotide-dependent oligomerization pathways of Nicotiana tabacum Rubisco activase

    Science.gov (United States)

    Wang, Quan; Serban, Andrew J.; Wachter, Rebekka M.; Moerner, W. E.

    2018-03-01

    Oligomerization plays an important role in the function of many proteins, but a quantitative picture of the oligomer distribution has been difficult to obtain using existing techniques. Here we describe a method that combines sub-stoichiometric labeling and recently developed single-molecule diffusometry to measure the size distribution of oligomers under equilibrium conditions in solution, one molecule at a time. We use this technique to characterize the oligomerization behavior of Nicotiana tabacum (Nt) Rubisco activase (Nt-Rca), a chaperone-like AAA-plus ATPase essential in regulating carbon fixation during photosynthesis. We directly observed monomers, dimers, and a tetramer/hexamer mixture and extracted their fractional abundance as a function of protein concentration. We show that the oligomerization pathway of Nt-Rca is nucleotide dependent: ATPγS binding strongly promotes tetramer/hexamer formation from dimers and results in a preferred tetramer/hexamer population for concentrations in the 1-10 μM range. Furthermore, we directly observed dynamic assembly and disassembly processes of single complexes in real time and from there estimated the rate of subunit exchange to be ˜0.1 s-1 with ATPγS. On the other hand, ADP binding destabilizes Rca complexes by enhancing the rate of subunit exchange by >2 fold. These observations provide a quantitative starting point to elucidate the structure-function relations of Nt-Rca complexes. We envision the method to fill a critical gap in defining and quantifying protein assembly pathways in the small-oligomer regime.

  18. Arc is a flexible modular protein capable of reversible self-oligomerization

    Science.gov (United States)

    Myrum, Craig; Baumann, Anne; Bustad, Helene J.; Flydal, Marte Innselset; Mariaule, Vincent; Alvira, Sara; Cuéllar, Jorge; Haavik, Jan; Soulé, Jonathan; Valpuesta, José Maria; Márquez, José Antonio; Martinez, Aurora; Bramham, Clive R.

    2015-01-01

    The immediate early gene product Arc (activity-regulated cytoskeleton-associated protein) is posited as a master regulator of long-term synaptic plasticity and memory. However, the physicochemical and structural properties of Arc have not been elucidated. In the present study, we expressed and purified recombinant human Arc (hArc) and performed the first biochemical and biophysical analysis of hArc's structure and stability. Limited proteolysis assays and MS analysis indicate that hArc has two major domains on either side of a central more disordered linker region, consistent with in silico structure predictions. hArc's secondary structure was estimated using CD, and stability was analysed by CD-monitored thermal denaturation and differential scanning fluorimetry (DSF). Oligomerization states under different conditions were studied by dynamic light scattering (DLS) and visualized by AFM and EM. Biophysical analyses show that hArc is a modular protein with defined secondary structure and loose tertiary structure. hArc appears to be pyramid-shaped as a monomer and is capable of reversible self-association, forming large soluble oligomers. The N-terminal domain of hArc is highly basic, which may promote interaction with cytoskeletal structures or other polyanionic surfaces, whereas the C-terminal domain is acidic and stabilized by ionic conditions that promote oligomerization. Upon binding of presenilin-1 (PS1) peptide, hArc undergoes a large structural change. A non-synonymous genetic variant of hArc (V231G) showed properties similar to the wild-type (WT) protein. We conclude that hArc is a flexible multi-domain protein that exists in monomeric and oligomeric forms, compatible with a diverse, hub-like role in plasticity-related processes. PMID:25748042

  19. Porous polyhedral and fusiform Co3O4 anode materials for high-performance lithium-ion batteries

    International Nuclear Information System (INIS)

    Huang, Guoyong; Xu, Shengming; Lu, Shasha; Li, Linyan; Sun, Hongyu

    2014-01-01

    Graphical abstract: - Abstract: Co 3 O 4 is commonly used as a potential anode material for Li-ion batteries (LIBs). In this study, novel porous polyhedral and fusiform Co 3 O 4 powders have been synthesized successfully through the hydrothermal method with different solvents followed by thermal treatment. It is shown that both of the polyhedrons (1.0-3.0 μm in side length) and the spindles (2.0-5.0 μm in length, 0.5-2.0 μm in width) are composed of similar irregular nanoparticles (20-200 nm in diameter, 20-40 nm in thickness) bonded to each other. Evaluated by electrochemical measurements, both of them have high initial discharge capacities (1374.4 mAhg −1 and 1326.3 mAhg −1 ) and enhanced cycling stabilities at the low rate (the capacity retention ratios at 0.1 C after 70 cycles are 91.6% and 92.2%, respectively). However, the rate capability of the spindles (93.8%, 90.1% and 98.9% of the second discharge capacities after 70 cycles at 0.5 C, 1 C and 2 C, respectively) is better than the polyhedrons’ (only 76.2%, 42.1% and 59.3% under the same conditions). Remarkable, the unique morphologies and special structures may be extended to synthesize other similar transition metal oxides (NiO, Fe 3 O 4 , et al.) as high performance anodes for LIBs

  20. Gravity Gradient Tensor of Arbitrary 3D Polyhedral Bodies with up to Third-Order Polynomial Horizontal and Vertical Mass Contrasts

    Science.gov (United States)

    Ren, Zhengyong; Zhong, Yiyuan; Chen, Chaojian; Tang, Jingtian; Kalscheuer, Thomas; Maurer, Hansruedi; Li, Yang

    2018-03-01

    During the last 20 years, geophysicists have developed great interest in using gravity gradient tensor signals to study bodies of anomalous density in the Earth. Deriving exact solutions of the gravity gradient tensor signals has become a dominating task in exploration geophysics or geodetic fields. In this study, we developed a compact and simple framework to derive exact solutions of gravity gradient tensor measurements for polyhedral bodies, in which the density contrast is represented by a general polynomial function. The polynomial mass contrast can continuously vary in both horizontal and vertical directions. In our framework, the original three-dimensional volume integral of gravity gradient tensor signals is transformed into a set of one-dimensional line integrals along edges of the polyhedral body by sequentially invoking the volume and surface gradient (divergence) theorems. In terms of an orthogonal local coordinate system defined on these edges, exact solutions are derived for these line integrals. We successfully derived a set of unified exact solutions of gravity gradient tensors for constant, linear, quadratic and cubic polynomial orders. The exact solutions for constant and linear cases cover all previously published vertex-type exact solutions of the gravity gradient tensor for a polygonal body, though the associated algorithms may differ in numerical stability. In addition, to our best knowledge, it is the first time that exact solutions of gravity gradient tensor signals are derived for a polyhedral body with a polynomial mass contrast of order higher than one (that is quadratic and cubic orders). Three synthetic models (a prismatic body with depth-dependent density contrasts, an irregular polyhedron with linear density contrast and a tetrahedral body with horizontally and vertically varying density contrasts) are used to verify the correctness and the efficiency of our newly developed closed-form solutions. Excellent agreements are obtained

  1. Metal-Organic Frameworks Triggered High-Efficiency Li storage in Fe-Based Polyhedral Nanorods for Lithium-ion Batteries

    International Nuclear Information System (INIS)

    Shen, Lisha; Song, Huawei; Wang, Chengxin

    2017-01-01

    Recently, metal organic framework (MOF) nanostructures have been frequently reported in the field of energy storage, specifically for Li-ion or Na-ion storage. By inter-separating the active sites of metal cluster and organic ligands, MOF nanostructures are exceptionally promising for realizing fast ion exchange and high-efficiency transportation and addressing the intricate issues that the energy-intensive Li-ion batteries have faced over many years. The related ion-storage mechanism remains to be explored. Is the traditional redox reaction mechanism operative for these nanostructure, as it is for transitional metal oxide? Herein, taking [Fe_3O(BDC)_3(H_2O)_2(NO_3)]n (Fe-MIL-88B) as an example, an Fe-based metal organic polyhedral nanorods of MIL–88 B structure was designed as an anode for Li-ion storage. When tested at 60 mA g"−"1, the nanoporous Fe-MIL–88 B polyhedral nanorods retained a reversible capacity of 744.5 mAh g"−"1 for more than 400 cycles. Ex situ characterizations of the post-cycled electrodes revealed that both the transition metal ions and the organic ligands contributed to the high reversible specific capacity. The polyhedral nanorods electrodes held the metal-organic skeleton together throughout the battery operation, although in a somewhat different manner than the pristine ones. This further substantiated that some MOF nanostructures are more appropriate than others for stable lithiation/delithiation processes. State-of-the-art CR2032 full cells showed that a high capacity of 86.8 mAh g"−"1 that was retained after 100 cycles (herein, the capacity for the full cell was calculated based on both the weight of the anode and the cathode, and the charge-discharge rate was 0.25C), when commercial LiFePO_4 powders were used as the cathode.

  2. Multi-PAS domain-mediated protein oligomerization of PpsR from Rhodobacter sphaeroides

    International Nuclear Information System (INIS)

    Heintz, Udo; Meinhart, Anton; Winkler, Andreas

    2014-01-01

    Crystal structures of two truncated variants of the transcription factor PpsR from R. sphaeroides are presented that enabled the phasing of a triple PAS domain construct. Together, these structures reveal the importance of α-helical PAS extensions for multi-PAS domain-mediated protein oligomerization and function. Per–ARNT–Sim (PAS) domains are essential modules of many multi-domain signalling proteins that mediate protein interaction and/or sense environmental stimuli. Frequently, multiple PAS domains are present within single polypeptide chains, where their interplay is required for protein function. Although many isolated PAS domain structures have been reported over the last decades, only a few structures of multi-PAS proteins are known. Therefore, the molecular mechanism of multi-PAS domain-mediated protein oligomerization and function is poorly understood. The transcription factor PpsR from Rhodobacter sphaeroides is such a multi-PAS domain protein that, in addition to its three PAS domains, contains a glutamine-rich linker and a C-terminal helix–turn–helix DNA-binding motif. Here, crystal structures of two N-terminally and C-terminally truncated PpsR variants that comprise a single (PpsR Q-PAS1 ) and two (PpsR N-Q-PAS1 ) PAS domains, respectively, are presented and the multi-step strategy required for the phasing of a triple PAS domain construct (PpsR ΔHTH ) is illustrated. While parts of the biologically relevant dimerization interface can already be observed in the two shorter constructs, the PpsR ΔHTH structure reveals how three PAS domains enable the formation of multiple oligomeric states (dimer, tetramer and octamer), highlighting that not only the PAS cores but also their α-helical extensions are essential for protein oligomerization. The results demonstrate that the long helical glutamine-rich linker of PpsR results from a direct fusion of the N-cap of the PAS1 domain with the C-terminal extension of the N-domain that plays an important

  3. Protic ionic liquids based on the dimeric and oligomeric anions: [(AcO)xH(x-1)]-.

    Science.gov (United States)

    Johansson, K M; Izgorodina, E I; Forsyth, M; MacFarlane, D R; Seddon, K R

    2008-05-28

    We describe a fluidity and conductivity study as a function of composition in N-methylpyrrolidine-acetic acid mixtures. The simple 1 : 1 acid-base mixture appears to form an ionic liquid, but its degree of ionicity is quite low and such liquids are better thought of as poorly dissociated mixtures of acid and base. The composition consisting of 3 moles acetic acid and 1 mole N-methylpyrrolidine is shown to form the highest ionicity mixture in this binary due to the presence of oligomeric anionic species [(AcO)(x)H(x-1)](-) stabilised by hydrogen bonds. These oligomeric species, being weaker bases than the acetate anion, shift the proton transfer equilibrium towards formation of ionic species, thus generating a higher degree of ionicity than is present at the 1 : 1 composition. A Walden plot analysis, thermogravimetric behaviour and proton NMR data, as well as ab initio calculations of the oligomeric species, all support this conclusion.

  4. The Agrobacterium tumefaciens Transcription Factor BlcR Is Regulated via Oligomerization

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Yi; Fiscus, Valena; Meng, Wuyi; Zheng, Zhida; Zhang, Lian-Hui; Fuqua, Clay; Chen, Lingling (IMCB-Singapore); (Indiana)

    2012-02-08

    The Agrobacterium tumefaciens BlcR is a member of the emerging isocitrate lyase transcription regulators that negatively regulates metabolism of {gamma}-butyrolactone, and its repressing function is relieved by succinate semialdehyde (SSA). Our crystal structure showed that BlcR folded into the DNA- and SSA-binding domains and dimerized via the DNA-binding domains. Mutational analysis identified residues, including Phe{sup 147}, that are important for SSA association; BlcR{sup F147A} existed as tetramer. Two BlcR dimers bound to target DNA and in a cooperative manner, and the distance between the two BlcR-binding sequences in DNA was critical for BlcR-DNA association. Tetrameric BlcR{sup F147A} retained DNA binding activity, and importantly, this activity was not affected by the distance separating the BlcR-binding sequences in DNA. SSA did not dissociate tetrameric BlcR{sup F147A} or BlcR{sup F147A}-DNA. As well as in the SSA-binding site, Phe{sup 147} is located in a structurally flexible loop that may be involved in BlcR oligomerization. We propose that SSA regulates BlcR DNA-binding function via oligomerization.

  5. An Asymmetric Deuterium Labeling Strategy to Identify Interprotomer and Intraprotomer NOEs in Oligomeric Proteins

    International Nuclear Information System (INIS)

    Jasanoff, Alan

    1998-01-01

    A major difficulty in determining the structure of an oligomeric protein by NMR is the problem of distinguishing inter- from intraprotomer NOEs. In order to address this issue in studies of the 27 kD compact trimeric domain of the MHC class II-associated invariant chain, we compared the 13C NOESY-HSQC spectrum of a uniformly 13C-labeled trimer with the spectrum of the same trimer labeled with 13C in only one protomer, and with deuterium in the other two protomers. The spectrum of the unmixed trimer included both inter- and intraprotomer NOEs while the spectrum of the mixed trimer included only intraprotomer peaks. NOEs clearly absent from the spectrum of the mixed trimer could be confidently assigned to interprotomer interactions. Asymmetrically labeled trimers were isolated by refolding a 13C-labeled shorter form of the protein with a 2H-labeled longer form, chromatographically purifying trimers with only one short chain, and then processing with trypsin to yield only protomers with the desired N- and C-termini. In contrast to earlier studies, in which statistical mixtures of differently labeled protomers were analyzed, our procedure generated only a well-defined 1:2 oligomer, and no other mixed oligomers were present. This increased the maximum possible concentration of NMR-active protomers and thus the sensitivity of the experiments. Related methods should be applicable to many oligomeric proteins, particularly those with slow protomer exchange rates

  6. Direct Evidence of Intrinsic Blue Fluorescence from Oligomeric Interfaces of Human Serum Albumin.

    Science.gov (United States)

    Bhattacharya, Arpan; Bhowmik, Soumitra; Singh, Amit K; Kodgire, Prashant; Das, Apurba K; Mukherjee, Tushar Kanti

    2017-10-10

    The molecular origin behind the concentration-dependent intrinsic blue fluorescence of human serum albumin (HSA) is not known yet. This unusual blue fluorescence is believed to be a characteristic feature of amyloid-like fibrils of protein/peptide and originates due to the delocalization of peptide bond electrons through the extended hydrogen bond networks of cross-β-sheet structure. Herein, by combining the results of spectroscopy, size exclusion chromatography, native gel electrophoresis, and confocal microscopy, we have shown that the intrinsic blue fluorescence of HSA exclusively originates from oligomeric interfaces devoid of any amyloid-like fibrillar structure. Our study suggests that this low energy fluorescence band is not due to any particular residue/sequence, but rather it is a common feature of self-assembled peptide bonds. The present findings of intrinsic blue fluorescence from oligomeric interfaces pave the way for future applications of this unique visual phenomenon for early stage detection of various protein aggregation related human diseases.

  7. The N-terminus of TDP-43 promotes its oligomerization and enhances DNA binding affinity

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Chung-ke [Institute of Biomedical Sciences, Academia Sinica, Taipei 115, Taiwan (China); Wu, Tzong-Huah [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China); Chemical Biology and Molecular Biophysics Program, Taiwan International Graduate Program, Institute of Biochemistry, Academia Sinica, Taipei 115, Taiwan (China); Institute of Bioinformatics and Structural Biology, National Tsing Hua University, Hsinchu 300, Taiwan (China); Wu, Chu-Ya [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China); Graduate Institute of Engineering, National Taiwan University of Science and Technology, Taipei 106, Taiwan (China); Chiang, Ming-hui; Toh, Elsie Khai-Woon [Institute of Biomedical Sciences, Academia Sinica, Taipei 115, Taiwan (China); Hsu, Yin-Chih; Lin, Ku-Feng [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China); Liao, Yu-heng [Institute of Biomedical Sciences, Academia Sinica, Taipei 115, Taiwan (China); Huang, Tai-huang, E-mail: bmthh@gate.sinica.edu.tw [Institute of Biomedical Sciences, Academia Sinica, Taipei 115, Taiwan (China); Department of Physics, National Taiwan Normal University, Taipei 106, Taiwan (China); Huang, Joseph Jen-Tse, E-mail: jthuang@chem.sinica.edu.tw [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China)

    2012-08-24

    Highlights: Black-Right-Pointing-Pointer The N-terminus of TDP-43 contains an independently folded structural domain (NTD). Black-Right-Pointing-Pointer The structural domains of TDP-43 are arranged in a beads-on-a-string fashion. Black-Right-Pointing-Pointer The NTD promotes TDP-43 oligomerization in a concentration-dependent manner. Black-Right-Pointing-Pointer The NTD may assist nucleic acid-binding activity of TDP-43. -- Abstract: TDP-43 is a DNA/RNA-binding protein associated with different neurodegenerative diseases such as amyotrophic lateral sclerosis (ALS) and frontotemporal lobar degeneration (FTLD-U). Here, the structural and physical properties of the N-terminus on TDP-43 have been carefully characterized through a combination of nuclear magnetic resonance (NMR), circular dichroism (CD) and fluorescence anisotropy studies. We demonstrate for the first time the importance of the N-terminus in promoting TDP-43 oligomerization and enhancing its DNA-binding affinity. An unidentified structural domain in the N-terminus is also disclosed. Our findings provide insights into the N-terminal domain function of TDP-43.

  8. Conformational detection of p53's oligomeric state by FlAsH Fluorescence.

    Science.gov (United States)

    Webber, Tawnya M; Allen, Andrew C; Ma, Wai Kit; Molloy, Rhett G; Kettelkamp, Charisse N; Dow, Caitlin A; Gage, Matthew J

    2009-06-19

    The p53 tumor suppressor protein is a critical checkpoint in prevention of tumor formation, and the function of p53 is dependent on proper formation of the active tetramer. In vitro studies have shown that p53 binds DNA most efficiently as a tetramer, though inactive p53 is predicted to be monomeric in vivo. We demonstrate that FlAsH binding can be used to distinguish between oligomeric states of p53, providing a potential tool to explore p53 oligomerization in vivo. The FlAsH tetra-cysteine binding motif has been incorporated along the dimer and tetramer interfaces in the p53 tetramerization domain to create reporters for the dimeric and tetrameric states of p53, though the geometry of the four cysteines is critical for efficient FlAsH binding. Furthermore, we demonstrate that FlAsH binding can be used to monitor tetramer formation in real-time. These results demonstrate the potential for using FlAsH fluorescence to monitor protein-protein interactions in vivo.

  9. Oligomerization of glycine and alanine catalyzed by iron oxides: implications for prebiotic chemistry.

    Science.gov (United States)

    Shanker, Uma; Bhushan, Brij; Bhattacharjee, G; Kamaluddin

    2012-02-01

    Iron oxide minerals are probable constituents of the sediments present in geothermal regions of the primitive earth. They might have adsorbed different organic monomers (amino acids, nucleotides etc.) and catalyzed polymerization processes leading to the formation of the first living cell. In the present work we tested the catalytic activity of three forms of iron oxides (Goethite, Akaganeite and Hematite) in the intermolecular condensation of each of the amino acids glycine and L-alanine. The effect of zinc oxide and titanium dioxide on the oligomerization has also been studied. Oligomerization studies were performed for 35 days at three different temperatures 50, 90 and 120°C without applying drying/wetting cycling. The products formed were characterized by HPLC and ESI-MS techniques. All three forms of iron oxides catalyzed peptide bond formation (23.2% of gly2 and 10.65% of ala2). The reaction was monitored every 7 days. Formation of peptides was observed to start after 7 days at 50°C. Maximum yield of peptides was found after 35 days at 90°C. Reaction at 120°C favors formation of diketopiperazine derivatives. It is also important to note that after 35 days of reaction, goethite produced dimer and trimer with the highest yield among the oxides tested. We suggest that the activity of goethite could probably be due to its high surface area and surface acidity.

  10. Phosphate and HEPES buffers potently affect the fibrillation and oligomerization mechanism of Alzheimer's Aβ peptide

    International Nuclear Information System (INIS)

    Garvey, Megan; Tepper, Katharina; Haupt, Caroline; Knuepfer, Uwe; Klement, Karolin; Meinhardt, Jessica; Horn, Uwe; Balbach, Jochen; Faendrich, Marcus

    2011-01-01

    Highlights: → Sodium phosphate buffer accelerated Aβ(1-40) nucleation relative to HEPES. → Aβ(1-40) fibrils formed in the two buffers show only minor structural differences. → NMR revealed that Aβ(1-40) histidine residues mediate buffer dependent changes. -- Abstract: The oligomerization of Aβ peptide into amyloid fibrils is a hallmark of Alzheimer's disease. Due to its biological relevance, phosphate is the most commonly used buffer system for studying the formation of Aβ and other amyloid fibrils. Investigation into the characteristics and formation of amyloid fibrils frequently relies upon material formed in vitro, predominantly in phosphate buffers. Herein, we examine the effects on the fibrillation and oligomerization mechanism of Aβ peptide that occur due solely to the influence of phosphate buffer. We reveal that significant differences in amyloid fibrillation are observed due to fibrillation being initiated in phosphate or HEPES buffer (at physiological pH and temperature). Except for the differing buffer ions, all experimental parameters were kept constant. Fibril formation was assessed using fluorescently monitored kinetic studies, microscopy, X-ray fiber diffraction and infrared and nuclear magnetic resonance spectroscopies. Based on this set up, we herein reveal profound effects on the mechanism and speed of Aβ fibrillation. The three histidine residues at positions 6, 13 and 14 of Aβ(1-40) are instrumental in these mechanistic changes. We conclude that buffer plays a more significant role in fibril formation than has been generally acknowledged.

  11. Multicoil2: predicting coiled coils and their oligomerization states from sequence in the twilight zone.

    Directory of Open Access Journals (Sweden)

    Jason Trigg

    Full Text Available The alpha-helical coiled coil can adopt a variety of topologies, among the most common of which are parallel and antiparallel dimers and trimers. We present Multicoil2, an algorithm that predicts both the location and oligomerization state (two versus three helices of coiled coils in protein sequences. Multicoil2 combines the pairwise correlations of the previous Multicoil method with the flexibility of Hidden Markov Models (HMMs in a Markov Random Field (MRF. The resulting algorithm integrates sequence features, including pairwise interactions, through multinomial logistic regression to devise an optimized scoring function for distinguishing dimer, trimer and non-coiled-coil oligomerization states; this scoring function is used to produce Markov Random Field potentials that incorporate pairwise correlations localized in sequence. Multicoil2 significantly improves both coiled-coil detection and dimer versus trimer state prediction over the original Multicoil algorithm retrained on a newly-constructed database of coiled-coil sequences. The new database, comprised of 2,105 sequences containing 124,088 residues, includes reliable structural annotations based on experimental data in the literature. Notably, the enhanced performance of Multicoil2 is evident when tested in stringent leave-family-out cross-validation on the new database, reflecting expected performance on challenging new prediction targets that have minimal sequence similarity to known coiled-coil families. The Multicoil2 program and training database are available for download from http://multicoil2.csail.mit.edu.

  12. Catalysis of the Oligomerization of O-Phospho-Serine, Aspartic Acid, or Glutamic Acid by Cationic Micelles

    Science.gov (United States)

    Bohler, Christof; Hill, Aubrey R., Jr.; Orgel, Leslie E.

    1996-01-01

    Treatment of relatively concentrated aqueous solutions of 0-phospho-serine (50 mM), aspartic acid (100 mM) or glutamic acid (100 mM) with carbonyldiimidazole leads to the formation of an activated intermediate that oligomerizes efficiently. When the concentration of amino acid is reduced tenfold, few long oligomers can be detected. Positively-charged cetyltrimethyl ammonium bromide micelles concentrate the negatively-charged activated intermediates of the amino acids at their surfaces and catalyze efficient oligomerization even from dilute solutions.

  13. Catalytic Oligomerization of Terminal Alkynes by Lanthanide Carbyls (η5-C5Me5)2LnCH(SiMe3)2 (Ln = Y, La, Ce)

    NARCIS (Netherlands)

    Heeres, H.J.; Teuben, J.H.

    1991-01-01

    Lanthanide and group 3 carbyls Cp*2LnCH(SiMe3)2 (1, Ln = Y; 2, Ln = La; 3, Ln = Ce) are active catalyst precursors for the oligomerization of terminal alkynes HC≡CR (R = alkyl, aryl, SiMe3). The regioselectivity and the extent of oligomerization depend strongly on the lanthanide applied as well as

  14. An Improved Computing Method for 3D Mechanical Connectivity Rates Based on a Polyhedral Simulation Model of Discrete Fracture Network in Rock Masses

    Science.gov (United States)

    Li, Mingchao; Han, Shuai; Zhou, Sibao; Zhang, Ye

    2018-06-01

    Based on a 3D model of a discrete fracture network (DFN) in a rock mass, an improved projective method for computing the 3D mechanical connectivity rate was proposed. The Monte Carlo simulation method, 2D Poisson process and 3D geological modeling technique were integrated into a polyhedral DFN modeling approach, and the simulation results were verified by numerical tests and graphical inspection. Next, the traditional projective approach for calculating the rock mass connectivity rate was improved using the 3D DFN models by (1) using the polyhedral model to replace the Baecher disk model; (2) taking the real cross section of the rock mass, rather than a part of the cross section, as the test plane; and (3) dynamically searching the joint connectivity rates using different dip directions and dip angles at different elevations to calculate the maximum, minimum and average values of the joint connectivity at each elevation. In a case study, the improved method and traditional method were used to compute the mechanical connectivity rate of the slope of a dam abutment. The results of the two methods were further used to compute the cohesive force of the rock masses. Finally, a comparison showed that the cohesive force derived from the traditional method had a higher error, whereas the cohesive force derived from the improved method was consistent with the suggested values. According to the comparison, the effectivity and validity of the improved method were verified indirectly.

  15. Comparison of the bacterial removal performance of silver nanoparticles and a polymer based quaternary amine functiaonalized silsesquioxane coated point-of-use ceramic water filters.

    Science.gov (United States)

    Zhang, Hongyin; Oyanedel-Craver, Vinka

    2013-09-15

    This study compares the disinfection performance of ceramic water filters impregnated with two antibacterial compounds: silver nanoparticles and a polymer based quaternary amine functiaonalized silsesquioxane (poly(trihydroxysilyl) propyldimethyloctadecyl ammonium chloride (TPA)). This study evaluated these compounds using ceramic disks manufactures with clay obtained from a ceramic filter factory located in San Mateo Ixtatan, Guatemala. Instead of using full size ceramic water filters, manufactured 6.5 cm diameter ceramic water filter disks were used. Results showed that TPA can achieve a log bacterial reduction value of 10 while silver nanoparticles reached up to 2 log reduction using a initial concentration of bacteria of 10(10)-10(11)CFU/ml. Similarly, bacterial transport demonstrated that ceramic filter disks painted with TPA achieved a bacterial log reduction value of 6.24, which is about 2 log higher than the values obtained for disks painted with silver nanoparticles (bacterial log reduction value: 4.42). The release of both disinfectants from the ceramic materials to the treated water was determined measuring the effluent concentrations in each test performed. Regarding TPA, about 3% of the total mass applied to the ceramic disks was released in the effluent over 300 min, which is slightly lower than the release percentage for silver nanoparticles (4%). This study showed that TPA provides a comparable disinfection performance than silver nanoparticles in ceramic water filter. Another advantage of using TPA is the cost as the price of TPA is considerable lower than silver nanoparticles. In spite of the use of TPA in several medical related products, there is only partial information regarding the health risk associated with the ingestion of this compound. Additional long-term toxicological information for TPA should be evaluated before its future application in ceramic water filters. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. A soluble star-shaped silsesquioxane-cored polymer-towards novel stabilization of pH-dependent high internal phase emulsions.

    Science.gov (United States)

    Xing, Yuxiu; Peng, Jun; Xu, Kai; Gao, Shuxi; Gui, Xuefeng; Liang, Shengyuan; Sun, Longfeng; Chen, Mingcai

    2017-08-30

    A well-defined pH-responsive star-shaped polymer containing poly(N,N-dimethylaminoethyl methacrylate) (PDMA) arms and a cage-like methacryloxypropyl silsesquioxane (CMSQ-T 10 ) core was used as an interfacial stabilizer for emulsions consisting of m-xylene and water. We explored the properties of the CMSQ/PDMA star-shaped polymer using the characteristic results of nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC), dynamic light scattering (DLS), and zeta potential and conductivity measurements. The interfacial tension results showed that the CMSQ/PDMA star-shaped polymer reduced the interfacial tension between water and oil in a pH-dependent manner. Gelled high internal phase emulsions (HIPEs) including o/w and w/o types were formed in the pH ranges of 1.2-5.8 and 9.1-12.3 with the CMSQ/PDMA star-shaped polymer as a stabilizer, when the oil fractions were 80-90 vol% and 10-20 vol%, respectively. The soluble star-shaped polymer aggregated spontaneously to form a microgel that adsorbed to the two immiscible phases. Images of the fluorescently labeled polymers demonstrated that there was a star-shaped polymer in the continuous phase, and the non-Pickering stabilization based on the percolating network of the star-shaped polymer also contributed to the stabilization of the HIPE. This pH-dependent HIPE was prepared with a novel stabilization mechanism consisting of microgel adsorption and non-Pickering stabilization. Moreover, the preparation of HIPEs provided the possibility of their application in porous materials and responsive materials.

  17. On a novel method to synthesize POSS-based hybrids: An example of the preparation of TPU based system

    Directory of Open Access Journals (Sweden)

    O. Monticelli

    2013-12-01

    Full Text Available A novel method to prepare polymer/polyhedral oligomeric silsesquioxanes (POSS hybrids by melt reactive blending is proposed in this paper, by the controlled polymer chain scission and reaction of chain ends with functional silsesquioxanes. Application to thermoplastic polyurethanes (TPU is addressed, taking advantage of the polyurethane chain scission equilibrium reaction, leading to the formation of highly reactive isocyanate and hydroxyl chain ends. Despite the isocyanate chemistry has been widely studied for the preparation of polymer/POSS hybrids by in situ copolymerisation, the exploitation of similar chemical processes in an industrially viable and environmental friendly melt blending process is currently an open research field. In this work, the reaction in the molten state of dihydroxyl-functionalised POSS with the polyurethane chain is demonstrated to produce a TPU/POSS hybrids. The effect of POSS concentration on nanomorphology, thermal properties and surface properties is studied, showing significant changes compared to pristine TPU. In particular, an increase of glass transition temperature is observed in the presence of reactive POSS (ΔT up to about 10°C in the presence of 10 wt% loading. Furthermore, an increase of surface water wettability, evidenced by the decrease of water contact angle from 95° for pristine TPU to 70° in TPU containing 10"wt% of reactive POSS, is found.

  18. Self-assembly of dodecaphenyl POSS thin films

    Science.gov (United States)

    Handke, Bartosz; Klita, Łukasz; Niemiec, Wiktor

    2017-12-01

    The self-assembly abilities of Dodecaphenyl Polyhedral Oligomeric Silsesquioxane thin films on Si(1 0 0) surfaces were studied. Due to their thermal properties - relatively low sublimation temperature and preservation of molecular structure - cage type silsesquioxanes are ideal material for the preparation of a thin films by Physical Vapor Deposition. The Ultra-High Vacuum environment and the deposition precision of the PVD method enable the study of early stages of thin film growth and its molecular organization. X-ray Reflectivity and Atomic Force Microscopy measurements allow to pursuit size-effects in the structure of thin films with thickness ranges from less than a single molecular layer up to several tens of layers. Thermal treatment of the thin films triggered phase change: from a poorly ordered polycrystalline film into a well-ordered multilayer structure. Self-assembly of the layers is the effect of the π-stacking of phenyl rings, which force molecules to arrange in a superlattice, forming stacks of alternating organic-inorganic layers.

  19. Synthesis and characterization of a new composite based on copper (II) and octa (aminopropil)silsesquioxane; Sintese e caracterizacao de novos compositos a base de cobre (II) e octa(aminopropil)silsesquioxano

    Energy Technology Data Exchange (ETDEWEB)

    Magossi, M.S. de; Carmo, D.R. do, E-mail: marymagossi@gmail.com [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Ilha Solteira, SP (Brazil). Faculdade de Engenharia

    2014-07-01

    In this work, a new compound based silsesquioxane and nitroprusside of copper was prepared starting from octa (aminopropyl)silsesquioxane following a new route of synthesis. The composite prepared as described ACCuN was preliminarily characterized by spectroscopic techniques, such as Infrared Spectroscopy in the Region of the Fourier transform (FTIR), Energy Dispersive X-ray (EDX), Scanning Electron Microscopy (SEM) and cyclic voltammetry (VC). The FTIR spectra showed absorption bands at 1106 cm{sup -1} due to stretching Si-O-Si{sub (νSi-O-Si)} characteristic of the structure of octa(aminopropylsilsesquioxane and absorption bands at 2063 cm{sup -1} ascribed to the stretching NO{sub (νN-O}) and 2192 cm{sup -1} attributed to the stretching C≡N{sub (ν≡}N{sub )}. SEM and EDX observed cluster of cubic particles with an average size of approximately 241 nm, containing Si, O, N, Cu and Fe. Cyclic voltammogram of the material (ACCuN) showed a redox couple with average potential Eθ '= 0.73 V. (author)

  20. Chaperonin of Group I: Oligomeric Spectrum and Biochemical and Biological Implications

    Directory of Open Access Journals (Sweden)

    Silvia Vilasi

    2018-01-01

    Full Text Available Chaperonins play various physiological roles and can also be pathogenic. Elucidation of their structure, e.g., oligomeric status and post-translational modifications (PTM, is necessary to understand their functions and mechanisms of action in health and disease. Group I chaperonins form tetradecamers with two stacked heptameric rings. The tetradecamer is considered the typical functional complex for folding of client polypeptides. However, other forms such as the monomer and oligomers with smaller number of subunits than the classical tetradecamer, also occur in cells. The properties and functions of the monomer and oligomers, and their roles in chaperonin-associated diseases are still incompletely understood. Chaperonin I in eukaryotes occurs in various locations, not just the mitochondrion, which is its canonical place of residence and function. Eukaryotic Chaperonin I, namely Hsp60 (designated HSP60 or HSPD1 in humans has, indeed, been found in the cytosol; the plasma-cell membrane; on the outer surface of cells; in the intercellular space; in biological liquids such as lymph, blood, and cerebrospinal fluid; and in secretions, for instance saliva and urine. Hsp60 has also been found in cell-derived vesicles such as exosomes. The functions of Hsp60 in all these non-canonical locales are still poorly characterized and one of the questions not yet answered is in what form, i.e., monomer or oligomer, is the chaperonin present in these non-canonical locations. In view of the steady increase in interest on chaperonopathies over the last several years, we have studied human HSP60 to determine its role in various diseases, its locations in cells and tissues and migrations in the body, and its post-translational modifications that might have an impact on its location and function. We also carried out experiments to characterize the oligomeric status of extramitochondrial of HSP60 in solution. Here, we provide an overview of our results, focusing on

  1. Interference with RUNX1/ETO Leukemogenic Function by Cell-Penetrating Peptides Targeting the NHR2 Oligomerization Domain

    Directory of Open Access Journals (Sweden)

    Yvonne Bartel

    2013-01-01

    Full Text Available The leukemia-associated fusion protein RUNX1/ETO is generated by the chromosomal translocation t(8;21 which appears in about 12% of all de novo acute myeloid leukemias (AMLs. Essential for the oncogenic potential of RUNX1/ETO is the oligomerization of the chimeric fusion protein through the nervy homology region 2 (NHR2 within ETO. In previous studies, we have shown that the intracellular expression of peptides containing the NHR2 domain inhibits RUNX1/ETO oligomerization, thereby preventing cell proliferation and inducing differentiation of RUNX1/ETO transformed cells. Here, we show that introduction of a recombinant TAT-NHR2 fusion polypeptide into the RUNX1/ETO growth-dependent myeloid cell line Kasumi-1 results in decreased cell proliferation and increased numbers of apoptotic cells. This effect was highly specific and mediated by binding the TAT-NHR2 peptide to ETO sequences, as TAT-polypeptides containing the oligomerization domain of BCR did not affect cell proliferation or apoptosis in Kasumi-1 cells. Thus, the selective interference with NHR2-mediated oligomerization by peptides represents a challenging but promising strategy for the inhibition of the leukemogenic potential of RUNX1/ETO in t(8;21-positive leukemia.

  2. 78 FR 65561 - D-Glucopyranose, oligomeric, decyl octyl glycosides; Exemption from the Requirement of a Tolerance

    Science.gov (United States)

    2013-11-01

    ... metabolize D-glucopyranose, oligomeric, C 10 -C 16 -alkyl glycosides to water-soluble substances... polyoxyethylene polymers and fatty acids; carriers such as clay and diatomaceous earth; thickeners such as... exposure through drinking water and in residential settings, but does not include occupational exposure...

  3. Regulation of complement by cartilage oligomeric matrix protein allows for a novel molecular diagnostic principle in rheumatoid arthritis

    DEFF Research Database (Denmark)

    Happonen, Kaisa E; Saxne, Tore; Aspberg, Anders

    2010-01-01

    Cartilage oligomeric matrix protein (COMP) is a structural component of cartilage, where it catalyzes collagen fibrillogenesis. Elevated amounts of COMP are found in serum during increased turnover of cartilage associated with active joint disease, such as rheumatoid arthritis (RA) and osteoarthr...

  4. A Small-Molecule Inhibitor of Bax and Bak Oligomerization Prevents Genotoxic Cell Death and Promotes Neuroprotection.

    Science.gov (United States)

    Niu, Xin; Brahmbhatt, Hetal; Mergenthaler, Philipp; Zhang, Zhi; Sang, Jing; Daude, Michael; Ehlert, Fabian G R; Diederich, Wibke E; Wong, Eve; Zhu, Weijia; Pogmore, Justin; Nandy, Jyoti P; Satyanarayana, Maragani; Jimmidi, Ravi K; Arya, Prabhat; Leber, Brian; Lin, Jialing; Culmsee, Carsten; Yi, Jing; Andrews, David W

    2017-04-20

    Aberrant apoptosis can lead to acute or chronic degenerative diseases. Mitochondrial outer membrane permeabilization (MOMP) triggered by the oligomerization of the Bcl-2 family proteins Bax/Bak is an irreversible step leading to execution of apoptosis. Here, we describe the discovery of small-molecule inhibitors of Bax/Bak oligomerization that prevent MOMP. We demonstrate that these molecules disrupt multiple, but not all, interactions between Bax dimer interfaces thereby interfering with the formation of higher-order oligomers in the MOM, but not recruitment of Bax to the MOM. Small-molecule inhibition of Bax/Bak oligomerization allowed cells to evade apoptotic stimuli and rescued neurons from death after excitotoxicity, demonstrating that oligomerization of Bax is essential for MOMP. Our discovery of small-molecule Bax/Bak inhibitors provides novel tools for the investigation of the mechanisms leading to MOMP and will ultimately facilitate development of compounds inhibiting Bax/Bak in acute and chronic degenerative diseases. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Kinetics in Signal Transduction Pathways Involving Promiscuous Oligomerizing Receptors Can Be Determined by Receptor Specificity : Apoptosis Induction by TRAIL

    NARCIS (Netherlands)

    Szegezdi, Eva; van der Sloot, Almer M.; Mahalingam, Devalingam; O'Leary, Lynda; Cool, Robbert H.; Munoz, Ines G.; Montoya, Guillermo; Quax, Wim J.; de Jong, Steven; Samali, Afshin; Serrano, Luis

    Here we show by computer modeling that kinetics and outcome of signal transduction in case of hetero-oligomerizing receptors of a promiscuous ligand largely depend on the relative amounts of its receptors. Promiscuous ligands can trigger the formation of nonproductive receptor complexes, which slows

  6. Orally administrated cinnamon extract reduces β-amyloid oligomerization and corrects cognitive impairment in Alzheimer's disease animal models.

    Directory of Open Access Journals (Sweden)

    Anat Frydman-Marom

    Full Text Available An increasing body of evidence indicates that accumulation of soluble oligomeric assemblies of β-amyloid polypeptide (Aβ play a key role in Alzheimer's disease (AD pathology. Specifically, 56 kDa oligomeric species were shown to be correlated with impaired cognitive function in AD model mice. Several reports have documented the inhibition of Aβ plaque formation by compounds from natural sources. Yet, evidence for the ability of common edible elements to modulate Aβ oligomerization remains an unmet challenge. Here we identify a natural substance, based on cinnamon extract (CEppt, which markedly inhibits the formation of toxic Aβ oligomers and prevents the toxicity of Aβ on neuronal PC12 cells. When administered to an AD fly model, CEppt rectified their reduced longevity, fully recovered their locomotion defects and totally abolished tetrameric species of Aβ in their brain. Furthermore, oral administration of CEppt to an aggressive AD transgenic mice model led to marked decrease in 56 kDa Aβ oligomers, reduction of plaques and improvement in cognitive behavior. Our results present a novel prophylactic approach for inhibition of toxic oligomeric Aβ species formation in AD through the utilization of a compound that is currently in use in human diet.

  7. Styrene oligomerization as a molecular probe reaction for zeolite acidity: a UV-Vis spectroscopy and DFT study

    NARCIS (Netherlands)

    Buurmans, I.L.C.; Pidko, E.A.; Groot, de J.M.; Stavitski, E.; Santen, van R.A.; Weckhuysen, B.M.

    2010-01-01

    A series of H-ZSM-5 crystallites with different framework Si/Al ratios was studied by analyzing the kinetics and reaction mechanism of the oligomerization of 4-fluorostyrene as molecular probe reaction for Brønsted acidity. The formation of carbocationic species was followed by UV-Vis spectroscopy.

  8. Human α4β2 nicotinic acetylcholine receptor as a novel target of oligomeric α-synuclein.

    Directory of Open Access Journals (Sweden)

    Qiang Liu

    Full Text Available Cigarette smoking is associated with a decreased incidence of Parkinson disease (PD through unknown mechanisms. Interestingly, a decrease in the numbers of α4β2 nicotinic acetylcholine receptors (α4β2-nAChRs in PD patients suggests an α4β2-nAChR-mediated cholinergic deficit in PD. Although oligomeric forms of α-synuclein have been recognized to be toxic and involved in the pathogenesis of PD, their direct effects on nAChR-mediated cholinergic signaling remains undefined. Here, we report for the first time that oligomeric α-synuclein selectively inhibits human α4β2-nAChR-mediated currents in a dose-dependent, non-competitive and use-independent manner. We show that pre-loading cells with guanyl-5'-yl thiophosphate fails to prevent this inhibition, suggesting that the α-synuclein-induced inhibition of α4β2-nAChR function is not mediated by nAChR internalization. By using a pharmacological approach and cultures expressing transfected human nAChRs, we have shown a clear effect of oligomeric α-synuclein on α4β2-nAChRs, but not on α4β4- or α7-nAChRs, suggesting nAChR subunit selectivity of oligomeric α-synuclein-induced inhibition. In addition, by combining the size exclusion chromatography and atomic force microscopy (AFM analyses, we find that only large (>4 nm oligomeric α-synuclein aggregates (but not monomeric, small oligomeric or fibrillar α-synuclein aggregates exhibit the inhibitory effect on human α4β2-nAChRs. Collectively, we have provided direct evidence that α4β2-nAChR is a sensitive target to mediate oligomeric α-synuclein-induced modulation of cholinergic signaling, and our data imply that therapeutic strategies targeted toward α4β2-nAChRs may have potential for developing new treatments for PD.

  9. Cartilage oligomeric matrix protein in patients with juvenile idiopathic arthritis: relation to growth and disease activity

    DEFF Research Database (Denmark)

    Bjørnhart, Birgitte; Juul, Anders; Nielsen, Susan

    2009-01-01

    OBJECTIVE: Cartilage oligomeric matrix protein (COMP) has been identified as a prognostic marker of progressive joint destruction in rheumatoid arthritis. In this population based study we evaluated associations between plasma concentrations of COMP, disease activity, and growth velocity...... in patients with recent-onset juvenile idiopathic arthritis (JIA). COMP levels in JIA and healthy children were compared with those in healthy adults. Plasma levels of insulin-like growth factor I (IGF-1), which has been associated with COMP expression and growth velocity, were studied in parallel. METHODS......: 87 patients with JIA entered the study, including oligoarticular JIA (n = 34), enthesitis-related arthritis (n = 8), polyarticular rheumatoid factor (RF)-positive JIA (n = 2), polyarticular RF-negative JIA (n = 27), systemic JIA (n = 6), and undifferentiated JIA (n = 10). Plasma levels of COMP were...

  10. Assembly of the intrinsic factor domains and oligomerization of the protein in the presence of cobalamin

    DEFF Research Database (Denmark)

    Fedosov, Sergey N; Fedosova, Natalya U; Berglund, Lars

    2004-01-01

    oligomerized. A mixture of two fragments IF(30) + IF(20) and Cbl produced a firm complex, IF(30+20).Cbl, which could not associate to dimers. In contrast to IF(30+20).Cbl, the saturated full-length monomers IF(50).Cbl dimerized with K(d) approximately 1 microM. We suggest a two-domain organization of the full......-length protein, where two distant units, IF(30) and IF(20), can be assembled only by Cbl. They are connected by a protease-sensitive link, whose native structure is likely to be important for dimerization. However, linkage between two domains is not compulsory for Cbl binding. Advantages of the two...

  11. Core-6 fucose and the oligomerization of the 1918 pandemic influenza viral neuraminidase

    International Nuclear Information System (INIS)

    Wu, Zhengliang L.; Zhou, Hui; Ethen, Cheryl M.; Reinhold, Vernon N.

    2016-01-01

    The 1918 H1N1 influenza virus was responsible for one of the most deadly pandemics in human history. Yet to date, the structure component responsible for its virulence is still a mystery. In order to search for such a component, the neuraminidase (NA) antigen of the virus was expressed, which led to the discovery of an active form (tetramer) and an inactive form (dimer and monomer) of the protein due to different glycosylation. In this report, the N-glycans from both forms were released and characterized by mass spectrometry. It was found that the glycans from the active form had 26% core-6 fucosylated, while the glycans from the inactive form had 82% core-6 fucosylated. Even more surprisingly, the stalk region of the active form was almost completely devoid of core-6-linked fucose. These findings were further supported by the results obtained from in vitro incorporation of azido fucose and "3H-labeled fucose using core-6 fucosyltransferase, FUT8. In addition, the incorporation of fucose did not change the enzymatic activity of the active form, implying that core-6 fucose is not directly involved in the enzymatic activity. It is postulated that core-6 fucose prohibits the oligomerization and subsequent activation of the enzyme. - Graphical abstract: Proposed mechanism for how core-fucose prohibits the tetramerization of the 1918 pandemic viral neuraminidase. Only the cross section of the stalk region with two N-linked glycans are depicted for clarity. (A) Carbohydrate–carbohydrate interaction on non-fucosylated monomer allows tetramerization. (B) Core-fucosylation disrupts the interaction and prevents the tetramerization. - Highlights: • Expressed 1918 pandemic influenza viral neuraminidase has inactive and active forms. • The inactive form contains high level of core-6 fucose, while the active form lacks such modification. • Core fucose could interfere the oligomerization of the neuraminidase and thus its activation. • This discovery may explain why

  12. Structural adaptation of the subunit interface of oligomeric thermophilic and hyperthermophilic enzymes.

    Science.gov (United States)

    Maugini, Elisa; Tronelli, Daniele; Bossa, Francesco; Pascarella, Stefano

    2009-04-01

    Enzymes from thermophilic and, particularly, from hyperthermophilic organisms are surprisingly stable. Understanding of the molecular origin of protein thermostability and thermoactivity attracted the interest of many scientist both for the perspective comprehension of the principles of protein structure and for the possible biotechnological applications through application of protein engineering. Comparative studies at sequence and structure levels were aimed at detecting significant differences of structural parameters related to protein stability between thermophilic and hyperhermophilic structures and their mesophilic homologs. Comparative studies were useful in the identification of a few recurrent themes which the evolution utilized in different combinations in different protein families. These studies were mostly carried out at the monomer level. However, maintenance of a proper quaternary structure is an essential prerequisite for a functional macromolecule. At the environmental temperatures experienced typically by hyper- and thermophiles, the subunit interactions mediated by the interface must be sufficiently stable. Our analysis was therefore aimed at the identification of the molecular strategies adopted by evolution to enhance interface thermostability of oligomeric enzymes. The variation of several structural properties related to protein stability were tested at the subunit interfaces of thermophilic and hyperthermophilic oligomers. The differences of the interface structural features observed between the hyperthermophilic and thermophilic enzymes were compared with the differences of the same properties calculated from pairwise comparisons of oligomeric mesophilic proteins contained in a reference dataset. The significance of the observed differences of structural properties was measured by a t-test. Ion pairs and hydrogen bonds do not vary significantly while hydrophobic contact area increases specially in hyperthermophilic interfaces. Interface

  13. Core-6 fucose and the oligomerization of the 1918 pandemic influenza viral neuraminidase

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Zhengliang L., E-mail: Leon.wu@bio-techne.com [Bio-Techne Inc., 614 McKinley Place NE, Minneapolis, MN 55413 (United States); Zhou, Hui [Gregg Hall, UNH Glycomics Center, University of New Hampshire (United States); Ethen, Cheryl M. [Bio-Techne Inc., 614 McKinley Place NE, Minneapolis, MN 55413 (United States); Reinhold, Vernon N., E-mail: Vernon.Reinhold@unh.edu [Gregg Hall, UNH Glycomics Center, University of New Hampshire (United States)

    2016-04-29

    The 1918 H1N1 influenza virus was responsible for one of the most deadly pandemics in human history. Yet to date, the structure component responsible for its virulence is still a mystery. In order to search for such a component, the neuraminidase (NA) antigen of the virus was expressed, which led to the discovery of an active form (tetramer) and an inactive form (dimer and monomer) of the protein due to different glycosylation. In this report, the N-glycans from both forms were released and characterized by mass spectrometry. It was found that the glycans from the active form had 26% core-6 fucosylated, while the glycans from the inactive form had 82% core-6 fucosylated. Even more surprisingly, the stalk region of the active form was almost completely devoid of core-6-linked fucose. These findings were further supported by the results obtained from in vitro incorporation of azido fucose and {sup 3}H-labeled fucose using core-6 fucosyltransferase, FUT8. In addition, the incorporation of fucose did not change the enzymatic activity of the active form, implying that core-6 fucose is not directly involved in the enzymatic activity. It is postulated that core-6 fucose prohibits the oligomerization and subsequent activation of the enzyme. - Graphical abstract: Proposed mechanism for how core-fucose prohibits the tetramerization of the 1918 pandemic viral neuraminidase. Only the cross section of the stalk region with two N-linked glycans are depicted for clarity. (A) Carbohydrate–carbohydrate interaction on non-fucosylated monomer allows tetramerization. (B) Core-fucosylation disrupts the interaction and prevents the tetramerization. - Highlights: • Expressed 1918 pandemic influenza viral neuraminidase has inactive and active forms. • The inactive form contains high level of core-6 fucose, while the active form lacks such modification. • Core fucose could interfere the oligomerization of the neuraminidase and thus its activation. • This discovery may explain

  14. An Intramolecular Salt Bridge in Bacillus thuringiensis Cry4Ba Toxin Is Involved in the Stability of Helix α-3, Which Is Needed for Oligomerization and Insecticidal Activity.

    Science.gov (United States)

    Pacheco, Sabino; Gómez, Isabel; Sánchez, Jorge; García-Gómez, Blanca-Ines; Soberón, Mario; Bravo, Alejandra

    2017-10-15

    Bacillus thuringiensis three-domain Cry toxins kill insects by forming pores in the apical membrane of larval midgut cells. Oligomerization of the toxin is an important step for pore formation. Domain I helix α-3 participates in toxin oligomerization. Here we identify an intramolecular salt bridge within helix α-3 of Cry4Ba (D111-K115) that is conserved in many members of the family of three-domain Cry toxins. Single point mutations such as D111K or K115D resulted in proteins severely affected in toxicity. These mutants were also altered in oligomerization, and the mutant K115D was more sensitive to protease digestion. The double point mutant with reversed charges, D111K-K115D, recovered both oligomerization and toxicity, suggesting that this salt bridge is highly important for conservation of the structure of helix α-3 and necessary to promote the correct oligomerization of the toxin. IMPORTANCE Domain I has been shown to be involved in oligomerization through helix α-3 in different Cry toxins, and mutations affecting oligomerization also elicit changes in toxicity. The three-dimensional structure of the Cry4Ba toxin reveals an intramolecular salt bridge in helix α-3 of domain I. Mutations that disrupt this salt bridge resulted in changes in Cry4Ba oligomerization and toxicity, while a double point reciprocal mutation that restored the salt bridge resulted in recovery of toxin oligomerization and toxicity. These data highlight the role of oligomer formation as a key step in Cry4Ba toxicity. Copyright © 2017 American Society for Microbiology.

  15. Forward calculation of gravity and its gradient using polyhedral representation of density interfaces: an application of spherical or ellipsoidal topographic gravity effect

    Science.gov (United States)

    Zhang, Yi; Chen, Chao

    2018-02-01

    A density interface modeling method using polyhedral representation is proposed to construct 3-D models of spherical or ellipsoidal interfaces such as the terrain surface of the Earth and applied to forward calculating gravity effect of topography and bathymetry for regional or global applications. The method utilizes triangular facets to fit undulation of the target interface. The model maintains almost equal accuracy and resolution at different locations of the globe. Meanwhile, the exterior gravitational field of the model, including its gravity and gravity gradients, is obtained simultaneously using analytic solutions. Additionally, considering the effect of distant relief, an adaptive computation process is introduced to reduce the computational burden. Then features and errors of the method are analyzed. Subsequently, the method is applied to an area for the ellipsoidal Bouguer shell correction as an example and the result is compared to existing methods, which shows our method provides high accuracy and great computational efficiency. Suggestions for further developments and conclusions are drawn at last.

  16. Facile hydrothermal synthesis of polyhedral Fe3O4 nanocrystals, influencing factors and application in the electrochemical detection of H2O2

    International Nuclear Information System (INIS)

    Yuan Kefeng; Ni Yonghong; Zhang Li

    2012-01-01

    Highlights: ► Fe 3 O 4 polyhedra had been successfully synthesized by a facile hydrothermal technology. ► The as-obtained product exhibited the room-temperature ferrimagnetic property. ► The final product could be prepared into an electrochemical sensor for the detection of H 2 O 2 . - Abstract: Polyhedral Fe 3 O 4 nanocrystals have been successfully synthesized by a facile hydrothermal technique, employing FeSO 4 ·7H 2 O, N 2 H 4 and NH 3 ·H 2 O as the reactants without the assistance of any surfactant. The phase of the as-obtained Fe 3 O 4 was characterized by X-ray powder diffraction (XRD) and further proved by Rietveld refinement of XRD data. Energy dispersive spectrometry (EDS) and scanning electron microscopy (SEM) were used for the composition and morphology analyses of the final product. Some factors influencing the formation of polyhedral Fe 3 O 4 nanocrystals were systematically investigated, including the reaction temperature and time, and the original volume ratio of NH 3 ·H 2 O/N 2 H 4 ·H 2 O. It was found that the as-prepared Fe 3 O 4 polyhedra exhibited a good electrochemical property in 0.1 M phosphate buffer solution (PBS) with pH 7.0 and could be prepared into an electrochemical sensor for the detection of H 2 O 2 . The linear response range of the sensor was 10.0 × 10 −6 to 140.0 × 10 −6 M and a sensitivity was 11.05 μA/mM. Furthermore, the room-temperature magnetic property of the product was also investigated.

  17. Computational Study of the Effect of Confinement within Microporous Structures on the Activity and Selectivity of Metallocene Catalysts for Ethylene Oligomerization

    KAUST Repository

    Toulhoat, Hervé; Lontsi Fomena, Mireille; de Bruin, Theodorus

    2011-01-01

    The effect of confinement within some zeolitic structures on the activity and selectivity of metallocene catalysts for the ethylene oligomerization has been investigated using grand canonical Monte Carlo simulations (GCMC). The following zeolite

  18. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    Energy Technology Data Exchange (ETDEWEB)

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  19. Characterization of oligomerization of a peptide from the ebola virus glycoprotein by small-angle neutron scattering

    International Nuclear Information System (INIS)

    Egorov, V. V.; Gorshkov, A. N.; Murugova, T. N.; Vasin, A. V.; Lebedev, D. V.; Isaev-Ivanov, V. V.; Kiselev, O. I.

    2016-01-01

    Transmission electron microscopy (TEM) and small-angle neutron scattering (SANS) studies showed that model peptides QNALVCGLRQ (G33) and QNALVCGLRG (G31) corresponding to region 551–560 of the GP protein of the Sudan Ebola virus are prone to oligomerization in solution. Both peptides can form amyloid-like fibrills. The G33 peptide forms fibrils within one day of incubation, whereas the fibrillogenesis of the G31 peptide is observed only after incubation for several months. The possible role of the observed processes in the pathogenesis and the possibility of applying a combination of the TEM and SANS techniques to search for new compounds that are able to influence the protein oligomerization are discussed

  20. Characterization of oligomerization of a peptide from the ebola virus glycoprotein by small-angle neutron scattering

    Energy Technology Data Exchange (ETDEWEB)

    Egorov, V. V., E-mail: vlaegur@omrb.pnpi.spb.ru [National Research Center “Kurchatov Institute”, Konstantinov Petersburg Nuclear Physics Institute (Russian Federation); Gorshkov, A. N. [Ministry of Health of the Russian Federation, Research Institute of Influenza (Russian Federation); Murugova, T. N. [Joint Institute for Nuclear Research (Russian Federation); Vasin, A. V. [Ministry of Health of the Russian Federation, Research Institute of Influenza (Russian Federation); Lebedev, D. V.; Isaev-Ivanov, V. V. [National Research Center “Kurchatov Institute”, Konstantinov Petersburg Nuclear Physics Institute (Russian Federation); Kiselev, O. I. [Ministry of Health of the Russian Federation, Research Institute of Influenza (Russian Federation)

    2016-01-15

    Transmission electron microscopy (TEM) and small-angle neutron scattering (SANS) studies showed that model peptides QNALVCGLRQ (G33) and QNALVCGLRG (G31) corresponding to region 551–560 of the GP protein of the Sudan Ebola virus are prone to oligomerization in solution. Both peptides can form amyloid-like fibrills. The G33 peptide forms fibrils within one day of incubation, whereas the fibrillogenesis of the G31 peptide is observed only after incubation for several months. The possible role of the observed processes in the pathogenesis and the possibility of applying a combination of the TEM and SANS techniques to search for new compounds that are able to influence the protein oligomerization are discussed.

  1. Purification, crystallization and preliminary crystallographic analysis of Est-Y29: a novel oligomeric β-lactamase

    International Nuclear Information System (INIS)

    Kim, SeungBum; Joo, Sangbum; Yoon, Sangyoung; Kim, Sungsoo; Moon, Jongkook; Ryu, Yeonwoo; Kim, Kyeong Kyu; Kim, T. Doohun

    2009-01-01

    Est-Y29, a novel oligomeric class C β-lactamase from a metagenomic library, was crystallized in space group I4 1 and diffraction data were collected to 1.49 Å resolution. β-Lactam antibiotics such as penicillins and cephalosporins have a four-atom ring as a common element in their structure. The β-lactamases, which catalyze the inactivation of these antibiotics, are of great interest because of their high incidence in pathogenic bacteria. A novel oligomeric class C β-lactamase (Est-Y29) from a metagenomic library was expressed, purified and crystallized. The recombinant protein was expressed in Escherichia coli with an N-terminal 6×His tag and purified to homogeneity. EstY-29 was crystallized and X-ray intensity data were collected to 1.49 Å resolution using synchrotron radiation

  2. Moyamoya disease-associated protein mysterin/RNF213 is a novel AAA+ ATPase, which dynamically changes its oligomeric state

    Science.gov (United States)

    Morito, Daisuke; Nishikawa, Kouki; Hoseki, Jun; Kitamura, Akira; Kotani, Yuri; Kiso, Kazumi; Kinjo, Masataka; Fujiyoshi, Yoshinori; Nagata, Kazuhiro

    2014-03-01

    Moyamoya disease is an idiopathic human cerebrovascular disorder that is characterized by progressive stenosis and abnormal collateral vessels. We recently identified mysterin/RNF213 as its first susceptibility gene, which encodes a 591-kDa protein containing enzymatically active P-loop ATPase and ubiquitin ligase domains and is involved in proper vascular development in zebrafish. Here we demonstrate that mysterin further contains two tandem AAA+ ATPase modules and forms huge ring-shaped oligomeric complex. AAA+ ATPases are known to generally mediate various biophysical and mechanical processes with the characteristic ring-shaped structure. Fluorescence correlation spectroscopy and biochemical evaluation suggested that mysterin dynamically changes its oligomeric forms through ATP/ADP binding and hydrolysis cycles. Thus, the moyamoya disease-associated gene product is a unique protein that functions as ubiquitin ligase and AAA+ ATPase, which possibly contributes to vascular development through mechanical processes in the cell.

  3. Characterization of oligomerization of a peptide from the ebola virus glycoprotein by small-angle neutron scattering

    Science.gov (United States)

    Egorov, V. V.; Gorshkov, A. N.; Murugova, T. N.; Vasin, A. V.; Lebedev, D. V.; Isaev-Ivanov, V. V.; Kiselev, O. I.

    2016-01-01

    Transmission electron microscopy (TEM) and small-angle neutron scattering (SANS) studies showed that model peptides QNALVCGLRQ (G33) and QNALVCGLRG (G31) corresponding to region 551-560 of the GP protein of the Sudan Ebola virus are prone to oligomerization in solution. Both peptides can form amyloid-like fibrills. The G33 peptide forms fibrils within one day of incubation, whereas the fibrillogenesis of the G31 peptide is observed only after incubation for several months. The possible role of the observed processes in the pathogenesis and the possibility of applying a combination of the TEM and SANS techniques to search for new compounds that are able to influence the protein oligomerization are discussed.

  4. Moyamoya disease-associated protein mysterin/RNF213 is a novel AAA+ ATPase, which dynamically changes its oligomeric state

    Science.gov (United States)

    Morito, Daisuke; Nishikawa, Kouki; Hoseki, Jun; Kitamura, Akira; Kotani, Yuri; Kiso, Kazumi; Kinjo, Masataka; Fujiyoshi, Yoshinori; Nagata, Kazuhiro

    2014-01-01

    Moyamoya disease is an idiopathic human cerebrovascular disorder that is characterized by progressive stenosis and abnormal collateral vessels. We recently identified mysterin/RNF213 as its first susceptibility gene, which encodes a 591-kDa protein containing enzymatically active P-loop ATPase and ubiquitin ligase domains and is involved in proper vascular development in zebrafish. Here we demonstrate that mysterin further contains two tandem AAA+ ATPase modules and forms huge ring-shaped oligomeric complex. AAA+ ATPases are known to generally mediate various biophysical and mechanical processes with the characteristic ring-shaped structure. Fluorescence correlation spectroscopy and biochemical evaluation suggested that mysterin dynamically changes its oligomeric forms through ATP/ADP binding and hydrolysis cycles. Thus, the moyamoya disease-associated gene product is a unique protein that functions as ubiquitin ligase and AAA+ ATPase, which possibly contributes to vascular development through mechanical processes in the cell. PMID:24658080

  5. Development, validation and evaluation of an analytical method for the determination of monomeric and oligomeric procyanidins in apple extracts.

    Science.gov (United States)

    Hollands, Wendy J; Voorspoels, Stefan; Jacobs, Griet; Aaby, Kjersti; Meisland, Ane; Garcia-Villalba, Rocio; Tomas-Barberan, Francisco; Piskula, Mariusz K; Mawson, Deborah; Vovk, Irena; Needs, Paul W; Kroon, Paul A

    2017-04-28

    There is a lack of data for individual oligomeric procyanidins in apples and apple extracts. Our aim was to develop, validate and evaluate an analytical method for the separation, identification and quantification of monomeric and oligomeric flavanols in apple extracts. To achieve this, we prepared two types of flavanol extracts from freeze-dried apples; one was an epicatechin-rich extract containing ∼30% (w/w) monomeric (-)-epicatechin which also contained oligomeric procyanidins (Extract A), the second was an oligomeric procyanidin-rich extract depleted of epicatechin (Extract B). The parameters considered for method optimisation were HPLC columns and conditions, sample heating, mass of extract and dilution volumes. The performance characteristics considered for method validation included standard linearity, method sensitivity, precision and trueness. Eight laboratories participated in the method evaluation. Chromatographic separation of the analytes was best achieved utilizing a Hilic column with a binary mobile phase consisting of acidic acetonitrile and acidic aqueous methanol. The final method showed linearity for epicatechin in the range 5-100μg/mL with a correlation co-efficient >0.999. Intra-day and inter-day precision of the analytes ranged from 2 to 6% and 2 to 13% respectively. Up to dp3, trueness of the method was >95% but decreased with increasing dp. Within laboratory precision showed RSD values <5 and 10% for monomers and oligomers, respectively. Between laboratory precision was 4 and 15% (Extract A) and 7 and 30% (Extract B) for monomers and oligomers, respectively. An analytical method for the separation, identification and quantification of procyanidins in an apple extract was developed, validated and assessed. The results of the inter-laboratory evaluation indicate that the method is reliable and reproducible. Copyright © 2017. Published by Elsevier B.V.

  6. Both Ca2+ and Zn2+ are essential for S100A12 protein oligomerization and function

    Directory of Open Access Journals (Sweden)

    Shekhtman Alexander

    2009-04-01

    Full Text Available Abstract Background Human S100A12 is a member of the S100 family of EF-hand calcium-modulated proteins that are associated with many diseases including cancer, chronic inflammation and neurological disorders. S100A12 is an important factor in host/parasite defenses and in the inflammatory response. Like several other S100 proteins, it binds zinc and copper in addition to calcium. Mechanisms of zinc regulation have been proposed for a number of S100 proteins e.g. S100B, S100A2, S100A7, S100A8/9. The interaction of S100 proteins with their targets is strongly dependent on cellular microenvironment. Results The aim of the study was to explore the factors that influence S100A12 oligomerization and target interaction. A comprehensive series of biochemical and biophysical experiments indicated that changes in the concentration of calcium and zinc led to changes in the oligomeric state of S100A12. Surface plasmon resonance confirmed that the presence of both calcium and zinc is essential for the interaction of S100A12 with one of its extracellular targets, RAGE – the Receptor for Advanced Glycation End products. By using a single-molecule approach we have shown that the presence of zinc in tissue culture medium favors both the oligomerization of exogenous S100A12 protein and its interaction with targets on the cell surface. Conclusion We have shown that oligomerization and target recognition by S100A12 is regulated by both zinc and calcium. Our present work highlighted the potential role of calcium-binding S100 proteins in zinc metabolism and, in particular, the role of S100A12 in the cross talk between zinc and calcium in cell signaling.

  7. Oligomeric adiponectin forms and their complexes in the blood of healthy donors and patients with type 2 diabetes mellitus.

    Science.gov (United States)

    Kogan, Alexander E; Filatov, Vladimir L; Kolosova, Olga V; Katrukha, Ivan A; Mironova, Ekaterina V; Zhuravleva, Natalya S; Nagibin, Oleg A; Kara, Andrei N; Bereznikova, Anastasiya V; Katrukha, Alexey G

    2013-01-01

    Adiponectin (Adn) is a protein that circulates in the blood in several oligomeric forms, namely low-, medium-, and high-molecular-weight forms. Adn may serve as a risk factor for type 2 diabetes mellitus (T2DM). The aims of this work were (1) to produce monoclonal antibodies (MAbs) specific to different Adn oligomeric forms, (2) to design immunoassays suitable for measuring the Adn forms present in human blood, and (3) to investigate the changes in Adn forms that occur in patients with T2DM. Gel filtration, fluoroimmunoassays, and Western blotting were utilized as major techniques in this study. MAbs recognizing various oligomeric forms of Adn were obtained. Complexes between Adn and complement component C1q and between the low molecular weight form of Adn and albumin were described in human blood. A decrease in the total Adn and Adn-albumin complex levels in the blood of patients with T2DM and no difference in the levels of the Adn-C1q complex in comparison with healthy volunteers were demonstrated. An Adn94-Adn63 fluoroimmunoassay was selected as the technique that most accurately measured the mass ratio of Adn oligomers in blood samples, and an Adn214-Adn27 assay that measured the low-molecular-weight form of Adn only.

  8. Detection of Amyloid Beta (Aβ) Oligomeric Composition Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry (MALDI MS)

    Science.gov (United States)

    Wang, Jasmine S.-H.; Whitehead, Shawn N.; Yeung, Ken K.-C.

    2018-02-01

    The use of MALDI MS as a fast and direct method to detect the Aβ oligomers of different masses is examined in this paper. Experimental results suggest that Aβ oligomers are ionized and detected as singly charged ions, and thus, the resulting mass spectrum directly reports the oligomer size distribution. Validation experiments were performed to verify the MS data against artifacts. Mass spectra collected from modified Aβ peptides with different propensities for aggregation were compared. Generally, the relative intensities of multimers were higher from samples where oligomerization was expected to be more favorable, and vice versa. MALDI MS was also able to detect the differences in oligomeric composition before and after the incubation/oligomerization step. Such differences in sample composition were also independently confirmed with an in vitro Aβ toxicity study on primary rat cortical neurons. An additional validation was accomplished through removal of oligomers from the sample using molecular weight cutoff filters; the resulting MS data correctly reflected the removal at the expected cutoff points. The results collectively validated the ability of MALDI MS to assess the monomeric/multimeric composition of Aβ samples. [Figure not available: see fulltext.

  9. Spa47 is an oligomerization-activated type three secretion system (T3SS) ATPase from Shigella flexneri.

    Science.gov (United States)

    Burgess, Jamie L; Jones, Heather B; Kumar, Prashant; Toth, Ronald T; Middaugh, C Russell; Antony, Edwin; Dickenson, Nicholas E

    2016-05-01

    Gram-negative pathogens often use conserved type three secretion systems (T3SS) for virulence. The Shigella type three secretion apparatus (T3SA) penetrates the host cell membrane and provides a unidirectional conduit for injection of effectors into host cells. The protein Spa47 localizes to the base of the apparatus and is speculated to be an ATPase that provides the energy for T3SA formation and secretion. Here, we developed an expression and purification protocol, producing active Spa47 and providing the first direct evidence that Spa47 is a bona fide ATPase. Additionally, size exclusion chromatography and analytical ultracentrifugation identified multiple oligomeric species of Spa47 with the largest greater than 8 fold more active for ATP hydrolysis than the monomer. An ATPase inactive Spa47 point mutant was then engineered by targeting a conserved Lysine within the predicted Walker A motif of Spa47. Interestingly, the mutant maintained a similar oligomerization pattern as active Spa47, but was unable to restore invasion phenotype when used to complement a spa47 null S. flexneri strain. Together, these results identify Spa47 as a Shigella T3SS ATPase and suggest that its activity is linked to oligomerization, perhaps as a regulatory mechanism as seen in some related pathogens. Additionally, Spa47 catalyzed ATP hydrolysis appears to be essential for host cell invasion, providing a strong platform for additional studies dissecting its role in virulence and providing an attractive target for anti-infective agents. © 2016 The Protein Society.

  10. The Pseudo signal peptide of the corticotropin-releasing factor receptor type 2A prevents receptor oligomerization.

    Science.gov (United States)

    Teichmann, Anke; Rutz, Claudia; Kreuchwig, Annika; Krause, Gerd; Wiesner, Burkhard; Schülein, Ralf

    2012-08-03

    N-terminal signal peptides mediate the interaction of native proteins with the translocon complex of the endoplasmic reticulum membrane and are cleaved off during early protein biogenesis. The corticotropin-releasing factor receptor type 2a (CRF(2(a))R) possesses an N-terminal pseudo signal peptide, which represents a so far unique domain within the large protein family of G protein-coupled receptors (GPCRs). In contrast to a conventional signal peptide, the pseudo signal peptide remains uncleaved and consequently forms a hydrophobic extension at the N terminus of the receptor. The functional consequence of the presence of the pseudo signal peptide is not understood. Here, we have analyzed the significance of this domain for receptor dimerization/oligomerization in detail. To this end, we took the CRF(2(a))R and the homologous corticotropin-releasing factor receptor type 1 (CRF(1)R) possessing a conventional cleaved signal peptide and conducted signal peptide exchange experiments. Using single cell and single molecule imaging methods (fluorescence resonance energy transfer and fluorescence cross-correlation spectroscopy, respectively) as well as biochemical experiments, we obtained two novel findings; we could show that (i) the CRF(2(a))R is expressed exclusively as a monomer, and (ii) the presence of the pseudo signal peptide prevents its oligomerization. Thus, we have identified a novel functional domain within the GPCR protein family, which plays a role in receptor oligomerization and which may be useful to study the functional significance of this process in general.

  11. Ion Channel Conformation and Oligomerization Assessment by Site-Directed Spin Labeling and Pulsed-EPR.

    Science.gov (United States)

    Pliotas, Christos

    2017-01-01

    Mechanosensitive (MS) ion channels are multimeric integral membrane proteins that respond to increased lipid bilayer tension by opening their nonselective pores to release solutes and relieve increased cytoplasmic pressure. These systems undergo major conformational changes during gating and the elucidation of their mechanism requires a deep understanding of the interplay between lipids and proteins. Lipids are responsible for transmitting lateral tension to MS channels and therefore play a key role in obtaining a molecular-detail model for mechanosensation. Site-directed spin labeling combined with electron paramagnetic resonance (EPR) spectroscopy is a powerful spectroscopic tool in the study of proteins. The main bottleneck for its use relates to challenges associated with successful isolation of the protein of interest, introduction of paramagnetic labels on desired sites, and access to specialized instrumentation and expertise. The design of sophisticated experiments, which combine a variety of existing EPR methodologies to address a diversity of specific questions, require knowledge of the limitations and strengths, characteristic of each particular EPR method. This chapter is using the MS ion channels as paradigms and focuses on the application of different EPR techniques to ion channels, in order to investigate oligomerization, conformation, and the effect of lipids on their regulation. The methodology we followed, from the initial strategic selection of mutants and sample preparation, including protein purification, spin labeling, reconstitution into lipid mimics to the complete set-up of the pulsed-EPR experiments, is described in detail. © 2017 Elsevier Inc. All rights reserved.

  12. Crystal structure of the Haemophilus influenzae Hap adhesin reveals an intercellular oligomerization mechanism for bacterial aggregation

    Science.gov (United States)

    Meng, Guoyu; Spahich, Nicole; Kenjale, Roma; Waksman, Gabriel; St Geme, Joseph W

    2011-01-01

    Bacterial biofilms are complex microbial communities that are common in nature and are being recognized increasingly as an important determinant of bacterial virulence. However, the structural determinants of bacterial aggregation and eventual biofilm formation have been poorly defined. In Gram-negative bacteria, a major subgroup of extracellular proteins called self-associating autotransporters (SAATs) can mediate cell–cell adhesion and facilitate biofilm formation. In this study, we used the Haemophilus influenzae Hap autotransporter as a prototype SAAT to understand how bacteria associate with each other. The crystal structure of the H. influenzae HapS passenger domain (harbouring the SAAT domain) was determined to 2.2 Å by X-ray crystallography, revealing an unprecedented intercellular oligomerization mechanism for cell–cell interaction. The C-terminal SAAT domain folds into a triangular-prism-like structure that can mediate Hap–Hap dimerization and higher degrees of multimerization through its F1–F2 edge and F2 face. The intercellular multimerization can give rise to massive buried surfaces that are required for overcoming the repulsive force between cells, leading to bacterial cell–cell interaction and formation of complex microcolonies. PMID:21841773

  13. Molecular cloning and functional characterization of duck nucleotide-binding oligomerization domain 1 (NOD1).

    Science.gov (United States)

    Li, Huilin; Jin, Hui; Li, Yaqian; Liu, Dejian; Foda, Mohamed Frahat; Jiang, Yunbo; Luo, Rui

    2017-09-01

    Nucleotide-binding oligomerization domain 1 (NOD1) is an imperative cytoplasmic pattern recognition receptor (PRR) and considered as a key member of the NOD-like receptor (NLR) family which plays a critical role in innate immunity through sensing microbial components derived from bacterial peptidoglycan. In the current study, the full-length of duck NOD1 (duNOD1) cDNA from duck embryo fibroblasts (DEFs) was cloned. Multiple sequence alignment and phylogenetic analysis demonstrated that duNOD1 exhibited a strong evolutionary relationship with chicken and rock pigeon NOD1. Tissue-specific expression analysis showed that duNOD1 was widely distributed in various organs, with the highest expression observed in the liver. Furthermore, duNOD1 overexpression induced NF-κB activation in DEFs and the CARD domain is crucial for duNOD1-mediated NF-κB activation. In addition, silencing the duNOD1 decreased the activity of NF-κB in DEFs stimulated by iE-DAP. Overexpression of duNOD1 significantly increased the expression of TNF-α, IL-6, and RANTES in DEFs. These findings highlight the crucial role of duNOD1 as an intracellular sensor in duck innate immune system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Cyclic GMP-AMP synthase is activated by double-stranded DNA-induced oligomerization.

    Science.gov (United States)

    Li, Xin; Shu, Chang; Yi, Guanghui; Chaton, Catherine T; Shelton, Catherine L; Diao, Jiasheng; Zuo, Xiaobing; Kao, C Cheng; Herr, Andrew B; Li, Pingwei

    2013-12-12

    Cyclic GMP-AMP synthase (cGAS) is a cytosolic DNA sensor mediating innate antimicrobial immunity. It catalyzes the synthesis of a noncanonical cyclic dinucleotide, 2',5' cGAMP, that binds to STING and mediates the activation of TBK1 and IRF-3. Activated IRF-3 translocates to the nucleus and initiates the transcription of the IFN-β gene. The structure of mouse cGAS bound to an 18 bp dsDNA revealed that cGAS interacts with dsDNA through two binding sites, forming a 2:2 complex. Enzyme assays and IFN-β reporter assays of cGAS mutants demonstrated that interactions at both DNA binding sites are essential for cGAS activation. Mutagenesis and DNA binding studies showed that the two sites bind dsDNA cooperatively and that site B plays a critical role in DNA binding. The structure of mouse cGAS bound to dsDNA and 2',5' cGAMP provided insight into the catalytic mechanism of cGAS. These results demonstrated that cGAS is activated by dsDNA-induced oligomerization. Copyright © 2013 Elsevier Inc. All rights reserved.

  15. Hydroxychloroquine induces inhibition of collagen type II and oligomeric matrix protein COMP expression in chondrocytes

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    Tao Li

    2016-06-01

    Full Text Available The aim of this study was to investigate the effect of hydroxychloroquine on the level of collagen type II and oligomeric matrix protein COMP expression in chondrocytes of knee osteoarthritis. The rate of growth in cartilage cells was analyzed using MTT assay whereas the Col-2 and COMP expression levels were detected by RT-PCR and Western blotting analyses. For the determination of MMP-13 expression, ELISA test was used. The results revealed no significant change in the rate of cartilage cell proliferation in hydroxychloroquine-treated compared to untreated cells. Hydroxychloro-quine treatment exhibited concentration- and time-dependent effect on the inhibition of collagen type II and COMP expression in chondrocytes. However, its treatment caused a significant enhancement in the expression levels of MMP-13 compared to the untreated cells. Therefore, hydroxychloro-quine promotes expression of MMP-13 and reduces collagen type II and COMP expression levels in chondrocytes without any significant change in the growth of cells.

  16. Hexokinase 2 from Saccharomyces cerevisiae: regulation of oligomeric structure by in vivo phosphorylation at serine-14.

    Science.gov (United States)

    Behlke, J; Heidrich, K; Naumann, M; Müller, E C; Otto, A; Reuter, R; Kriegel, T

    1998-08-25

    Homodimeric hexokinase 2 from Saccharomyces cerevisiae is known to have two sites of phosphorylation: for serine-14 the modification in vivo increases with glucose exhaustion [Kriegel et al. (1994) Biochemistry 33, 148-152], while for serine-157 it occurs in vitro with ATP in the presence of nonphosphorylateable five-carbon analogues of glucose [Heidrich et al. (1997) Biochemistry 36, 1960-1964]. We show now by site-directed mutagenesis and sedimentation analysis that serine-14 phosphorylation affects the oligomeric state of hexokinase, its substitution by glutamate causing complete dissociation; glutamate exchange for serine-157 does not. Phosphorylation of wild-type hexokinase at serine-14 likewise causes dissociation in vitro. In view of the higher glucose affinity of monomeric hexokinase and the high hexokinase concentration in yeast [Womack, F., and Colowick, S. P. (1978) Arch. Biochem. Biophys. 191, 742-747; Mayes, E. L., Hoggett, J. G., and Kellett, G. L. (1983) Eur. J. Biochem. 133, 127-134], we speculate that the in vivo phosphorylation at serine-14 as transiently occurring in glucose derepression might provide a mechanism to improve glucose utilization from low level and/or that nuclear localization of the monomer might be involved in the signal transduction whereby glucose causes catabolite repression.

  17. Formation of semisolid, oligomerized aqueous SOA: lab simulations of cloud processing.

    Science.gov (United States)

    Hawkins, Lelia N; Baril, Molly J; Sedehi, Nahzaneen; Galloway, Melissa M; De Haan, David O; Schill, Gregory P; Tolbert, Margaret A

    2014-02-18

    Glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone form N-containing and oligomeric compounds during simulated cloud processing with small amines. Using a novel hygroscopicity tandem differential mobility analysis (HTDMA) system that allows varied humidification times, the hygroscopic growth (HG) of each of the resulting products of simulated cloud processing was measured. Continuous water uptake (gradual deliquescence) was observed beginning at ∼ 40% RH for all aldehyde-methylamine products. Particles containing ionic reaction products of either glyoxal or glycine were most hygroscopic, with HG between 1.16 and 1.20 at 80% RH. Longer humidification times (up to 20 min) produced an increase in growth factors for glyoxal-methylamine (19% by vol) and methylglyoxal-methylamine (8% by vol) aerosol, indicating that unusually long equilibration times can be required for HTDMA measurements of such particles. Glyoxal- and methylglyoxal-methylamine aerosol particles shattered in Raman microscopy impact-flow experiments, revealing that the particles were semisolid. Similar experiments on glycolaldehyde- and hydroxyacetone-methylamine aerosol found that the aerosol particles were liquid when dried for glyoxal > glycolaldehyde = hydroxyacetone, likely caused by the speed of oligomer formation in each system.

  18. MAK33 antibody light chain amyloid fibrils are similar to oligomeric precursors.

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    Manuel Hora

    Full Text Available Little structural information is available so far on amyloid fibrils consisting of immunoglobulin light chains. It is not understood which features of the primary sequence of the protein result in fibril formation. We report here MAS solid-state NMR studies to identify the structured core of κ-type variable domain light chain fibrils. The core contains residues of the CDR2 and the β-strands D, E, F and G of the native immunoglobulin fold. The assigned core region of the fibril is distinct in comparison to the core identified in a previous solid-state NMR study on AL-09 by Piehl at. al, suggesting that VL fibrils can adopt different topologies. In addition, we investigated a soluble oligomeric intermediate state, previously termed the alternatively folded state (AFS, using NMR and FTIR spectroscopy. The NMR oligomer spectra display a high degree of similarity when compared to the fibril spectra, indicating a high structural similarity of the two aggregation states. Based on comparison to the native state NMR chemical shifts, we suggest that fibril formation via domain-swapping seems unlikely. Moreover, we used our results to test the quality of different amyloid prediction algorithms.

  19. IntraGolgi distribution of the Conserved Oligomeric Golgi (COG) complex

    International Nuclear Information System (INIS)

    Vasile, Eliza; Oka, Toshihiko; Ericsson, Maria; Nakamura, Nobuhiro; Krieger, Monty

    2006-01-01

    The Conserved Oligomeric Golgi (COG) complex is an eight-subunit (Cog1-8) peripheral Golgi protein involved in membrane trafficking and glycoconjugate synthesis. COG appears to participate in retrograde vesicular transport and is required to maintain normal Golgi structure and function. COG mutations interfere with normal transport, distribution, and/or stability of Golgi proteins associated with glycoconjugate synthesis and trafficking, and lead to failure of spermatogenesis in Drosophila melanogaster, misdirected migration of gonadal distal tip cells in Caenorhabditis elegans, and type II congenital disorders of glycosylation in humans. The mechanism by which COG influences Golgi structure and function is unclear. Immunogold electron microscopy was used to visualize the intraGolgi distribution of a functional, hemagglutinin epitope-labeled COG subunit, Cog1-HA, that complements the Cog1-deficiency in Cog1-null Chinese hamster ovary cells. COG was found to be localized primarily on or in close proximity to the tips and rims of the Golgi's cisternae and their associated vesicles and on vesicles and vesiculo-tubular structures seen on both the cis and trans-Golgi Network faces of the cisternal stacks, in some cases on COPI containing vesicles. These findings support the proposal that COG is directly involved in controlling vesicular retrograde transport of Golgi resident proteins throughout the Golgi apparatus

  20. Optimization of oligomeric enzyme activity in ionic liquids using Rhodotorula glutinis yeast phenylalanine ammonia lyase.

    Science.gov (United States)

    Barron, Christiaan C; Sponagle, Brandon J D; Arivalagan, Pugazhendhi; D'Cunha, Godwin B

    2017-01-01

    Phenylalanine ammonia lyase (E.C.4.3.1.24, PAL) activity of Rhodotorula glutinis yeast has been demonstrated in four commonly used ionic liquids. PAL forward reaction was carried out in 1-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO 4 ]), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF 6 ]) and 1-butyl-3-methylimidazolium lactate ([BMIM][lactate]). Our experiments have revealed that PAL is catalytically active in ionic liquids and the enzyme activity in ([BMIM][PF 6 ]) is comparable to that obtained in aqueous buffer medium. Different conditions were optimized for maximal PAL forward activity including time of incubation (30.0min) L -phenylalanine substrate concentration (30.0mM), nature of buffer (50.0mM Tris-HCl), pH (9.0), temperature (37°C), and speed of agitation (100 rev min -1 ). Under these optimized conditions, about 83% conversion of substrate to product was obtained for the PAL forward reaction that was determined using UV spectroscopy at 290nm. PAL reverse reaction in ([BMIM][PF 6 ]) was determined spectrophotometrically at 520nm; and about 59% substrate conversion was obtained. This data provides further knowledge in enzyme biocatalysis in non-aqueous media, and may be of importance when studying the function of other oligomeric/multimeric proteins and enzymes in ionic liquids. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. Bimolecular Fluorescence Complementation of Alpha-synuclein Demonstrates its Oligomerization with Dopaminergic Phenotype in Mice

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    Waijiao Cai

    2018-03-01

    Full Text Available Alpha-synuclein (αSyn is encoded by the first causal gene identified in Parkinson's disease (PD and is the main component of Lewy bodies, a pathological hallmark of PD. aSyn-based animal models have contributed to our understanding of PD pathophysiology and to the development of therapeutics. Overexpression of human wildtype αSyn by viral vectors in rodents recapitulates the loss of dopaminergic neurons from the substantia nigra, another defining pathological feature of the disease. The development of a rat model exhibiting bimolecular fluorescence complementation (BiFC of αSyn by recombinant adeno-associated virus facilitates detection of the toxic αSyn oligomers species. We report here neurochemical, neuropathological and behavioral characterization of BiFC of αSyn in mice. Overexpression and oligomerization of αSyn through BiFC is detected by conjugated fluorescence. Reduced striatal dopamine and loss of nigral dopaminergic neurons are accompanied neuroinflammation and abnormal motor activities. Our mouse model may provide a valuable tool to study the role of αSyn in PD and to explore therapeutic approaches. Keywords: Parkinson's disease, Alpha-synuclein, Mouse model, Oligomers, Neuroinflammation

  2. The role of Vif oligomerization and RNA chaperone activity in HIV-1 replication.

    Science.gov (United States)

    Batisse, Julien; Guerrero, Santiago; Bernacchi, Serena; Sleiman, Dona; Gabus, Caroline; Darlix, Jean-Luc; Marquet, Roland; Tisné, Carine; Paillart, Jean-Christophe

    2012-11-01

    The viral infectivity factor (Vif) is essential for the productive infection and dissemination of HIV-1 in non-permissive cells that involve most natural HIV-1 target cells. Vif counteracts the packaging of two cellular cytidine deaminases named APOBEC3G (A3G) and A3F by diverse mechanisms including the recruitment of an E3 ubiquitin ligase complex and the proteasomal degradation of A3G/A3F, the inhibition of A3G mRNA translation or by a direct competition mechanism. In addition, Vif appears to be an active partner of the late steps of viral replication by participating in virus assembly and Gag processing, thus regulating the final stage of virion formation notably genomic RNA dimerization and by inhibiting the initiation of reverse transcription. Vif is a small pleiotropic protein with multiple domains, and recent studies highlighted the importance of Vif conformation and flexibility in counteracting A3G and in binding RNA. In this review, we will focus on the oligomerization and RNA chaperone properties of Vif and show that the intrinsic disordered nature of some Vif domains could play an important role in virus assembly and replication. Experimental evidence demonstrating the RNA chaperone activity of Vif will be presented. Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Complex structure of the fission yeast SREBP-SCAP binding domains reveals an oligomeric organization.

    Science.gov (United States)

    Gong, Xin; Qian, Hongwu; Shao, Wei; Li, Jingxian; Wu, Jianping; Liu, Jun-Jie; Li, Wenqi; Wang, Hong-Wei; Espenshade, Peter; Yan, Nieng

    2016-11-01

    Sterol regulatory element-binding protein (SREBP) transcription factors are master regulators of cellular lipid homeostasis in mammals and oxygen-responsive regulators of hypoxic adaptation in fungi. SREBP C-terminus binds to the WD40 domain of SREBP cleavage-activating protein (SCAP), which confers sterol regulation by controlling the ER-to-Golgi transport of the SREBP-SCAP complex and access to the activating proteases in the Golgi. Here, we biochemically and structurally show that the carboxyl terminal domains (CTD) of Sre1 and Scp1, the fission yeast SREBP and SCAP, form a functional 4:4 oligomer and Sre1-CTD forms a dimer of dimers. The crystal structure of Sre1-CTD at 3.5 Å and cryo-EM structure of the complex at 5.4 Å together with in vitro biochemical evidence elucidate three distinct regions in Sre1-CTD required for Scp1 binding, Sre1-CTD dimerization and tetrameric formation. Finally, these structurally identified domains are validated in a cellular context, demonstrating that the proper 4:4 oligomeric complex formation is required for Sre1 activation.

  4. Design of a minimal protein oligomerization domain by a structural approach.

    Science.gov (United States)

    Burkhard, P; Meier, M; Lustig, A

    2000-12-01

    Because of the simplicity and regularity of the alpha-helical coiled coil relative to other structural motifs, it can be conveniently used to clarify the molecular interactions responsible for protein folding and stability. Here we describe the de novo design and characterization of a two heptad-repeat peptide stabilized by a complex network of inter- and intrahelical salt bridges. Circular dichroism spectroscopy and analytical ultracentrifugation show that this peptide is highly alpha-helical and 100% dimeric tinder physiological buffer conditions. Interestingly, the peptide was shown to switch its oligomerization state from a dimer to a trimer upon increasing ionic strength. The correctness of the rational design principles used here is supported by details of the atomic structure of the peptide deduced from X-ray crystallography. The structure of the peptide shows that it is not a molten globule but assumes a unique, native-like conformation. This de novo peptide thus represents an attractive model system for the design of a molecular recognition system.

  5. RNAi reduces expression and intracellular retention of mutant cartilage oligomeric matrix protein.

    Directory of Open Access Journals (Sweden)

    Karen L Posey

    2010-04-01

    Full Text Available Mutations in cartilage oligomeric matrix protein (COMP, a large extracellular glycoprotein expressed in musculoskeletal tissues, cause two skeletal dysplasias, pseudoachondroplasia and multiple epiphyseal dysplasia. These mutations lead to massive intracellular retention of COMP, chondrocyte death and loss of growth plate chondrocytes that are necessary for linear growth. In contrast, COMP null mice have only minor growth plate abnormalities, normal growth and longevity. This suggests that reducing mutant and wild-type COMP expression in chondrocytes may prevent the toxic cellular phenotype causing the skeletal dysplasias. We tested this hypothesis using RNA interference to reduce steady state levels of COMP mRNA. A panel of shRNAs directed against COMP was tested. One shRNA (3B reduced endogenous and recombinant COMP mRNA dramatically, regardless of expression levels. The activity of the shRNA against COMP mRNA was maintained for up to 10 weeks. We also demonstrate that this treatment reduced ER stress. Moreover, we show that reducing steady state levels of COMP mRNA alleviates intracellular retention of other extracellular matrix proteins associated with the pseudoachondroplasia cellular pathology. These findings are a proof of principle and the foundation for the development of a therapeutic intervention based on reduction of COMP expression.

  6. Sedimentation Velocity Analysis of Large Oligomeric Chromatin Complexes Using Interference Detection.

    Science.gov (United States)

    Rogge, Ryan A; Hansen, Jeffrey C

    2015-01-01

    Sedimentation velocity experiments measure the transport of molecules in solution under centrifugal force. Here, we describe a method for monitoring the sedimentation of very large biological molecular assemblies using the interference optical systems of the analytical ultracentrifuge. The mass, partial-specific volume, and shape of macromolecules in solution affect their sedimentation rates as reflected in the sedimentation coefficient. The sedimentation coefficient is obtained by measuring the solute concentration as a function of radial distance during centrifugation. Monitoring the concentration can be accomplished using interference optics, absorbance optics, or the fluorescence detection system, each with inherent advantages. The interference optical system captures data much faster than these other optical systems, allowing for sedimentation velocity analysis of extremely large macromolecular complexes that sediment rapidly at very low rotor speeds. Supramolecular oligomeric complexes produced by self-association of 12-mer chromatin fibers are used to illustrate the advantages of the interference optics. Using interference optics, we show that chromatin fibers self-associate at physiological divalent salt concentrations to form structures that sediment between 10,000 and 350,000S. The method for characterizing chromatin oligomers described in this chapter will be generally useful for characterization of any biological structures that are too large to be studied by the absorbance optical system. © 2015 Elsevier Inc. All rights reserved.

  7. Role of redox environment on the oligomerization of higher molecular weight adiponectin

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    Nuñez Martha

    2011-05-01

    Full Text Available Abstract Background Adiponectin is an adipocyte-secreted hormone with insulin-sensitizing and anti-inflammatory actions. The assembly of trimeric, hexameric, and higher molecular weight (HMW species of adiponectin is a topic of significant interest because physiological actions of adiponectin are oligomer-specific. In addition, adiponectin assembly is an example of oxidative oligomerization of multi-subunit protein complexes in endoplasmic reticulum (ER. Results We previously reported that trimers assemble into HMW adiponectin via intermediates stabilized by disulfide bonds, and complete oxidation of available cysteines locks adiponectin in hexameric conformation. In this study, we examined the effects of redox environment on the rate of oligomer formation and the distribution of oligomers. Reassembly of adiponectin under oxidizing conditions accelerated disulfide bonding but favored formation of hexamers over the HMW species. Increased ratios of HMW to hexameric adiponectin could be achieved rapidly under oxidizing conditions by promoting disulfide rearrangement. Conclusions Based upon these observations, we propose oxidative assembly of multi-subunit adiponectin complexes in a defined and stable redox environment is favored under oxidizing conditions coupled with high rates of disulfide rearrangement.

  8. Reversible unfolding of infectious prion assemblies reveals the existence of an oligomeric elementary brick.

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    Angélique Igel-Egalon

    2017-09-01

    Full Text Available Mammalian prions, the pathogens that cause transmissible spongiform encephalopathies, propagate by self-perpetuating the structural information stored in the abnormally folded, aggregated conformer (PrPSc of the host-encoded prion protein (PrPC. To date, no structural model related to prion assembly organization satisfactorily describes how strain-specified structural information is encoded and by which mechanism this information is transferred to PrPC. To achieve progress on this issue, we correlated the PrPSc quaternary structural transition from three distinct prion strains during unfolding and refolding with their templating activity. We reveal the existence of a mesoscopic organization in PrPSc through the packing of a highly stable oligomeric elementary subunit (suPrP, in which the strain structural determinant (SSD is encoded. Once kinetically trapped, this elementary subunit reversibly loses all replicative information. We demonstrate that acquisition of the templating interface and infectivity requires structural rearrangement of suPrP, in concert with its condensation. The existence of such an elementary brick scales down the SSD support to a small oligomer and provide a basis of reflexion for prion templating process and propagation.

  9. Structural fingerprints and their evolution during oligomeric vs. oligomer-free amyloid fibril growth.

    Science.gov (United States)

    Foley, Joseph; Hill, Shannon E; Miti, Tatiana; Mulaj, Mentor; Ciesla, Marissa; Robeel, Rhonda; Persichilli, Christopher; Raynes, Rachel; Westerheide, Sandy; Muschol, Martin

    2013-09-28

    Deposits of fibrils formed by disease-specific proteins are the molecular hallmark of such diverse human disorders as Alzheimer's disease, type II diabetes, or rheumatoid arthritis. Amyloid fibril formation by structurally and functionally unrelated proteins exhibits many generic characteristics, most prominently the cross β-sheet structure of their mature fibrils. At the same time, amyloid formation tends to proceed along one of two separate assembly pathways yielding either stiff monomeric filaments or globular oligomers and curvilinear protofibrils. Given the focus on oligomers as major toxic species, the very existence of an oligomer-free assembly pathway is significant. Little is known, though, about the structure of the various intermediates emerging along different pathways and whether the pathways converge towards a common or distinct fibril structures. Using infrared spectroscopy we probed the structural evolution of intermediates and late-stage fibrils formed during in vitro lysozyme amyloid assembly along an oligomeric and oligomer-free pathway. Infrared spectroscopy confirmed that both pathways produced amyloid-specific β-sheet peaks, but at pathway-specific wavenumbers. We further found that the amyloid-specific dye thioflavin T responded to all intermediates along either pathway. The relative amplitudes of thioflavin T fluorescence responses displayed pathway-specific differences and could be utilized for monitoring the structural evolution of intermediates. Pathway-specific structural features obtained from infrared spectroscopy and Thioflavin T responses were identical for fibrils grown at highly acidic or at physiological pH values and showed no discernible effects of protein hydrolysis. Our results suggest that late-stage fibrils formed along either pathway are amyloidogenic in nature, but have distinguishable structural fingerprints. These pathway-specific fingerprints emerge during the earliest aggregation events and persist throughout the

  10. Cartilage oligomeric matrix protein enhances matrix assembly during chondrogenesis of human mesenchymal stem cells.

    Science.gov (United States)

    Haleem-Smith, Hana; Calderon, Raul; Song, Yingjie; Tuan, Rocky S; Chen, Faye H

    2012-04-01

    Cartilage oligomeric matrix protein/thrombospondin-5 (COMP/TSP5) is an abundant cartilage extracellular matrix (ECM) protein that interacts with major cartilage ECM components, including aggrecan and collagens. To test our hypothesis that COMP/TSP5 functions in the assembly of the ECM during cartilage morphogenesis, we have employed mesenchymal stem cell (MSC) chondrogenesis in vitro as a model to examine the effects of COMP over-expression on neo-cartilage formation. Human bone marrow-derived MSCs were transfected with either full-length COMP cDNA or control plasmid, followed by chondrogenic induction in three-dimensional pellet or alginate hydrogel culture. MSC chondrogenesis and ECM production was estimated based on quantitation of sulfated glycosaminoglycan (sGAG) accumulation, immunohistochemistry of the presence and distribution of cartilage ECM proteins, and real-time RT-PCR analyis of mRNA expression of cartilage markers. Our results showed that COMP over-expression resulted in increased total sGAG content during the early phase of MSC chondrogenesis, and increased immuno-detectable levels of aggrecan and collagen type II in the ECM of COMP-transfected pellet and alginate cultures, indicating more abundant cartilaginous matrix. COMP transfection did not significantly increase the transcript levels of the early chondrogenic marker, Sox9, or aggrecan, suggesting that enhancement of MSC cartilage ECM was effected at post-transcriptional levels. These findings strongly suggest that COMP functions in mesenchymal chondrogenesis by enhancing cartilage ECM organization and assembly. The action of COMP is most likely mediated not via direct changes in cartilage matrix gene expression but via interactions of COMP with other cartilage ECM proteins, such as aggrecan and collagens, that result in enhanced assembly and retention.

  11. Binding and Oligomerization of Modified and Native Bt Toxins in Resistant and Susceptible Pink Bollworm.

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    Josue Ocelotl

    Full Text Available Insecticidal proteins from Bacillus thuringiensis (Bt are used extensively in sprays and transgenic crops for pest control, but their efficacy is reduced when pests evolve resistance. Better understanding of the mode of action of Bt toxins and the mechanisms of insect resistance is needed to enhance the durability of these important alternatives to conventional insecticides. Mode of action models agree that binding of Bt toxins to midgut proteins such as cadherin is essential for toxicity, but some details remain unresolved, such as the role of toxin oligomers. In this study, we evaluated how Bt toxin Cry1Ac and its genetically engineered counterpart Cry1AcMod interact with brush border membrane vesicles (BBMV from resistant and susceptible larvae of Pectinophora gossypiella (pink bollworm, a global pest of cotton. Compared with Cry1Ac, Cry1AcMod lacks 56 amino acids at the amino-terminus including helix α-1; previous work showed that Cry1AcMod formed oligomers in vitro without cadherin and killed P. gossypiella larvae harboring cadherin mutations linked with >1000-fold resistance to Cry1Ac. Here we found that resistance to Cry1Ac was associated with reduced oligomer formation and insertion. In contrast, Cry1AcMod formed oligomers in BBMV from resistant larvae. These results confirm the role of cadherin in oligomerization of Cry1Ac in susceptible larvae and imply that forming oligomers without cadherin promotes toxicity of Cry1AcMod against resistant P. gossypiella larvae that have cadherin mutations.

  12. Biophysical investigation of type A PutAs reveals a conserved core oligomeric structure

    Energy Technology Data Exchange (ETDEWEB)

    Korasick, David A. [Department of Biochemistry, University of Missouri, Columbia MO USA; Singh, Harkewal [Department of Chemistry, University of Missouri, Columbia MO USA; Pemberton, Travis A. [Department of Chemistry, University of Missouri, Columbia MO USA; Luo, Min [Department of Chemistry, University of Missouri, Columbia MO USA; Dhatwalia, Richa [Department of Chemistry, University of Missouri, Columbia MO USA; Tanner, John J. [Department of Biochemistry, University of Missouri, Columbia MO USA; Department of Chemistry, University of Missouri, Columbia MO USA

    2017-08-01

    Many enzymes form homooligomers, yet the functional significance of self-association is seldom obvious. Herein, we examine the connection between oligomerization and catalytic function for proline utilization A (PutA) enzymes. PutAs are bifunctional enzymes that catalyze both reactions of proline catabolism. Type A PutAs are the smallest members of the family, possessing a minimal domain architecture consisting of N-terminal proline dehydrogenase and C-terminal l-glutamate-γ-semialdehyde dehydrogenase modules. Type A PutAs form domain-swapped dimers, and in one case (Bradyrhizobium japonicum PutA), two of the dimers assemble into a ring-shaped tetramer. Whereas the dimer has a clear role in substrate channeling, the functional significance of the tetramer is unknown. To address this question, we performed structural studies of four-type A PutAs from two clades of the PutA tree. The crystal structure of Bdellovibrio bacteriovorus PutA covalently inactivated by N-propargylglycine revealed a fold and substrate-channeling tunnel similar to other PutAs. Small-angle X-ray scattering (SAXS) and analytical ultracentrifugation indicated that Bdellovibrio PutA is dimeric in solution, in contrast to the prediction from crystal packing of a stable tetrameric assembly. SAXS studies of two other type A PutAs from separate clades also suggested that the dimer predominates in solution. To assess whether the tetramer of B. japonicum PutA is necessary for catalytic function, a hot spot disruption mutant that cleanly produces dimeric protein was generated. The dimeric variant exhibited kinetic parameters similar to the wild-type enzyme. These results implicate the domain-swapped dimer as the core structural and functional unit of type A PutAs.

  13. Oligomerization of Bacillus subtilis DesR is required for fine tuning regulation of membrane fluidity.

    Science.gov (United States)

    Najle, Sebastián R; Inda, María E; de Mendoza, Diego; Cybulski, Larisa E

    2009-10-01

    The DesK-DesR two-component system regulates the order of membrane lipids in the bacterium Bacillus subtilis by controlling the expression of the des gene coding for the delta 5-acyl-lipid desaturase. To activate des transcription, the membrane-bound histidine kinase DesK phosphorylates the response regulator DesR. This covalent modification of the regulatory domain of dimeric DesR promotes, in a cooperative fashion, the hierarchical occupation of two adjacent, non-identical, DesR-P binding sites, so that there is a shift in the equilibrium toward the tetrameric active form of the response regulator. However, the mechanism of regulation of DesR activity by phosphorylation and oligomerization is not well understood. We employed deletion analysis and reporter fusions to study the role of the N-terminal domain on DesR activity. In addition, electromobility shift assays were used to analyze the binding capacity of the transcription factor to deletion mutants of the des promoter. We show that DesR lacking the N-terminal domain is still able to bind to the des promoter. We also demonstrate that if the RA site is moved closer to the -35 region of Pdes, the adjacent site RB is dispensable for activation. Our results indicate that the unphosphorylated regulatory domain of DesR obstructs the access of the recognition helix of DesR to its DNA target. In addition, we present evidence showing that RB is physiologically relevant to control the activation of the des gene when the levels of DesR-P reach a critical threshold.

  14. Structural fingerprints and their evolution during oligomeric vs. oligomer-free amyloid fibril growth

    Science.gov (United States)

    Foley, Joseph; Hill, Shannon E.; Miti, Tatiana; Mulaj, Mentor; Ciesla, Marissa; Robeel, Rhonda; Persichilli, Christopher; Raynes, Rachel; Westerheide, Sandy; Muschol, Martin

    2013-09-01

    Deposits of fibrils formed by disease-specific proteins are the molecular hallmark of such diverse human disorders as Alzheimer's disease, type II diabetes, or rheumatoid arthritis. Amyloid fibril formation by structurally and functionally unrelated proteins exhibits many generic characteristics, most prominently the cross β-sheet structure of their mature fibrils. At the same time, amyloid formation tends to proceed along one of two separate assembly pathways yielding either stiff monomeric filaments or globular oligomers and curvilinear protofibrils. Given the focus on oligomers as major toxic species, the very existence of an oligomer-free assembly pathway is significant. Little is known, though, about the structure of the various intermediates emerging along different pathways and whether the pathways converge towards a common or distinct fibril structures. Using infrared spectroscopy we probed the structural evolution of intermediates and late-stage fibrils formed during in vitro lysozyme amyloid assembly along an oligomeric and oligomer-free pathway. Infrared spectroscopy confirmed that both pathways produced amyloid-specific β-sheet peaks, but at pathway-specific wavenumbers. We further found that the amyloid-specific dye thioflavin T responded to all intermediates along either pathway. The relative amplitudes of thioflavin T fluorescence responses displayed pathway-specific differences and could be utilized for monitoring the structural evolution of intermediates. Pathway-specific structural features obtained from infrared spectroscopy and Thioflavin T responses were identical for fibrils grown at highly acidic or at physiological pH values and showed no discernible effects of protein hydrolysis. Our results suggest that late-stage fibrils formed along either pathway are amyloidogenic in nature, but have distinguishable structural fingerprints. These pathway-specific fingerprints emerge during the earliest aggregation events and persist throughout the

  15. Association of Nucleotide-binding Oligomerization Domain Receptors with Peptic Ulcer and Gastric Cancer.

    Science.gov (United States)

    Mohammadian Amiri, Rajeeh; Tehrani, Mohsen; Taghizadeh, Shirin; Shokri-Shirvani, Javad; Fakheri, Hafez; Ajami, Abolghasem

    2016-10-01

    Host innate immunity can affect the clinical outcomes of Helicobacter pylori infection, including gastritis, gastric ulcer, gastric adenocarcinoma, and MALT lymphoma. Nucleotide binding oligomerization domain (NOD)-1 and -2 are two molecules of innate immunity which are involved in the host defense against H. pylori. This study aimed to evaluate the effect of the expression level of NOD1 and NOD2 on the susceptibility to gastric cancer as well as peptic ulcer in individuals with H. pylori infection. The gene expression levels of these molecules were compared in three groups of non-ulcer dyspepsia (NUD) as a control group (n=52); peptic ulcer disease (PUD), (n=53); and gastric cancer (GC), (n=39). Relative expression levels of NOD1 in patients with GC were higher than those of NUD and PUD (p<0.001 and P<0.001, respectively). Similarly in case of NOD1, PUD group showed higher level of expression than NUD group (p<0.01). However, there was no significant difference between H. pylori -positive and -negative patients in NUD, PUD, or GC groups. Moreover, the expression levels of NOD2 showed no significant difference among NUD, PUD, or GC groups, while among H. pylori-positive patients, it was higher in GC group than NUD  and PUD groups (p<0.05 and p<0.01, respectively). In addition, positive correlation coefficients were attained between NOD1 and NOD2 expressions in patients with NUD (R2 Linear=0.349, p<0.001), PUD (R2 Linear=0.695, p<0.001), and GC (R2 Linear=0.385, p<0.001). Collectively, the results suggest that the chronic activation of NOD1 and NOD2 receptors might play a role in the development of gastric cancer.

  16. CARTILAGE OLIGOMERIC MATRIX PROTEIN ENHANCES MATRIX ASSEMBLY DURING CHONDROGENESIS OF HUMAN MESENCHYMAL STEM CELLS

    Science.gov (United States)

    Haleem-Smith, Hana; Calderon, Raul; Song, Yingjie; Tuan, Rocky S.; Chen, Faye H.

    2011-01-01

    Cartilage oligomeric matrix protein/thrombospondin-5 (COMP/TSP5) is an abundant cartilage extracellular matrix (ECM) protein that interacts with major cartilage ECM components, including aggrecan and collagens. To test our hypothesis that COMP/TSP5 functions in the assembly of the ECM during cartilage morphogenesis, we have employed mesenchymal stem cell (MSC) chondrogenesis in vitro as a model to examine the effects of COMP over-expression on neo-cartilage formation. Human bone marrow-derived MSCs were transfected with either full-length COMP cDNA or control plasmid, followed by chondrogenic induction in three-dimensional pellet or alginate-hydrogel culture. MSC chondrogenesis and ECM production was estimated based on quantitation of sulfated glycosaminoglycan (sGAG) accumulation, immunohistochemistry of the presence and distribution of cartilage ECM proteins, and real-time RT-PCR analyis of mRNA expression of cartilage markers. Our results showed that COMP over-expression resulted in increased total sGAG content during the early phase of MSC chondrogenesis, and increased immuno-detectable levels of aggrecan and collagen type II in the ECM of COMP-transfected pellet and alginate cultures, indicating more abundant cartilaginous matrix. COMP transfection did not significantly increase the transcript levels of the early chondrogenic marker, Sox9, or aggrecan, suggesting that enhancement of MSC cartilage ECM was effected at post-transcriptional levels. These findings strongly suggest that COMP functions in mesenchymal chondrogenesis by enhancing cartilage ECM organization and assembly. The action of COMP is most likely mediated not via direct changes in cartilage matrix gene expression but via interactions of COMP with other cartilage ECM proteins, such as aggrecan and collagens, that result in enhanced assembly and retention. PMID:22095699

  17. Reversibility and two state behaviour in the thermal unfolding of oligomeric TIM barrel proteins.

    Science.gov (United States)

    Romero-Romero, Sergio; Costas, Miguel; Rodríguez-Romero, Adela; Alejandro Fernández-Velasco, D

    2015-08-28

    Temperature is one of the main variables that modulate protein function and stability. Thermodynamic studies of oligomeric proteins, the dominant protein natural form, have been often hampered because irreversible aggregation and/or slow reactions are common. There are no reports on the reversible equilibrium thermal unfolding of proteins composed of (β/α)8 barrel subunits, albeit this "TIM barrel" topology is one of the most abundant and versatile in nature. We studied the eponymous TIM barrel, triosephosphate isomerase (TIM), belonging to five species of different bacterial taxa. All of them were found to be catalytically efficient dimers. The three-dimensional structure of four enzymes was solved at high/medium resolution. Irreversibility and kinetic control were observed in the thermal unfolding of two TIMs, while for the other three the thermal unfolding was found to follow a two-state equilibrium reversible process. Shifts in the global stability curves of these three proteins are related to the organismal temperature range of optimal growth and modulated by variations in maximum stability temperature and in the enthalpy change at that temperature. Reversibility appears to correlate with the low isoelectric point, the absence of a residual structure in the unfolded state, small cavity volume in the native state, low conformational stability and a low melting temperature. Furthermore, the strong coupling between dimer dissociation and monomer unfolding may reduce aggregation and favour reversibility. It is therefore very thought-provoking to find that a common topological ensemble, such as the TIM barrel, can unfold/refold in the Anfinsen way, i.e. without the help of the cellular machinery.

  18. High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries.

    Science.gov (United States)

    Hendriks, Koen H; Robinson, Sophia G; Braten, Miles N; Sevov, Christo S; Helms, Brett A; Sigman, Matthew S; Minteer, Shelley D; Sanford, Melanie S

    2018-02-28

    Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation while maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. These studies provide a template for the future design of other redox-active oligomers for this application.

  19. The cysteines of the extracellular loop are crucial for trafficking of human organic cation transporter 2 to the plasma membrane and are involved in oligomerization.

    Science.gov (United States)

    Brast, Sabine; Grabner, Alexander; Sucic, Sonja; Sitte, Harald H; Hermann, Edwin; Pavenstädt, Hermann; Schlatter, Eberhard; Ciarimboli, Giuliano

    2012-03-01

    Human organic cation transporter 2 (hOCT2) is involved in transport of many endogenous and exogenous organic cations, mainly in kidney and brain cells. Because the quaternary structure of transmembrane proteins plays an essential role for their cellular trafficking and function, we investigated whether hOCT2 forms oligomeric complexes, and if so, which part of the transporter is involved in the oligomerization. A yeast 2-hybrid mating-based split-ubiquitin system (mbSUS), fluorescence resonance energy transfer, Western blot analysis, cross-linking experiments, immunofluorescence, and uptake measurements of the fluorescent organic cation 4-(4-(dimethylamino)styryl)-N-methylpyridinium were applied to human embryonic kidney 293 (HEK293) cells transfected with hOCT2 and partly also to freshly isolated human proximal tubules. The role of cysteines for oligomerization and trafficking of the transporter to the plasma membranes was investigated in cysteine mutants of hOCT2. hOCT2 formed oligomers both in the HEK293 expression system and in native human kidneys. The cysteines of the large extracellular loop are important to enable correct folding, oligomeric assembly, and plasma membrane insertion of hOCT2. Mutation of the first and the last cysteines of the loop at positions 51 and 143 abolished oligomer formation. Thus, the cysteines of the extracellular loop are important for correct trafficking of the transporter to the plasma membrane and for its oligomerization.

  20. Contribution to the reconstruction of scenes made of cylindrical and polyhedral objects from sequences of images obtained by a moving camera

    International Nuclear Information System (INIS)

    Viala, Marc

    1992-01-01

    Environment perception is an important process which enables a robot to perform actions in an unknown scene. Although many sensors exist to 'give sight', the camera seems to play a leading part. This thesis deals with the reconstruction of scenes made of cylindrical and polyhedral objects from sequences of images provided by a moving camera. Two methods are presented. Both are based on the evolution of apparent contours of objects in a sequence. The first approach has been developed considering that camera motion is known. Despite the good results obtained by this method, the specific conditions it requires makes its use limited. In order to avoid an accurate evaluation of camera motion, we introduce another method allowing, at the same time, to estimate the object parameters and camera positions. In this approach, only is needed a 'poor' knowledge of camera displacements supplied by the control system of the robotic platform, in which the camera is embedded. An optimal integration of a priori information, as well as the dynamic feature of the state model to estimate, lead us to use the Kalman filter. Experiments conducted with synthetic and real images proved the reliability of these methods. Camera calibration set-up is also suggested to achieve the most accurate scene models resulting from reconstruction processes. (author) [fr

  1. MxiN Differentially Regulates Monomeric and Oligomeric Species of the Shigella Type Three Secretion System ATPase Spa47.

    Science.gov (United States)

    Case, Heather B; Dickenson, Nicholas E

    2018-04-17

    Shigella rely entirely on the action of a single type three secretion system (T3SS) to support cellular invasion of colonic epithelial cells and to circumvent host immune responses. The ATPase Spa47 resides at the base of the Shigella needle-like type three secretion apparatus (T3SA), supporting protein secretion through the apparatus and providing a likely means for native virulence regulation by Shigella and a much needed target for non-antibiotic therapeutics to treat Shigella infections. Here, we show that MxiN is a differential regulator of Spa47 and that its regulatory impact is determined by the oligomeric state of the Spa47 ATPase, with which it interacts. In vitro and in vivo characterization shows that interaction of MxiN with Spa47 requires the six N-terminal residues of Spa47 that are also necessary for stable Spa47 oligomer formation and activation. This interaction with MxiN negatively influences the activity of Spa47 oligomers while upregulating the ATPase activity of monomeric Spa47. Detailed kinetic analyses of monomeric and oligomeric Spa47 in the presence and absence of MxiN uncover additional mechanistic insights into the regulation of Spa47 by MxiN, suggesting that the MxiN/Spa47 species resulting from interaction with monomeric and oligomeric Spa47 are functionally distinct and that both could be involved in Shigella T3SS regulation. Uncovering regulation of Spa47 by MxiN addresses an important gap in the current understanding of how Shigella controls T3SA activity and provides the first description of differential T3SS ATPase regulation by a native T3SS protein.

  2. In situ oligomerization of 2-(thiophen-3-yl)acetate intercalated into Zn{sub 2}Al layered double hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Tronto, Jairo, E-mail: jairotronto@ufv.br [Universidade Federal de Viçosa, Instituto de Ciências Exatas e Tecnológicas, Campus de Rio Parsanaíba, Rodovia BR 354 km 310, Cx. Postal 22, CEP, 38.810-000 Rio Paranaíba, MG (Brazil); Pinto, Frederico G.; Costa, Liovando M. da [Universidade Federal de Viçosa, Instituto de Ciências Exatas e Tecnológicas, Campus de Rio Parsanaíba, Rodovia BR 354 km 310, Cx. Postal 22, CEP, 38.810-000 Rio Paranaíba, MG (Brazil); Leroux, Fabrice; Dubois, Marc [Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6296, ICCF, BP 80026, F-6317 Clermont-Ferrand (France); Valim, João B. [Universidade de São Paulo, Faculdade de Filosofia Ciências e Letras de Ribeirão Preto, Departamento de Química, Av. dos Bandeirantes 3900, CEP 14.040-901, Ribeirão Preto, SP (Brazil)

    2015-01-15

    A layered double hydroxide (LDH) with cation composition Zn{sub 2}Al was intercalated with 2-(thiophen-3-yl)acetate (3-TA) monomers. To achieve in situ polymerization and/or oligomerization of the intercalated monomers, soft thermal treatments were carried out, and subsequent hybrid LDH materials were analyzed by means of several characterization techniques using powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), {sup 13}C CP–MAS nuclear magnetic resonance (NMR), electron spin resonance (EPR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP–OES), and elemental analysis. PXRD analysis suggested that the intercalated monomers formed a bilayer. Thermal treatment of the hybrid LDH assembly above 120 °C provokes partially the breakdown of the layered structure, generating the phase zincite. EPR results indicated that vicinal monomers (oligomerization) were bound to each other after hydrothermal or thermal treatment, leading to a polaron response characteristic of electron conductivity localized on a restricted number of thiophene-based monomer segments. Localized unpaired electrons exist in the material and interact with the {sup 27}Al nuclei of the LDH layers by superhyperfine coupling. These unpaired electrons also interact with the surface of ZnO (O{sup 2−} vacancies), formed during the thermal treatments. - Graphical abstract: We synthesized a layered double hydroxide (LDH) with cation composition Zn{sub 2}Al, intercalated with 2-(thiophen-3-yl)acetate (3-TA) monomers, by coprecipitation at constant pH. We thermally treated the material, to achieve in situ polymerization and/or oligomerization of the intercalated monomers. - Highlights: • A Zn{sub 2}Al–LDH was intercalated with 2-(thiophen-3-yl)acetate monomers. • To achieve in situ oligomerization of the monomers, thermal treatments were made.

  3. Oligomerization of adenosin-5´-O-ylmethylphosphonate, an isopolar AMP analogue: Evaluation of the route to short oligoadenylates

    Czech Academy of Sciences Publication Activity Database

    Pressová, Martina; Buděšínský, Miloš; Kóšiová, Ivana; Kopecký, V. Jr.; Cvačka, Josef; Kašička, Václav; Šimák, Ondřej; Točík, Zdeněk; Rosenberg, Ivan

    2010-01-01

    Roč. 93, č. 3 (2010), s. 277-289 ISSN 0006-3525 R&D Projects: GA MŠk(CZ) LC06077; GA MŠk(CZ) LC06061; GA AV ČR KAN200520801; GA ČR GA203/09/0820; GA ČR GA202/09/0193 Grant - others:EMIL-FW6(XE) 503569 Institutional research plan: CEZ:AV0Z40550506 Keywords : spontaneous oligomerization * oligoadenylates * phosphonate linkage Subject RIV: CC - Organic Chemistry Impact factor: 2.572, year: 2010

  4. Implication of the oligomeric state of the N-terminal PTX3 domain in cumulus matrix assembly.

    Science.gov (United States)

    Ievoli, Elena; Lindstedt, Ragnar; Inforzato, Antonio; Camaioni, Antonella; Palone, Francesca; Day, Anthony J; Mantovani, Alberto; Salvatori, Giovanni; Salustri, Antonietta

    2011-06-01

    Pentraxin 3 (PTX3) plays a key role in the formation of the hyaluronan-rich matrix of the cumulus oophorus surrounding ovulated eggs that is required for successful fertilization and female fertility. PTX3 is a multimeric protein consisting of eight identical protomers held together by a combination of non-covalent interactions and disulfide bonds. Recent findings suggest that the oligomeric status of PTX3 is important for stabilizing the cumulus matrix. Because the role of PTX3 in the cumulus resides in the unique N-terminal sequence of the protomer, we investigated further this issue by testing the ability of distinct Cys/Ser mutants of recombinant N-terminal region of PTX3 (N(_)PTX3) with different oligomeric arrangement to promote in vitro normal expansion in cumuli from Ptx3-null mice. Here we report that the dimer of the N(_)PTX3 is unable to rescue cumulus matrix organization, and that the tetrameric assembly of the protein is the minimal oligomeric state required for accomplishing this function. We have previously demonstrated that PTX3 binds to HCs of IαI and TSG-6, which are essential for cumulus matrix formation and able to interact with hyaluronan. Interestingly, here we show by solid-phase binding experiments that the dimer of the N(_)PTX3 retains the ability to bind to both IαI and TSG-6, suggesting that the octameric structure of PTX3 provides multiple binding sites for each of these ligands. These findings support the hypothesis that PTX3 contributes to cumulus matrix organization by cross-linking HA polymers through interactions with multiple HCs of IαI and/or TSG-6. The N-terminal PTX3 tetrameric oligomerization was recently reported to be also required for recognition and inhibition of FGF2. Given that this growth factor has been detected in the mammalian preovulatory follicle, we wondered whether FGF2 negatively influences cumulus expansion and PTX3 may also serve in vivo to antagonize its activity. We found that a molar excess of FGF2, above

  5. Predicting success of oligomerized pool engineering (OPEN for zinc finger target site sequences

    Directory of Open Access Journals (Sweden)

    Goodwin Mathew J

    2010-11-01

    Full Text Available Abstract Background Precise and efficient methods for gene targeting are critical for detailed functional analysis of genomes and regulatory networks and for potentially improving the efficacy and safety of gene therapies. Oligomerized Pool ENgineering (OPEN is a recently developed method for engineering C2H2 zinc finger proteins (ZFPs designed to bind specific DNA sequences with high affinity and specificity in vivo. Because generation of ZFPs using OPEN requires considerable effort, a computational method for identifying the sites in any given gene that are most likely to be successfully targeted by this method is desirable. Results Analysis of the base composition of experimentally validated ZFP target sites identified important constraints on the DNA sequence space that can be effectively targeted using OPEN. Using alternate encodings to represent ZFP target sites, we implemented Naïve Bayes and Support Vector Machine classifiers capable of distinguishing "active" targets, i.e., ZFP binding sites that can be targeted with a high rate of success, from those that are "inactive" or poor targets for ZFPs generated using current OPEN technologies. When evaluated using leave-one-out cross-validation on a dataset of 135 experimentally validated ZFP target sites, the best Naïve Bayes classifier, designated ZiFOpT, achieved overall accuracy of 87% and specificity+ of 90%, with an ROC AUC of 0.89. When challenged with a completely independent test set of 140 newly validated ZFP target sites, ZiFOpT performance was comparable in terms of overall accuracy (88% and specificity+ (92%, but with reduced ROC AUC (0.77. Users can rank potentially active ZFP target sites using a confidence score derived from the posterior probability returned by ZiFOpT. Conclusion ZiFOpT, a machine learning classifier trained to identify DNA sequences amenable for targeting by OPEN-generated zinc finger arrays, can guide users to target sites that are most likely to function

  6. The neuroprotective effects of milk fat globule-EGF factor 8 against oligomeric amyloid β toxicity

    Directory of Open Access Journals (Sweden)

    Li Endong

    2012-06-01

    Full Text Available Abstract Background Phosphatidylserine receptor is a key molecule that mediates the phagocytosis of apoptotic cells. Milk fat globule-EGF factor 8 (MFG-E8 is a phosphatidylserine receptor that is expressed on various macrophage lineage cells, including microglia in the central nervous system (CNS. Targeted clearance of degenerated neurons by microglia is essential to maintain healthy neural networks. We previously showed that the CX3C chemokine fractalkine is secreted from degenerated neurons and accelerates microglial clearance of neuronal debris via inducing the release of MFG-E8. However, the mechanisms by which microglia produce MFG-E8 and the precise functions of MFG-E8 are unknown. Methods The release of MFG-E8 from microglia treated with conditioned medium from neurons exposed to neurotoxic substances, glutamate or oligomeric amyloid β (oAβ was measured by ELISA. The neuroprotective effects of MFG-E8 and MFG-E8 − induced microglial phagocytosis of oAβ were assessed by immunocytochemistry. The effects of MFG-E8 on the production of the anti-oxidative enzyme hemeoxygenase-1 (HO-1 were determined by ELISA and immunocytochemisty. Results MFG-E8 was induced in microglia treated with conditioned medium from neurons that had been exposed to neurotoxicants, glutamate or oAβ. MFG-E8 significantly attenuated oAβ-induced neuronal cell death in a primary neuron − microglia coculture system. Microglial phagocytosis of oAβ was accelerated by MFG-E8 treatment due to increased CD47 expression in the absence of neurotoxic molecule production, such as tumor necrosis factor-α, nitric oxide, and glutamate. MFG-E8 − treated microglia induced nuclear factor E(2 − related factor 2 (Nrf2 − mediated HO-1 production, which also contributed to neuroprotection. Conclusions These results suggest that microglia release MFG-E8 in response to signals from degenerated neurons and that MFG-E8 protects oAβ-induced neuronal cell death

  7. Protective Effects of Testosterone on Presynaptic Terminals against Oligomeric β-Amyloid Peptide in Primary Culture of Hippocampal Neurons

    Directory of Open Access Journals (Sweden)

    Chi-Fai Lau

    2014-01-01

    Full Text Available Increasing lines of evidence support that testosterone may have neuroprotective effects. While observational studies reported an association between higher bioavailable testosterone or brain testosterone levels and reduced risk of Alzheimer’s disease (AD, there is limited understanding of the underlying neuroprotective mechanisms. Previous studies demonstrated that testosterone could alleviate neurotoxicity induced by β-amyloid (Aβ, but these findings mainly focused on neuronal apoptosis. Since synaptic dysfunction and degeneration are early events during the pathogenesis of AD, we aim to investigate the effects of testosterone on oligomeric Aβ-induced synaptic changes. Our data suggested that exposure of primary cultured hippocampal neurons to oligomeric Aβ could reduce the length of neurites and decrease the expression of presynaptic proteins including synaptophysin, synaptotagmin, and synapsin-1. Aβ also disrupted synaptic vesicle recycling and protein folding machinery. Testosterone preserved the integrity of neurites and the expression of presynaptic proteins. It also attenuated Aβ-induced impairment of synaptic exocytosis. By using letrozole as an aromatase antagonist, we further demonstrated that the effects of testosterone on exocytosis were unlikely to be mediated through the estrogen receptor pathway. Furthermore, we showed that testosterone could attenuate Aβ-induced reduction of HSP70, which suggests a novel mechanism that links testosterone and its protective function on Aβ-induced synaptic damage. Taken together, our data provide further evidence on the beneficial effects of testosterone, which may be useful for future drug development for AD.

  8. DC-SIGN neck domain is a pH-sensor controlling oligomerization: SAXS and hydrodynamic studies of extracellular domain.

    Science.gov (United States)

    Tabarani, Georges; Thépaut, Michel; Stroebel, David; Ebel, Christine; Vivès, Corinne; Vachette, Patrice; Durand, Dominique; Fieschi, Franck

    2009-08-07

    DC-SIGN is a C-type lectin receptor of dendritic cells and is involved in the early stages of numerous infectious diseases. DC-SIGN is organized into a tetramer enabling multivalent interaction with pathogens. Once formed, the DC-SIGN-pathogen complex can be internalized into compartments of increasing acidity. We have studied the pH dependence of the oligomerization state and conformation of the entire extracellular domain and neck region. We present evidence for equilibrium between the monomeric and tetrameric states of the extracellular domain, which exhibits a marked dependence with respect to both pH and ionic strength. Using solution x-ray scattering we have obtained a molecular envelope of the extracellular domain in which a model has been built. Our results highlight the central role of the neck domain in the pH-sensitive control of the oligomerization state, in the extended conformation of the protein, and in carbohydrate recognition domain organization and presentation. This work opens new insight into the molecular mechanism of ligand release and points to new avenues to block the first step of this important infection pathway.

  9. Selective binding and oligomerization of the murine granulocyte colony-stimulating factor receptor by a low molecular weight, nonpeptidyl ligand.

    Science.gov (United States)

    Doyle, Michael L; Tian, Shin-Shay; Miller, Stephen G; Kessler, Linda; Baker, Audrey E; Brigham-Burke, Michael R; Dillon, Susan B; Duffy, Kevin J; Keenan, Richard M; Lehr, Ruth; Rosen, Jon; Schneeweis, Lumelle A; Trill, John; Young, Peter R; Luengo, Juan I; Lamb, Peter

    2003-03-14

    Granulocyte colony-stimulating factor regulates neutrophil production by binding to a specific receptor, the granulocyte colony-stimulating factor receptor, expressed on cells of the granulocytic lineage. Recombinant forms of granulocyte colony-stimulating factor are used clinically to treat neutropenias. As part of an effort to develop granulocyte colony-stimulating factor mimics with the potential for oral bioavailability, we previously identified a nonpeptidyl small molecule (SB-247464) that selectively activates murine granulocyte colony-stimulating factor signal transduction pathways and promotes neutrophil formation in vivo. To elucidate the mechanism of action of SB-247464, a series of cell-based and biochemical assays were performed. The activity of SB-247464 is strictly dependent on the presence of zinc ions. Titration microcalorimetry experiments using a soluble murine granulocyte colony-stimulating factor receptor construct show that SB-247464 binds to the extracellular domain of the receptor in a zinc ion-dependent manner. Analytical ultracentrifugation studies demonstrate that SB-247464 induces self-association of the N-terminal three-domain fragment in a manner that is consistent with dimerization. SB-247464 induces internalization of granulocyte colony-stimulating factor receptor on intact cells, consistent with a mechanism involving receptor oligomerization. These data show that small nonpeptidyl compounds are capable of selectively binding and inducing productive oligomerization of cytokine receptors.

  10. Nanomolar oligomerization and selective co-aggregation of α-synuclein pathogenic mutants revealed by single-molecule fluorescence

    Science.gov (United States)

    Sierecki, Emma; Giles, Nichole; Bowden, Quill; Polinkovsky, Mark E.; Steinbeck, Janina; Arrioti, Nicholas; Rahman, Diya; Bhumkar, Akshay; Nicovich, Philip R.; Ross, Ian; Parton, Robert G.; Böcking, Till; Gambin, Yann

    2016-01-01

    Protein aggregation is a hallmark of many neurodegenerative diseases, notably Alzheimer’s and Parkinson’s disease. Parkinson’s disease is characterized by the presence of Lewy bodies, abnormal aggregates mainly composed of α-synuclein. Moreover, cases of familial Parkinson’s disease have been linked to mutations in α-synuclein. In this study, we compared the behavior of wild-type (WT) α-synuclein and five of its pathological mutants (A30P, E46K, H50Q, G51D and A53T). To this end, single-molecule fluorescence detection was coupled to cell-free protein expression to measure precisely the oligomerization of proteins without purification, denaturation or labelling steps. In these conditions, we could detect the formation of oligomeric and pre-fibrillar species at very short time scale and low micromolar concentrations. The pathogenic mutants surprisingly segregated into two classes: one group forming large aggregates and fibrils while the other tending to form mostly oligomers. Strikingly, co-expression experiments reveal that members from the different groups do not generally interact with each other, both at the fibril and monomer levels. Together, this data paints a completely different picture of α-synuclein aggregation, with two possible pathways leading to the development of fibrils. PMID:27892477

  11. Fingolimod phosphate attenuates oligomeric amyloid β-induced neurotoxicity via increased brain-derived neurotrophic factor expression in neurons.

    Directory of Open Access Journals (Sweden)

    Yukiko Doi

    Full Text Available The neurodegenerative processes that underlie Alzheimer's disease are mediated, in part, by soluble oligomeric amyloid β, a neurotoxic protein that inhibits hippocampal long-term potentiation, disrupts synaptic plasticity, and induces the production of reactive oxygen species. Here we show that the sphingosine-1-phosphate (S1P receptor (S1PR agonist fingolimod phosphate (FTY720-P-a new oral drug for multiple sclerosis-protects neurons against oligomeric amyloid β-induced neurotoxicity. We confirmed that primary mouse cortical neurons express all of the S1P receptor subtypes and FTY720-P directly affects the neurons. Treatment with FTY720-P enhanced the expression of brain-derived neurotrophic factor (BDNF in neurons. Moreover, blocking BDNF-TrkB signaling with a BDNF scavenger, TrkB inhibitor, or ERK1/2 inhibitor almost completely ablated these neuroprotective effects. These results suggested that the neuroprotective effects of FTY720-P are mediated by upregulated neuronal BDNF levels. Therefore, FTY720-P may be a promising therapeutic agent for neurodegenerative diseases, such as Alzheimer's disease.

  12. A novel POSS-coated quantum dot for biological application

    Directory of Open Access Journals (Sweden)

    Rizvi SB

    2012-08-01

    Full Text Available Sarwat B Rizvi,1 Lara Yildirimer,1 Shirin Ghaderi,1 Bala Ramesh,1 Alexander M Seifalian,1,2 Mo Keshtgar1,21UCL Centre for Nanotechnology and Regenerative Medicine, Division of Surgery and Interventional Science, University College London, United Kingdom; 2Royal Free Hampstead NHS Trust Hospital, London, United KingdomAbstract: Quantum dots (QDs are fluorescent semiconductor nanocrystals that have the potential for major advancements in the field of nanomedicine through their unique photophysical properties. They can potentially be used as fluorescent probes for various biomedical imaging applications, including cancer localization, detection of micrometastasis, image guided surgery, and targeted drug delivery. Their main limitation is toxicity, which requires a biologically compatible surface coating to shield the toxic core from the surrounding environment. However, this leads to an increase in QD size that may lead to problems of excretion and systemic sequestration. We describe a one pot synthesis, characterization, and in vitro cytotoxicity of a novel polyhedral oligomeric silsesquioxane (POSS-coated CdTe-cored QD using mercaptosuccinic acid (MSA and D-cysteine as stabilizing agents. Characterization was performed using transmission electron microscopy Fourier transform infrared spectroscopy, and photoluminescence studies. POSS-coated QDs demonstrated high colloidal stability and enhanced photostability on high degrees of ultraviolet (UV excitation compared to QDs coated with MSA and D-cysteine alone (P value < 0.05. In vitro toxicity studies showed that both POSS and MSA-QDs were significantly less toxic than ionized salts of Cd+2 and Te-2. Confocal microscopy confirmed high brightness of POSS-QDs in cells at both 1 and 24 hours, indicating that these QDs are rapidly taken up by cells and remain photostable in a biological environment. We therefore conclude that a POSS coating confers biological compatibility, photostability, and colloidal

  13. Electrorheological fluids and methods

    Science.gov (United States)

    Green, Peter F.; McIntyre, Ernest C.

    2015-06-02

    Electrorheological fluids and methods include changes in liquid-like materials that can flow like milk and subsequently form solid-like structures under applied electric fields; e.g., about 1 kV/mm. Such fluids can be used in various ways as smart suspensions, including uses in automotive, defense, and civil engineering applications. Electrorheological fluids and methods include one or more polar molecule substituted polyhedral silsesquioxanes (e.g., sulfonated polyhedral silsesquioxanes) and one or more oils (e.g., silicone oil), where the fluid can be subjected to an electric field.

  14. Skeleton polyhedral rearrangements of 8-alkyl-7,9-dicarba-nido-undecaborate(-1) anion to 11-alkyl-2,7-dicarba-nido-undecaborane(13) and to 9-alkyl-7,8-dicarba-nido-undecaborate(-1) anion. Molecular structure of 2,7-Me2-11-PhCH2-2,7-C2B9H10

    International Nuclear Information System (INIS)

    Zakharkin, K.I.; Zhigareva, G.G.; Antonovich, V.A.; Yanovskij, A.I.; Struchkov, Yu.T.

    1986-01-01

    Using the methods of 1 H and 11 B NMR-spectroscopy and X-ray diffraction analysis skeleton polyhedral rearrangements of carboranes are studied. During protonation of anion 8-R-7, 9-R' 2 -7, 9-C 2 B 9 H 9 - the skeleton polyhedral rearrangement in the series of nido-carboranes, resulting in 2,7-R' 2 -11-R-2, 7-C 2 B 9 H 10 (R=Me, PhCH 2 , R'=H, Me) is observed. The rearrangement is reversible. On the detachment of two protons from 2,7-Me 2 -11-PhCH 2 -2,7-C 2 B 9 H 10 and during subsequent protonation the skeleton polyhedral rearrangement with the formation of anion 9-PhCH 2 -7,8-Me 2 -7,8-C 2 B 9 H 9 - takes place

  15. A Silsesquioxane Organically Modified with 4-Amino-5-(4-pyridyl-4H-1,2,4-triazole-3-thiol: Thermal Behavior and Its Electrochemical Detection of Sulfhydryl Compounds

    Directory of Open Access Journals (Sweden)

    D. R. Do Carmo

    2014-01-01

    Full Text Available The octakis(3-chloropropylsilsesquioxane (SS was organofunctionalized with 4-amino-5-4(pyridyl-4H-1,2,4-triazole-3-thiol. The product formed (SA was undergo another reactions in two steps, first with copper and so hexacyanoferrate (III to form CuHSA. The organofunctionalized silsesquioxane was characterized by the following techniques: scanning electron microscopy (SEM, Fourier transform infrared (FTIR, nuclear magnetic resonance (NMR in solid state, and thermogravimetric analysis in air and nitrogen atmosphere. The composite CuHSA was incorporated into a graphite paste electrode and the electrochemical behavior studies were conducted with cyclic voltammetry. The cyclic voltammogram of the modified graphite paste electrode with CuHSA showed one redox couple with formal potential Eθ′=0.75 V versus Ag/AgCl(sat (KCl 1.0 mol L−1; v = 20 mV s−1 attributed to the redox process Fe(II(CN6/Fe(III(CN6 of the binuclear complex formed. The redox couple presents an electrocatalytic response of sulfhydryl compounds such as n-acetylcysteine and l-cysteine. For determination of n-acetylcysteine and l-cysteine the modified graphite paste electrode showed a linear region in the concentration range of 2 to 20 mmol L−1. The modified electrode was chemically and electrochemically stable and showed good reproducibility.

  16. Constitutive homo- and hetero-oligomerization of TbetaRII-B, an alternatively spliced variant of the mouse TGF-beta type II receptor

    DEFF Research Database (Denmark)

    Krishnaveni, Manda S; Hansen, Jakob Lerche; Seeger, Werner

    2006-01-01

    , but the oligomerization pattern and dynamics of TbetaRII splice variants in live cells has not been demonstrated thus far. Using co-immunoprecipitation and bioluminescence resonance energy transfer (BRET), we demonstrate that the mouse TbetaRII receptor splice variant TbetaRII-B is capable of forming ligand...

  17. Iron-induced oligomerization of human FXN81-210 and bacterial CyaY frataxin and the effect of iron chelators

    DEFF Research Database (Denmark)

    Ahlgren, Eva Christina; Fekry, Mostafa; Wiemann, Mathias

    2017-01-01

    long forms, FXN42-210 and FXN56-210, have been shown to spontaneously form oligomeric particles stabilized by the extended N-terminal sequence. The short variant FXN81-210, on other hand, has only been observed in the monomeric state. However, a highly homologous E. coli frataxin CyaY, which also lacks...

  18. Oligomeric forms of the metastasis-related Mts1 (S100A4) protein stimulate neuronal differentiation in cultures of rat hippocampal neurons

    DEFF Research Database (Denmark)

    Novitskaya, V; Grigorian, M; Kriajevska, M

    2000-01-01

    protein family. The oligomeric but not the dimeric form of Mts1 strongly induces differentiation of cultured hippocampal neurons. A mutant with a single Y75F amino acid substitution, which stabilizes the dimeric form of Mts1, is unable to promote neurite extension. Disulfide bonds do not play an essential...

  19. DFT study on the impact of the methylaluminoxane cocatalyst in ethylene oligomerization using a titanium-based catalyst

    KAUST Repository

    Pasha, Farhan Ahmad

    2015-01-26

    A computational study within the framework of density functional theory is presented on the oligomerization of ethylene to yield 1-hexene using [(η5-C5H4CMe2C6H5)]TiCl3/MAO] catalyst. This study explicitly takes into account a methylaluminoxane (MAO) cocatalyst model, where the MAO cluster has become an anionic species after having abstracted one chloride anion, yielding a cationic activated catalyst. Hence, the reaction profile was calculated using the zwitterionic system, and the potential energy surface has been compared to the cationic catalytic system. Modest differences were found between the two free energy profiles. However, we show for the first time that the use of a realistic zwitterionic model is required to obtain a Brønsted-Evans-Polanyi relationship between the energy barriers and reaction energies.

  20. DFT study on the impact of the methylaluminoxane cocatalyst in ethylene oligomerization using a titanium-based catalyst

    KAUST Repository

    Pasha, Farhan Ahmad; Basset, Jean-Marie; Toulhoat, Hervé ; De Bruin, Theodorus J M

    2015-01-01

    A computational study within the framework of density functional theory is presented on the oligomerization of ethylene to yield 1-hexene using [(η5-C5H4CMe2C6H5)]TiCl3/MAO] catalyst. This study explicitly takes into account a methylaluminoxane (MAO) cocatalyst model, where the MAO cluster has become an anionic species after having abstracted one chloride anion, yielding a cationic activated catalyst. Hence, the reaction profile was calculated using the zwitterionic system, and the potential energy surface has been compared to the cationic catalytic system. Modest differences were found between the two free energy profiles. However, we show for the first time that the use of a realistic zwitterionic model is required to obtain a Brønsted-Evans-Polanyi relationship between the energy barriers and reaction energies.

  1. Effects of Bentonite on p-Methoxybenzyl Acetate: A Theoretical Model for Oligomerization via an Electrophilic-Substitution Mechanism

    Directory of Open Access Journals (Sweden)

    Manuel Salmón

    2011-02-01

    Full Text Available Tonsil Actisil FF, a commercial bentonitic clay, promotes the formation of a series of electrophilic-aromatic-substitution products from para-methoxybenzyl acetate in carbon disulfide. The molecules obtained correspond to linear isomeric dimers, trimers, tetramers and a pentamer, according to their spectroscopic data. A clear indication of the title mechanistic pathway for the oligomerization growth was obtained from the analysis of a set of computational-chemistry calculations using the density-functional-theory level B3LYP/6-311++G(d,p. The corresponding conclusions were based on the computed dipole moments, the HOMO/LUMO distributions, and a natural-populations analysis of the studied molecules.

  2. Cartilage oligomeric matrix protein deficiency promotes early onset and the chronic development of collagen-induced arthritis

    DEFF Research Database (Denmark)

    Geng, Hui; Carlsen, Stefan; Nandakumar, Kutty

    2008-01-01

    ABSTRACT: INTRODUCTION: Cartilage oligomeric matrix protein (COMP) is a homopentameric protein in cartilage. The development of arthritis, like collagen-induced arthritis (CIA), involves cartilage as a target tissue. We have investigated the development of CIA in COMP-deficient mice. METHODS: COMP......-deficient mice in the 129/Sv background were backcrossed for 10 generations against B10.Q mice, which are susceptible to chronic CIA. COMP-deficient and wild-type mice were tested for onset, incidence, and severity of arthritis in both the collagen and collagen antibody-induced arthritis models. Serum anti......-collagen II and anti-COMP antibodies as well as serum COMP levels in arthritic and wild-type mice were measured by enzyme-linked immunosorbent assay. RESULTS: COMP-deficient mice showed a significant early onset and increase in the severity of CIA in the chronic phase, whereas collagen II-antibody titers were...

  3. Substitution of proline32 by α-methylproline preorganizes β2-microglobulin for oligomerization but not for aggregation into amyloids.

    Science.gov (United States)

    Torbeev, Vladimir; Ebert, Marc-Olivier; Dolenc, Jozica; Hilvert, Donald

    2015-02-25

    Conversion of soluble folded proteins into insoluble amyloids generally proceeds in three distinct mechanistic stages: (1) initial protein misfolding into aggregation-competent conformers, (2) subsequent formation of oligomeric species and, finally, (3) self-assembly into extended amyloid fibrils. In the work reported herein, we interrogated the amyloidogenesis mechanism of human β2-microglobulin (β2m), which is thought to be triggered by a pivotal cis-trans isomerization of a proline residue at position 32 in the polypeptide, with nonstandard amino acids. Using chemical protein synthesis we prepared a β2m analogue in which Pro32 was replaced by the conformationally constrained amino acid α-methylproline (MePro). The strong propensity of MePro to adopt a trans prolyl bond led to enhanced population of a non-native [trans-MePro32]β2m protein conformer, which readily formed oligomers at neutral pH. In the presence of the antibiotic rifamycin SV, which inhibits amyloid growth of wild-type β2m, [MePro32]β2m was nearly quantitatively converted into different spherical oligomeric species. Self-assembly into amyloid fibrils was not observed in the absence of seeding, however, even at low pH (<3), where wild-type β2m spontaneously forms amyloids. Nevertheless, we found that aggregation-preorganized [MePro32]β2m can act in a prion-like fashion, templating misfolded conformations in a natively folded protein. Overall, these results provide detailed insight into the role of cis-trans isomerization of Pro32 and ensuing structural rearrangements that lead to initial β2m misfolding and aggregation. They corroborate the view that conformational protein dynamics enabled by reversible Pro32 cis-trans interconversion rather than simple population of the trans conformer is critical for both nucleation and subsequent growth of β2m amyloid structures.

  4. Assessment of Escherichia coli selenophosphate synthetase oligomeric states by analytical ultracentrifugation and small angle X-ray scattering

    Energy Technology Data Exchange (ETDEWEB)

    Silva, I.R.; Faim, F.M.; Oliveira Neto, M.; Thiemann, O.H. [Universidade de Sao Paulo (USP-SC), Sao Carlos, SP (Brazil); Borges, J.C. [Universidade de Sao Paulo (IQSC/USP), Sao Carlos, SP (Brazil). Inst. de Quimica

    2012-07-01

    Full text: Selenium is an essential micronutrient for many organisms and is present in selenium-containing proteins as selenocysteine (Sec) and RNAs as selenouridine. Specific selenium incorporation into selenoproteins and RNAs requires the generation of a biologically active selenium donor compound, selenophosphate, which is produced from the activation of selenide with adenosine 5-triphosphate (ATP) in a reaction catalyzed by Selenophosphate Synthetase (SELD). Therefore, SELD is a key enzyme of the selenium pathway in the cell. The Escherichia coli SELD open reading frame was cloned into pET28a (Novagen) expression vector and the recombinant protein was over expressed in Escherichia coli BL21(DE3) strain. In order to purify the protein, we used metal-chelate affinity chromatography followed by a gel filtration step. Analytical Ultracentrifugation (AUC) and Small Angle X-ray Scattering (SAXS) were employed to study the oligomeric states of the soluble protein. The results of AUC revealed dimer-tetramer and tetramer-octamer equilibrium at low concentrations of protein, with dissociation constants of 70 2 and 560 40 M, respectively. Moreover, the SAXS results pointed the oligomeric state of the protein at higher concentrations as predominantly dimeric and the p(r) and the SAXS envelope revealed the SELD as elongated. We also performed initial crystallization trials with protein samples at 7 mg/ml in 96-well sitting-drop crystallization plates at room temperature using a crystallization robot. Needle crystals appeared after some days. X-ray diffraction for these crystals were tested in the MX2 beamline at the Brazilian Synchrotron Laboratory (LNLS Campinas). We are now working to improve these crystals in order to obtain suitable crystals for structure determination. (author)

  5. Structural basis for TatA oligomerization: an NMR study of Escherichia coli TatA dimeric structure.

    Directory of Open Access Journals (Sweden)

    Yi Zhang

    Full Text Available Many proteins are transported across lipid membranes by protein translocation systems in living cells. The twin-arginine transport (Tat system identified in bacteria and plant chloroplasts is a unique system that transports proteins across membranes in their fully-folded states. Up to date, the detailed molecular mechanism of this process remains largely unclear. The Escherichia coli Tat system consists of three essential transmembrane proteins: TatA, TatB and TatC. Among them, TatB and TatC form a tight complex and function in substrate recognition. The major component TatA contains a single transmembrane helix followed by an amphipathic helix, and is suggested to form the translocation pore via self-oligomerization. Since the TatA oligomer has to accommodate substrate proteins of various sizes and shapes, the process of its assembly stands essential for understanding the translocation mechanism. A structure model of TatA oligomer was recently proposed based on NMR and EPR observations, revealing contacts between the transmembrane helices from adjacent subunits. Herein we report the construction and stabilization of a dimeric TatA, as well as the structure determination by solution NMR spectroscopy. In addition to more extensive inter-subunit contacts between the transmembrane helices, we were also able to observe interactions between neighbouring amphipathic helices. The side-by-side packing of the amphipathic helices extends the solvent-exposed hydrophilic surface of the protein, which might be favourable for interactions with substrate proteins. The dimeric TatA structure offers more detailed information of TatA oligomeric interface and provides new insights on Tat translocation mechanism.

  6. Sorption Behavior of Compressed CO2 and CH4 on Ultrathin Hybrid Poly(POSS-imide) Layers.

    Science.gov (United States)

    Raaijmakers, Michiel J T; Ogieglo, Wojciech; Wiese, Martin; Wessling, Matthias; Nijmeijer, Arian; Benes, Nieck E

    2015-12-09

    Sorption of compressed gases into thin polymeric films is essential for applications including gas sensors and membrane based gas separation. For glassy polymers, the sorption behavior is dependent on the nonequilibrium status of the polymer. The uptake of molecules by a polymer is generally accompanied by dilation, or swelling, of the polymer material. In turn, this dilation can result in penetrant induced plasticization and physical aging that affect the nonequilibrium status of the polymer. Here, we investigate the dilation and sorption behavior of ultrathin membrane layers of a hybrid inorganic-organic network material that consists of alternating polyhedral oligomeric silsesquioxane and imide groups, upon exposure to compressed carbon dioxide and methane. The imide precursor contains fluoroalkene groups that provide affinity toward carbon dioxide, while the octa-functionalized silsesquioxane provides a high degree of cross-linking. This combination allows for extremely high sorption capacities, while structural rearrangements of the network are hindered. We study the simultaneous uptake of gases and dilation of the thin films at high pressures using spectroscopic ellipsometry measurements. Ellipsometry provides the changes in both the refractive index and the film thickness, and allows for accurate quantification of sorption and swelling. In contrast, gravimetric and volumetric measurements only provide a single parameter; this does not allow an accurate correction for, for instance, the changes in buoyancy because of the extensive geometrical changes of highly swelling films. The sorption behavior of the ultrathin hybrid layers depends on the fluoroalkene group content. At low pressure, the apparent molar volume of the gases is low compared to the liquid molar volume of carbon dioxide and methane, respectively. At high gas concentrations in the polymer film, the apparent molar volume of carbon dioxide and methane exceeds that of the liquid molar volume, and

  7. Hamiltonian cycles in polyhedral maps

    Indian Academy of Sciences (India)

    Dipendu Maity

    2017-08-24

    Aug 24, 2017 ... and [3] for graph theory related terminology. ... edges of M which are dual to edges of C and form a set E by putting these dual edges ...... In this process, consider components of G . Now, proper tree is a tree that touches all ...

  8. Zinc and the iron donor frataxin regulate oligomerization of the scaffold protein to form new Fe-S cluster assembly centers.

    Science.gov (United States)

    Galeano, B K; Ranatunga, W; Gakh, O; Smith, D Y; Thompson, J R; Isaya, G

    2017-06-21

    Early studies of the bacterial Fe-S cluster assembly system provided structural details for how the scaffold protein and the cysteine desulfurase interact. This work and additional work on the yeast and human systems elucidated a conserved mechanism for sulfur donation but did not provide any conclusive insights into the mechanism for iron delivery from the iron donor, frataxin, to the scaffold. We previously showed that oligomerization is a mechanism by which yeast frataxin (Yfh1) can promote assembly of the core machinery for Fe-S cluster synthesis both in vitro and in cells, in such a manner that the scaffold protein, Isu1, can bind to Yfh1 independent of the presence of the cysteine desulfurase, Nfs1. Here, in the absence of Yfh1, Isu1 was found to exist in two forms, one mostly monomeric with limited tendency to dimerize, and one with a strong propensity to oligomerize. Whereas the monomeric form is stabilized by zinc, the loss of zinc promotes formation of dimer and higher order oligomers. However, upon binding to oligomeric Yfh1, both forms take on a similar symmetrical trimeric configuration that places the Fe-S cluster coordinating residues of Isu1 in close proximity of iron-binding residues of Yfh1. This configuration is suitable for docking of Nfs1 in a manner that provides a structural context for coordinate iron and sulfur donation to the scaffold. Moreover, distinct structural features suggest that in physiological conditions the zinc-regulated abundance of monomeric vs. oligomeric Isu1 yields [Yfh1]·[Isu1] complexes with different Isu1 configurations that afford unique functional properties for Fe-S cluster assembly and delivery.

  9. Age- and brain region-dependent α-synuclein oligomerization is attributed to alterations in intrinsic enzymes regulating α-synuclein phosphorylation in aging monkey brains.

    Science.gov (United States)

    Chen, Min; Yang, Weiwei; Li, Xin; Li, Xuran; Wang, Peng; Yue, Feng; Yang, Hui; Chan, Piu; Yu, Shun

    2016-02-23

    We previously reported that the levels of α-syn oligomers, which play pivotal pathogenic roles in age-related Parkinson's disease (PD) and dementia with Lewy bodies, increase heterogeneously in the aging brain. Here, we show that exogenous α-syn incubated with brain extracts from older cynomolgus monkeys and in Lewy body pathology (LBP)-susceptible brain regions (striatum and hippocampus) forms higher amounts of phosphorylated and oligomeric α-syn than that in extracts from younger monkeys and LBP-insusceptible brain regions (cerebellum and occipital cortex). The increased α-syn phosphorylation and oligomerization in the brain extracts from older monkeys and in LBP-susceptible brain regions were associated with higher levels of polo-like kinase 2 (PLK2), an enzyme promoting α-syn phosphorylation, and lower activity of protein phosphatase 2A (PP2A), an enzyme inhibiting α-syn phosphorylation, in these brain extracts. Further, the extent of the age- and brain-dependent increase in α-syn phosphorylation and oligomerization was reduced by inhibition of PLK2 and activation of PP2A. Inversely, phosphorylated α-syn oligomers reduced the activity of PP2A and showed potent cytotoxicity. In addition, the activity of GCase and the levels of ceramide, a product of GCase shown to activate PP2A, were lower in brain extracts from older monkeys and in LBP-susceptible brain regions. Our results suggest a role for altered intrinsic metabolic enzymes in age- and brain region-dependent α-syn oligomerization in aging brains.

  10. Correlation between crystallization behaviour and interfacial interactions in plasticized PLA/POSS nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Kodal, Mehmet, E-mail: mehmet.kodal@kocaeli.edu.tr; Şirin, Hümeyra; Özkoç, Güralp, E-mail: guralp.ozkoc@kocaeli.edu.tr [Department of Chemical Engineering, Kocaeli University, 41380, Kocaeli Turkey (Turkey)

    2016-03-09

    In this study, the correlation between crystallization behavior and surface chemistry of polyhedral oligomeric silsesquioxanes (POSS) for plasticized poly(lactic acid) (PLA)/POSS nanocomposites was investigated. Four different kinds of POSS particles having different chemical structures were used. Poly(ethylene glycol) (PEG, 8000 g/mol) was utilized as the plasticiser. The nanocomposites were melt-compounded in an Xplore Instruments 15 cc twin screw microcompounder at 180°C barrel temperature and 100 rpm screw speed. Non-isothermal crystallization behaviour of PLA/PEG/POSS nanocomposites were evaluated from common kinetic models such as Avrami and Avrami-Ozawa and Kissinger by using the thermal data obtained from differantial scanning calorimetry (DSC). A polarized optical microscope (POM) equipped with a hot-stage was used to examine the morphology during the crystal growth. In order to investigate the interfacial interactions between POSS particles and plasticized PLA, thermodynamic work of adhesion approach was adopted using the experimentally determined surface energies. A strong correlation was obtained between interfacial chemistry and the nucleation rate in plasticized PLA/POSS nanocomposites. It was found that the polar interactions were the dominating factor which determines the nucleation activity of the POSS particles.

  11. Characteristic of Hybrid Cellulose-Amino Functionalized POSS-Silica Nanocomposite and Antimicrobial Activity

    Directory of Open Access Journals (Sweden)

    Sivalingam Ramesh

    2015-01-01

    Full Text Available Recently, cellulose has much attention as an emerging renewable nanomaterial which holds promising properties having unique piezoelectricity, insulating, and biodegradable nature for various applications. Also, the modified properties of cellulose by appropriate chemical modifications in various functional groups with outstanding properties or significantly improved physical, chemical, biological, and electronic properties will widen the way for it to be utilized in different usages. Therefore, in this paper, cellulose-functionalized polyhedral oligomeric silsesquioxanes (POSS based materials were considered an important class of high-performance hybrid nanocomposite materials. To functionalize the regenerated cellulose, amino functionalized POSS material was synthesized via sol-gel covalent crosslinking process in presence of amino coupling agent. In this reaction, tetraethoxsilane (TEOS and γ-aminopropyltriethoxy silane (γ-APTES as coupling agent for metal precursors were selected. The chemical structure of cellulose-amine functionalized bonding and covalent crosslinking hybrids was confirmed by FTIR and 1H NMR spectral analysis. From the TEM results, well-dispersed hybrid cellulose-functionalized POSS-silica composites are observed. The resulting cellulose-POSS-silica hybrid nanocomposites materials provided significantly improved the optical transparency, and thermal and morphological properties to compare the cellulose-silica hybrid materials. Further, antimicrobial test against pathogenic bacteria was carried out.

  12. Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies.

    Science.gov (United States)

    Wang, Lei; Zhang, Chongyin; Cong, Houluo; Li, Lei; Zheng, Sixun; Li, Xiuhong; Wang, Jie

    2013-07-11

    In this work, we investigated the effect of topological structures of block copolymers on the formation of the nanophase in epoxy thermosets containing amphiphilic block copolymers. Two block copolymers composed of poly(ε-caprolactone) (PCL) and poly(2,2,2-trifluoroethyl acrylate) (PTFEA) blocks were synthesized to possess linear and star-shaped topologies. The star-shaped block copolymer composed a polyhedral oligomeric silsesquioxane (POSS) core and eight poly(ε-caprolactone)-block-poly(2,2,2-trifluoroethyl acrylate) (PCL-b-PTFEA) diblock copolymer arms. Both block copolymers were synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process; they were controlled to have identical compositions of copolymerization and lengths of blocks. Upon incorporating both block copolymers into epoxy thermosets, the spherical PTFEA nanophases were formed in all the cases. However, the sizes of PTFEA nanophases from the star-like block copolymer were significantly lower than those from the linear diblock copolymer. The difference in the nanostructures gave rise to the different glass transition behavior of the nanostructured thermosets. The dependence of PTFEA nanophases on the topologies of block copolymers is interpreted in terms of the conformation of the miscible subchain (viz. PCL) at the surface of PTFEA microdomains and the restriction of POSS cages on the demixing of the thermoset-philic block (viz. PCL).

  13. Gypsum (CaSO4·2H2O) Scaling on Polybenzimidazole and Cellulose Acetate Hollow Fiber Membranes under Forward Osmosis

    Science.gov (United States)

    Chen, Si Cong; Su, Jincai; Fu, Feng-Jiang; Mi, Baoxia; Chung, Tai-Shung

    2013-01-01

    We have examined the gypsum (CaSO4·2H2O) scaling phenomena on membranes with different physicochemical properties in forward osmosis (FO) processes. Three hollow fiber membranes made of (1) cellulose acetate (CA), (2) polybenzimidazole (PBI)/polyethersulfone (PES) and (3) PBI-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) were studied. For the first time in FO processes, we have found that surface ionic interactions dominate gypsum scaling on the membrane surface. A 70% flux reduction was observed on negatively charged CA and PBI membrane surfaces, due to strong attractive forces. The PBI membrane surface also showed a slightly positive charge at a low pH value of 3 and exhibited a 30% flux reduction. The atomic force microscopy (AFM) force measurements confirmed a strong repulsive force between gypsum and PBI at a pH value of 3. The newly developed PBI-POSS/PAN membrane had ridge morphology and a contact angle of 51.42° ± 14.85° after the addition of hydrophilic POSS nanoparticles and 3 min thermal treatment at 95 °C. Minimal scaling and an only 1.3% flux reduction were observed at a pH value of 3. Such a ridge structure may reduce scaling by not providing a locally flat surface to the crystallite at a pH value of 3; thus, gypsum would be easily washed away from the surface. PMID:24957062

  14. PES/POSS Soluble Veils as Advanced Modifiers for Multifunctional Fiber Reinforced Composites

    Directory of Open Access Journals (Sweden)

    Gianluca Cicala

    2017-07-01

    Full Text Available Novel polyhedral oligomeric silsesquioxanes (POSS-filled thermoplastic electrospun veils were used to tailor the properties of the interlaminar region of epoxy-based composites. The veils were designed to be soluble upon curing in the epoxy matrix, so that POSS could be released within the interlaminar region. Three different POSS contents, varying from 1 to 10 wt %, were tested while the percentage of coPolyethersulphone (coPES dissolved in the epoxy resin was kept to a fixed value of 10 wt %. Good quality veils could be obtained at up to 10 wt % of POSS addition, with the nanofibers’ diameters varying from 861 nm for the coPES to 428 nm upon POSS addition. The feasibility of the soluble veils to disperse POSS in the interlaminar region was proved, and the effect of POSS on phase morphology and viscoelastic properties studied. POSS was demonstrated to significantly affect the morphology and viscoelastic properties of epoxy composites, especially for the percentages 1% and 5%, which enabled the composites to avoid POSS segregates occurring. A dynamic mechanical analysis showed a significant improvement to the storage modulus, and a shift of more than 30 °C due to the POSS cages hindering the motion of the molecular chains and network junctions.

  15. Giant surfactants of poly(ethylene oxide)- b-polystyrene-(molecular nanoparticle): nanoparticle-driven self-assembly with sub-10-nm nanostructures in thin films

    Science.gov (United States)

    Hsu, Chih-Hao; Lin, Zhiwei; Dong, Xue-Hui; Hsieh, I.-Fan; Cheng, Stephen Z. D.

    2014-03-01

    Giant surfactants are built upon precisely attaching shape- and volume-persistent molecular nanoparticles (MNP) to polymeric flexible tails. The unique class of self-assembling materials, giant surfactants, has been demonstrated to form self-assembled ordered nanostructures, and their self-assembly behaviors are remarkably sensitive to primary chemical structures. In this work, two sets of giant surfactants with functionalized MNP attached to diblock copolymer tails were studied in thin films. Carboxylic acid-functionalized [60]fullerene (AC60) tethered with PEO- b-PS (PEO-PS-AC60) represents an ABA' (hydrophilic-hydrophobic-hydrophilic) giant surfactant, and fluoro-functionalized polyhedral oligomeric silsesquioxane (FPOSS) tethered with PEO- b-PS (PEO-PS-FPOSS) represents an ABC (hydrophilic-hydrophobic-omniphobic) one. The dissimilar chemical natures of the MNPs result in different arrangement of MNPs in self-assembled structures, the dispersion of AC60 in PEO domain and the single domain of FPOSS. Moreover, the chemically bonded MNPs could induce the originally disordered small molecular PEO- b-PS to form ordered cylindrical and lamellar structure, as evidenced by TEM and GISAXS, leading to sub-10-nm nanostructures of copolymer in the thin film state.

  16. Organic-inorganic hybrid carbon dots for cell imaging

    Science.gov (United States)

    Liu, Huan; Zhang, Hongwen; Li, Jiayu; Tang, Yuying; Cao, Yu; Jiang, Yan

    2018-04-01

    In this paper, nitrogen-doped carbon dots (CDs) had been synthesized directly by one-step ultrasonic treatment under mild conditions. During the functionalization process, Octa-aminopropyl polyhedral oligomeric silsesquioxane hydrochloride salt (OA-POSS) was used as stabilizing and passivation agent, which lead to self-assembling of CDs in aqueous medium solution. OA-POSS was obtained via hydrolytic condensation of γ-aminopropyl triethoxy silane (APTES). The average size of CDs prepared was approximately 3.3 nm with distribution between 2.5 nm and 4.5 nm. The prepared organic-inorganic hybrid carbon dots have several characteristics such as photoluminescence emission wavelength, efficient cellular uptake, and good biocompatibility. The results indicate that OA-POSS can maintain the fluorescence properties of the carbon dots effectively, and reduced cytotoxicity provides the possibility for biomedical applications. More than 89% of the Hela cells were viable when incubated with 2 mg ml‑1 or lesser organic-inorganic hybrid carbon dots. Thus, it provides a potential for multicolor imaging with HeLa cells.

  17. Real-time two-dimensional imaging of potassium ion distribution using an ion semiconductor sensor with charged coupled device technology.

    Science.gov (United States)

    Hattori, Toshiaki; Masaki, Yoshitomo; Atsumi, Kazuya; Kato, Ryo; Sawada, Kazuaki

    2010-01-01

    Two-dimensional real-time observation of potassium ion distributions was achieved using an ion imaging device based on charge-coupled device (CCD) and metal-oxide semiconductor technologies, and an ion selective membrane. The CCD potassium ion image sensor was equipped with an array of 32 × 32 pixels (1024 pixels). It could record five frames per second with an area of 4.16 × 4.16 mm(2). Potassium ion images were produced instantly. The leaching of potassium ion from a 3.3 M KCl Ag/AgCl reference electrode was dynamically monitored in aqueous solution. The potassium ion selective membrane on the semiconductor consisted of plasticized poly(vinyl chloride) (PVC) with bis(benzo-15-crown-5). The addition of a polyhedral oligomeric silsesquioxane to the plasticized PVC membrane greatly improved adhesion of the membrane onto Si(3)N(4) of the semiconductor surface, and the potential response was stabilized. The potential response was linear from 10(-2) to 10(-5) M logarithmic concentration of potassium ion. The selectivity coefficients were K(K(+),Li(+))(pot) = 10(-2.85), K(K(+),Na(+))(pot) = 10(-2.30), K(K(+),Rb(+))(pot) =10(-1.16), and K(K(+),Cs(+))(pot) = 10(-2.05).

  18. Surface morphology and dewettability of self-organized thermosets involving epoxy and POSS-capped poly(ethylene oxide) telechelics

    International Nuclear Information System (INIS)

    Wang, Lei; Zheng, Sixun

    2012-01-01

    A heptaphenyl polyhedral oligomeric silsesquioxane-capped poly(ethylene oxide) (POSS-capped PEO) telechelics was synthesized via the Huisgen 1,3-dipolar cycloaddition between 3-azidopropylheptaphenyl POSS and α,ω-dialkynyl-terminated poly(ethylene oxide). The organic–inorganic amphiphile was incorporated into epoxy to obtain the organic–inorganic nanocomposites. The morphology of the nanocomposites was investigated by means of atomic force microscopy (AFM) and dynamic mechanical thermal analysis (DMTA). It was found that the epoxy thermosets containing POSS-capped PEO telechelics were microphase-separated. The formation of the nanophases in the thermosets followed a self-assembly mechanism. The static contact angle measurements show that the nanocomposites displayed a significant enhancement in surface hydrophobicity as well as reduction in surface free energy. The improvement in surface dewettability was ascribed to the enrichment of POSS cages at the surface of the nanocomposites and the formation of the specific surface morphology as evidenced by X-ray photoelectron spectroscopy (XPS) and surface atomic force microscopy (AFM). -- Highlights: ► POSS-capped PEO telechelics was synthesized via click chemistry approach. ► The organic–inorganic amphiphile can be self-assembled into the nanophases in epoxy. ► The hybrid nanocomposites were successfully prepared via a self-assembly approach. ► The nanocomposites displayed a significant enhancement in surface hydrophobicity.

  19. Determination of grafting conversion degree in PS/PS-graft-POSS/POSS hybrid nanocomposites obtained through reactive processing

    International Nuclear Information System (INIS)

    Bianchi, Otavio; Repenning, Gustavo B.; Mauler, Raquel S.; Oliveira, Ricardo V.B.; Canto, Leonardo B.

    2011-01-01

    Hybrid nanocomposites of polystyrene (PS) and polyhedral oligomeric silsesquioxanes (POSS) - PS/PS-graft-POSS/POSS - with different grafting degrees were prepared by reactive melt processing using dicumyl peroxide (DCP) as initiator in the presence or absence of styrene monomer as radical transfer agent. Gel permeation chromatography (GPC) using triple-detector and proton nuclear magnetic resonance (NMR 1 H) analyses were used together to determine the conversion degree of PS-graft-POSS as a function of the reactive processing conditions adopted. GPC was employed to evaluate the effects of grafting (PS-graft-POSS) and PS chains degradation (β scission) that occur simultaneously during processing on the variation of average molecular masses and distributions for each PS/POSS sample. PS/POSS systems processed with styrene showed higher weight average molecular weights (M w ) and lower polydispersity indexes (M w /M n ), as a result of higher grafting (PS-graft-POSS) conversion (28-40%) and lower PS chain degradation level, as compared to PS/POSS systems processed without styrene in which the degree of grafting conversion was around 25-28%. (author)

  20. On the decoupling of relaxation modes in a molecular liquid caused by isothermal introduction of 2 nm structural inhomogeneities.

    Science.gov (United States)

    Ueno, Kazuhide; Angell, C Austen

    2011-12-08

    To support a new interpretation of the origin of the dynamic heterogeneity observed pervasively in fragile liquids as they approach their glass transition temperatures T(g), we demonstrate that the introduction of ~2 nm structural inhomogeneities into a homogeneous glass former leads to a decoupling of diffusion from viscosity similar to that observed during the cooling of orthoterphenyl (OTP) below T(A,) where Arrhenius behavior is lost. Further, the decoupling effect grows stronger as temperature decreases (and viscosity increases). The liquid is cresol, and the ~2 nm inhomogeneities are cresol-soluble asymmetric derivatized tetrasiloxy-based (polyhedral oligomeric silsesquioxane (POSS)) molecules. The decoupling is the phenomenon predicted by Onsager in discussing the approach to a liquid-liquid phase separation with decreasing temperature. In the present case the observations support the notion of a polyamorphic transition in fragile liquids that is hidden below the glass transition. A similar decoupling can be expected as a globular protein is dissolved in dilute aqueous solutions or in protic ionic liquids. © 2011 American Chemical Society

  1. Periodic imidazolium-bridged hybrid monolith for high-efficiency capillary liquid chromatography with enhanced selectivity.

    Science.gov (United States)

    Qiao, Xiaoqiang; Zhang, Niu; Han, Manman; Li, Xueyun; Qin, Xinying; Shen, Shigang

    2017-03-01

    A novel periodic imidazolium-bridged hybrid monolithic column was developed. With diene imidazolium ionic liquid 1-allyl-3-vinylimidazolium bromide as both cross-linker and organic functionalized reagent, a new periodic imidazolium-bridged hybrid monolithic column was facilely prepared in capillary with homogeneously distributed cationic imidazolium by a one-step free-radical polymerization with polyhedral oligomeric silsesquioxane methacryl substituted. The successful preparation of the new column was verified by Fourier transform infrared spectroscopy, scanning electron microscopy, elemental analysis, and surface area analysis. Most interestingly, the bonded amount of 1-allyl-3-vinylimidazolium bromide of the new column is three times higher than that of the conventional imidazolium-embedded hybrid monolithic column and the specific surface area of the column reached 478 m 2 /g. The new column exhibited high stability, excellent separation efficiency, and enhanced separation selectivity. The column efficiency reached 151 000 plates/m for alkylbenzenes. Furthermore, the new column was successfully used for separation of highly polar nucleosides and nucleic acid bases with pure water as mobile phase and even bovine serum albumin tryptic digest. All these results demonstrate the periodic imidazolium-bridged hybrid monolithic column is a good separation media and can be used for chromatographic separation of small molecules and complex biological samples with high efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Preparation and evaluation of a novel hybrid monolithic column based on pentafluorobenzyl imidazolium bromide ionic liquid.

    Science.gov (United States)

    Shan, Yuanhong; Qiao, Lizhen; Shi, Xianzhe; Xu, Guowang

    2015-01-02

    To develop a novel hybrid monolithic column based on pentafluorobenzyl imidazolium bromide ionic liquid, a new ionic liquid monomer was synthesized from 1-vinylimidazole and pentafluorobenzyl bromide. By employing a facile one-step copolymerization of polyhedral-oligomeric-silsesquioxane-type (POSS) cross-linking agent and the home-made ionic liquid monomer, the hybrid monolithic columns were in situ fabricated in fused-silica capillary. The morphology of monolithic column was characterized by scanning electron microscope (SEM) and the chemical composition was confirmed by Fourier-transform infrared spectroscopy (FT-IR) and elemental analysis. Excellent mechanical stability and slight swelling propensity were exhibited which was ascribed to the rigid hybrid monolithic skeleton. Reproducibility results of run-to-run, column-to-column, batch-to-batch and day-to-day were investigated and the RSDs were less than 0.46%, 1.84%, 3.96% and 3.17%, respectively. The mixed-mode retention mechanism with hydrophobic interaction, π-π stacking, ion-exchange, electrostatic interaction and dipole-dipole interaction was explored systematically using analytes with different structure types. Satisfied separation capability and column efficiency were achieved for the analysis of small molecular compounds such as alkylbenzenes, polycyclic aromatic hydrocarbons, nucleosides and halogenated compounds. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. A Biodesigned Nanocomposite Biomaterial for Auricular Cartilage Reconstruction.

    Science.gov (United States)

    Nayyer, Leila; Jell, Gavin; Esmaeili, Ali; Birchall, Martin; Seifalian, Alexander M

    2016-05-01

    Current biomaterials for auricular replacement are associated with high rates of infection and extrusion. The development of new auricular biomaterials that mimic the mechanical properties of native tissue and promote desirable cellular interactions may prevent implant failure. A porous 3D nanocomposite scaffold (NS) based on POSS-PCU (polyhedral oligomeric silsesquioxane nanocage into polycarbonate based urea-urethane) is developed with an elastic modulus similar to native ear. In vitro biological interactions on this NS reveal greater protein adsorption, increased fibroblast adhesion, proliferation, and collagen production compared with Medpor (the current synthetic auricular implant). In vivo, the POSS-PCU with larger pores (NS2; 150-250 μm) have greater tissue ingrowth (≈5.8× and ≈1.4 × increase) than the POSS-PCU with smaller pores (NS1; 100-50 μm) and when compared to Medpor (>100 μm). The NS2 with the larger pores demonstrates a reduced fibrotic encapsulation compared with NS1 and Medpor (≈4.1× and ≈1.6×, respectively; P response for all materials may indicate that the elastic modulus and pore size of the implant scaffold could be important design considerations for influencing fibrotic responses to auricular and other soft tissue implants. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Nanopatterning via Self-Assembly of a Lamellar-Forming Polystyrene-block-Poly(dimethylsiloxane Diblock Copolymer on Topographical Substrates Fabricated by Nanoimprint Lithography

    Directory of Open Access Journals (Sweden)

    Dipu Borah

    2018-01-01

    Full Text Available The self-assembly of a lamellar-forming polystyrene-block-poly(dimethylsiloxane (PS-b-PDMS diblock copolymer (DBCP was studied herein for surface nanopatterning. The DBCP was synthesized by sequential living anionic polymerization of styrene and hexamethylcyclotrisiloxane (D3. The number average molecular weight (Mn, polydispersity index (Mw/Mn and PS volume fraction (φps of the DBCP were MnPS = 23.0 kg mol−1, MnPDMS = 15.0 kg mol−1, Mw/Mn = 1.06 and φps = 0.6. Thin films of the DBCP were cast and solvent annealed on topographically patterned polyhedral oligomeric silsesquioxane (POSS substrates. The lamellae repeat distance or pitch (λL and the width of the PDMS features (dL are ~35 nm and ~17 nm, respectively, as determined by SEM. The chemistry of the POSS substrates was tuned, and the effects on the self-assembly of the DBCP noted. The PDMS nanopatterns were used as etching mask in order to transfer the DBCP pattern to underlying silicon substrate by a complex plasma etch process yielding sub-15 nm silicon features.

  5. Design and Characterization of Liquidlike POSS-Based Hybrid Nanomaterials Synthesized via Ionic Bonding and Their Interactions with CO 2

    KAUST Repository

    Petit, Camille

    2013-10-01

    Liquidlike nanoparticle organic hybrid materials (NOHMs) were designed and synthesized by ionic grafting of polymer chains onto nanoscale silica units called polyhedral oligomeric silsesquioxane (POSS). The properties of these POSS-based NOHMs relevant to CO2 capture, in particular thermal stability, swelling, viscosity, as well as their interactions with CO 2, were investigated using thermogravimetric analyses, differential scanning calorimetry, and NMR and ATR FT-IR spectroscopies. The results indicate that POSS units significantly enhance the thermal stability of the hybrid materials, and their porous nature also contributes to the overall CO 2 capture capacity of NOHMs. The viscosity of the synthesized NOHMs was comparable to those reported for ionic liquids, and rapidly decreased as the temperature increased. The sorption of CO2 in POSS-based NOHMs also reduced their viscosities. The swelling behavior of POSS-based NOHMs was similar to that of previously studied nanoparticle-based NOHMs, and this generally resulted in less volume increase in NOHMs compared to their corresponding polymers for the same amount of CO2 loading. © 2013 American Chemical Society.

  6. A targeted nanoglobular contrast agent from host-guest self-assembly for MR cancer molecular imaging.

    Science.gov (United States)

    Zhou, Zhuxian; Han, Zhen; Lu, Zheng-Rong

    2016-04-01

    The clinical application of nanoparticular Gd(III) based contrast agents for tumor molecular MRI has been hindered by safety concerns associated with prolonged tissue retention, although they can produce strong tumor enhancement. In this study, a targeted well-defined cyclodextrin-based nanoglobular contrast agent was developed through self-assembly driven by host-guest interactions for safe and effective cancer molecular MRI. Multiple β-cyclodextrins attached POSS (polyhedral oligomeric silsesquioxane) nanoglobule was used as host molecule. Adamantane-modified macrocyclic Gd(III) contrast agent, cRGD (cyclic RGDfK peptide) targeting ligand and fluorescent probe was used as guest molecules. The targeted host-guest nanoglobular contrast agent cRGD-POSS-βCD-(DOTA-Gd) specifically bond to αvβ3 integrin in malignant 4T1 breast tumor and provided greater contrast enhancement than the corresponding non-targeted agent. The agent also provided significant fluorescence signal in tumor tissue. The histological analysis of the tumor tissue confirmed its specific and effective targeting to αvβ3 integrin. The targeted imaging agent has a potential for specific cancer molecular MR and fluorescent imaging. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Surface-initiated ring-opening metathesis polymerization (SI-ROMP) to attach a tethered organic corona onto CdSe/ZnS core/shell quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Vatansever, Fatma, E-mail: vatansever.fatma@mgh.harvard.edu; Hamblin, Michael R., E-mail: hamblin@helix.mgh.harvard.edu [Massachusetts General Hospital, Wellman Center for Photomedicine (United States)

    2016-10-15

    Core–shell CdSe/ZnS quantum dots (QDs) are useful as tunable photostable fluorophores for multiple applications in industry, biology, and medicine. However, to achieve the optimum optical properties, the surface of the QDs must be passivated to remove charged sites that might bind extraneous substances and allow aggregation. Here we describe a method of growing an organic polymer corona onto the QD surface using the bottom-up approach of surface-initiated ring-opening metathesis polymerization (SI-ROMP) with Grubbs catalyst. CdSe/ZnS QDs were first coated with mercaptopropionic acid by displacing the original tri-octylphosphine oxide layer, and then reacted with 7-octenyl dimethyl chlorosilane. The resulting octenyl double bonds allowed the attachment of ruthenium alkylidene groups as a catalyst. A subsequent metathesis reaction with strained bicyclic monomers (norbornene-dicarbonyl chloride (NDC), and a mixture of NDC and norbornenylethylisobutyl-polyhedral oligomeric silsesquioxane (norbornoPOSS)) allowed the construction of tethered organic homo-polymer or co-polymer layers onto the QD. Compounds were characterized by FT-IR, 1H-NMR, X-ray photoelectron spectroscopy, differential scanning calorimetry, and transmission electron microscopy. Atomic force microscopy showed that the coated QDs were separate and non-aggregated with a range of diameter of 48–53 nm.

  8. Thickness-Dependent Order-to-Order Transitions of Bolaform-like Giant Surfactant in Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, Chih-Hao; Yue, Kan; Wang, Jing; Dong, Xue-Hui; Xia, Yanfeng; Jiang, Zhang [X-ray; Thomas, Edwin L. [Department; Cheng, Stephen Z. D.

    2017-09-07

    Controlling self-assembled nanostructures in thin films allows the bottom-up fabrication of ordered nanoscale patterns. Here we report the unique thickness-dependent phase behavior in thin films of a bolaform-like giant surfactant, which consists of butyl- and hydroxyl-functionalized polyhedral oligomeric silsesquioxane (BPOSS and DPOSS) cages telechelically located at the chain ends of a polystyrene (PS) chain with 28 repeating monomers on average. In the bulk, BPOSS-PS28-DPOSS forms a double gyroid (DG) phase. Both grazing incidence small angle X-ray scattering and transmission electron microscopy techniques are combined to elucidate the thin film structures. Interestingly, films with thicknesses thinner than 200 nm exhibit an irreversible phase transition from hexagonal perforated layer (HPL) to compressed hexagonally packed cylinders (c-HEX) at 130 °C, while films with thickness larger than 200 nm show an irreversible transition from HPL to DG at 200 °C. The thickness-controlled transition pathway suggests possibilities to obtain diverse patterns via thin film self-assembly.

  9. Low Loss Nanostructured Polymers for Chip-scale Waveguide Amplifiers.

    Science.gov (United States)

    Chen, George F R; Zhao, Xinyu; Sun, Yang; He, Chaobin; Tan, Mei Chee; Tan, Dawn T H

    2017-06-13

    On-chip waveguide amplifiers offer higher gain in small device sizes and better integration with photonic devices than the commonly available fiber amplifiers. However, on-chip amplifiers have yet to make its way into the mainstream due to the limited availability of materials with ideal light guiding and amplification properties. A low-loss nanostructured on-chip channel polymeric waveguide amplifier was designed, characterized, fabricated and its gain experimentally measured at telecommunication wavelength. The active polymeric waveguide core comprises of NaYF 4 :Yb,Er,Ce core-shell nanocrystals dispersed within a SU8 polymer, where the nanoparticle interfacial characteristics were tailored using hydrolyzed polyhedral oligomeric silsesquioxane-graft-poly(methyl methacrylate) to improve particle dispersion. Both the enhanced IR emission intensity from our nanocrystals using a tri-dopant scheme and the reduced scattering losses from our excellent particle dispersion at a high solid loading of 6.0 vol% contributed to the outstanding optical performance of our polymeric waveguide. We achieved one of the highest reported gain of 6.6 dB/cm using a relatively low coupled pump power of 80 mW. These polymeric waveguide amplifiers offer greater promise for integrated optical circuits due to their processability and integration advantages which will play a key role in the emerging areas of flexible communication and optoelectronic devices.

  10. Hydrogen bonding strength of diblock copolymers affects the self-assembled structures with octa-functionalized phenol POSS nanoparticles.

    Science.gov (United States)

    Lu, Yi-Syuan; Yu, Chia-Yu; Lin, Yung-Chih; Kuo, Shiao-Wei

    2016-02-28

    In this study, the influence of the functional groups by the diblock copolymers of poly(styrene-b-4-vinylpyridine) (PS-b-P4VP), poly(styrene-b-2-vinylpyridine) (PS-b-P2VP), and poly(styrene-b-methyl methacrylate) (PS-b-PMMA) on their blends with octa-functionalized phenol polyhedral oligomeric silsesquioxane (OP-POSS) nanoparticles (NPs) was investigated. The relative hydrogen bonding strengths in these blends follow the order PS-b-P4VP/OP-POSS > PS-b-P2VP/OP-POSS > PS-b-PMMA/OP-POSS based on the Kwei equation from differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopic analyses. Small-angle X-ray scattering and transmission electron microscopic analyses show that the morphologies of the self-assembly structures are strongly dependent on the hydrogen bonding strength at relatively higher OP-POSS content. The PS-b-P4VP/OP-POSS hybrid complex system with the strongest hydrogen bonds shows the order-order transition from lamellae to cylinders and finally to body-centered cubic spheres upon increasing OP-POSS content. However, PS-b-P2VP/OP-POSS and PS-b-PMMA/OP-POSS hybrid complex systems, having relatively weaker hydrogen bonds, transformed from lamellae to cylinder structures at lower OP-POSS content (50 wt%).

  11. vQRS Based on Hybrids of CNT with PMMA-POSS and PS-POSS Copolymers to Reach the Sub-PPM Detection of Ammonia and Formaldehyde at Room Temperature Despite Moisture

    Directory of Open Access Journals (Sweden)

    Abhishek Sachan

    2017-07-01

    Full Text Available Nanocomposite-based quantum resistive vapour sensors (vQRS have been developed from the assembly of hybrid copolymers of polyhedral oligomeric silsesquioxane (POSS and poly(methyl methacrylate (PMMA or poly(styrene (PS with carbon nanotubes (CNT. The originality of the resulting conducting architecture is expected to be responsible for the ability of the transducer to detect sub-ppm concentrations of ammonia and formaldehyde at room temperature despite the presence of humidity. In particular, the boosting effect of POSS is evidenced in CNT-based nanocomposite vQRS. The additive fabrication by spraying layer-by-layer provides (sLbL is an effective method to control the reproducibility of the transducers’ chemo-resistive responses. In dry atmosphere, the two types of sensors showed a high sensitivity towards both hazardous gases, as they were able to detect 300 ppb of formaldehyde and 500 ppb of ammonia with a sufficiently good signal to noise ratio (SNR > 10. They also exhibited a quick response times less than 5 s for both vapours and, even in the presence of 100 ppm of water, they were able to detect small amounts of gases (1.5 ppm of NH3 and 9 ppm of CH2O. The results suggest promising applications of POSS-based vQRS for air quality or volatolome monitoring.

  12. Tangible nanocomposites with diverse properties for heart valve application

    International Nuclear Information System (INIS)

    Vellayappan, Muthu Vignesh; Balaji, Arunpandian; Subramanian, Aruna Priyadarshini; John, Agnes Aruna; Jaganathan, Saravana Kumar; Supriyanto, Eko; Yusof, Mustafa; Murugesan, Selvakumar; Mohandas, Hemanth

    2015-01-01

    Cardiovascular disease claims millions of lives every year throughout the world. Biomaterials are used widely for the treatment of this fatal disease. With the advent of nanotechnology, the use of nanocomposites has become almost inevitable in the field of biomaterials. The versatile properties of nanocomposites, such as improved durability and biocompatibility, make them an ideal choice for various biomedical applications. Among the various nanocomposites, polyhedral oligomeric silsesquioxane-poly(carbonate-urea)urethane, bacterial cellulose with polyvinyl alcohol, carbon nanotubes, graphene oxide and nano-hydroxyapatite nanocomposites have gained popularity as putative choices for biomaterials in cardiovascular applications owing to their superior properties. In this review, various studies performed utilizing these nanocomposites for improving the mechanical strength, anti-calcification potential and hemocompatibility of heart valves are reviewed and summarized. The primary motive of this work is to shed light on the emerging nanocomposites for heart valve applications. Furthermore, we aim to promote the prospects of these nanocomposites in the campaign against cardiovascular diseases. (review)

  13. Preparation of open tubular capillary columns by in situ ring-opening polymerization and their applications in cLC-MS/MS analysis of tryptic digest.

    Science.gov (United States)

    Wang, Hongwei; Yao, Yating; Li, Ya; Ma, Shujuan; Peng, Xiaojun; Ou, Junjie; Ye, Mingliang

    2017-08-01

    An open tubular (OT) column (25 μm i.d.) was prepared by in situ ring-opening polymerization of octaglycidyldimethylsilyl polyhedral oligomeric silsesquioxanes (POSS-epoxy) with 4-aminophenyl disulfide (APDS) in a binary porogenic system of ethanol/H 2 O. It was found that porogenic composition played an important role in the formation of OT stationary phases. The ratio of ethanol/H 2 O at 6/1 (v/v) would lead to the fabrication of hybrid monoliths, while the ratio of ethanol/H 2 O at 13/1 (v/v) would result in the synthesis of OT phases. In addition, the effects of precursor content and reaction duration on the thickness of OT stationary phases were investigated. Either lower precursor content or shorter reaction duration would produce thinner layer of OT column. The repeatability of OT columns was evaluated through relative standard deviation (RSD%) with benzene as the analyte. The run-to-run, column-to-column and batch-to-batch repeatabilities were 1.7%, 4.8% and 5.6%, respectively, exhibiting satisfactory repeatability of the OT column. Then tryptic digest of mouse liver proteins was used to evaluate the performance of the resulting OT columns (25 μm i.d. × 2.5 m in length) by cLC-MS/MS analysis, demonstrating their potential in proteome analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Chemical modification of hybrid nanostructures (POSS for application as lubricant

    Directory of Open Access Journals (Sweden)

    Caroline Luvison

    2014-08-01

    Full Text Available Polyhedral oligomeric silsesquioxanes (POSS are hybrid structures type RSiO15n, with n organic groups R. These molecules can be easily functionalized by simply changing the chemical constitution of the organic groups. In this work, chemical modification of POSS-NH2 was performed by amidation reaction with butyric acid at elevated temperature, 160°C. The formation of the amide group is evinced by the appearance of NH angular deformation band at 1540 cm-1 in the FTIR spectra. Approximately 40% of the amino groups reacted, according to titration results. The formation of the amide groups resulted in a shift of the glass transition temperature (Tg from -36.9°C to -25.6°C for the modified-POSS sample. Both POSS-NH2 and modified-POSS samples exhibited similar thermal degradation pattern. Analysis of the pairs distribution function (PDF has determined that the hybrid nanoparticles are separated by a periodic distance of approximately 1.32 nm. POSS-NH2 and modified-POSS exhibit newtonian behavior, which will range from 10-1 s-1 and 1000 s-1. The viscosity decreased with increasing temperature, a typical behavior of liquid lubricants.

  15. Correlation between crystallization behaviour and interfacial interactions in plasticized PLA/POSS nanocomposites

    International Nuclear Information System (INIS)

    Kodal, Mehmet; Şirin, Hümeyra; Özkoç, Güralp

    2016-01-01

    In this study, the correlation between crystallization behavior and surface chemistry of polyhedral oligomeric silsesquioxanes (POSS) for plasticized poly(lactic acid) (PLA)/POSS nanocomposites was investigated. Four different kinds of POSS particles having different chemical structures were used. Poly(ethylene glycol) (PEG, 8000 g/mol) was utilized as the plasticiser. The nanocomposites were melt-compounded in an Xplore Instruments 15 cc twin screw microcompounder at 180°C barrel temperature and 100 rpm screw speed. Non-isothermal crystallization behaviour of PLA/PEG/POSS nanocomposites were evaluated from common kinetic models such as Avrami and Avrami-Ozawa and Kissinger by using the thermal data obtained from differantial scanning calorimetry (DSC). A polarized optical microscope (POM) equipped with a hot-stage was used to examine the morphology during the crystal growth. In order to investigate the interfacial interactions between POSS particles and plasticized PLA, thermodynamic work of adhesion approach was adopted using the experimentally determined surface energies. A strong correlation was obtained between interfacial chemistry and the nucleation rate in plasticized PLA/POSS nanocomposites. It was found that the polar interactions were the dominating factor which determines the nucleation activity of the POSS particles.

  16. Gypsum (CaSO42H2O) scaling on polybenzimidazole and cellulose acetate hollow fiber membranes under forward osmosis

    KAUST Repository

    Chen, Si Cong

    2013-11-08

    We have examined the gypsum (CaSO42H2O) scaling phenomena on membranes with different physicochemical properties in forward osmosis (FO) processes. Three hollow fiber membranes made of (1) cellulose acetate (CA), (2) polybenzimidazole (PBI)/polyethersulfone (PES) and (3) PBI-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) were studied. For the first time in FO processes, we have found that surface ionic interactions dominate gypsum scaling on the membrane surface. A 70% flux reduction was observed on negatively charged CA and PBI membrane surfaces, due to strong attractive forces. The PBI membrane surface also showed a slightly positive charge at a low pH value of 3 and exhibited a 30% flux reduction. The atomic force microscopy (AFM) force measurements confirmed a strong repulsive force between gypsum and PBI at a pH value of 3. The newly developed PBI-POSS/PAN membrane had ridge morphology and a contact angle of 51.42 14.85 after the addition of hydrophilic POSS nanoparticles and 3 min thermal treatment at 95 C. Minimal scaling and an only 1.3% flux reduction were observed at a pH value of 3. Such a ridge structure may reduce scaling by not providing a locally flat surface to the crystallite at a pH value of 3; thus, gypsum would be easily washed away from the surface. 2013 by the authors; licensee MDPI, Basel, Switzerland.

  17. N-terminal aliphatic residues dictate the structure, stability, assembly, and small molecule binding of the coiled-coil region of cartilage oligomeric matrix protein.

    Science.gov (United States)

    Gunasekar, Susheel K; Asnani, Mukta; Limbad, Chandani; Haghpanah, Jennifer S; Hom, Wendy; Barra, Hanna; Nanda, Soumya; Lu, Min; Montclare, Jin Kim

    2009-09-15

    The coiled-coil domain of cartilage oligomeric matrix protein (COMPcc) assembles into a homopentamer that naturally recognizes the small molecule 1,25-dihydroxyvitamin D(3) (vit D). To identify the residues critical for the structure, stability, oligomerization, and binding to vit D as well as two other small molecules, all-trans-retinol (ATR) and curcumin (CCM), here we perform an alanine scanning mutagenesis study. Ten residues lining the hydrophobic pocket of COMPcc were mutated into alanine; of the mutated residues, the N-terminal aliphatic residues L37, L44, V47, and L51 are responsible for maintaining the structure and function. Furthermore, two polar residues, T40 and Q54, within the N-terminal region when converted into alanine improve the alpha-helical structure, stability, and self-assembly behavior. Helical stability, oligomerization, and binding appear to be linked in a manner in which mutations that abolish helical structure and assembly bind poorly to vit D, ATR, and CCM. These results provide not only insight into COMPcc and its functional role but also useful guidelines for the design of stable, pentameric coiled-coils capable of selectively storing and delivering various small molecules.

  18. Browse Title Index

    African Journals Online (AJOL)

    Items 201 - 250 of 990 ... I: Synthesis, characterization and thermal properties of a novel polyhedral cubic silsesquioxane, Abstract PDF. Enock O. Dare, Gabriel A. Olatunji, David S. .... Vol 25, No 2 (2011), Saturated properties prediction in critical region by a quartic equation of state, Abstract PDF. Yong Wang, Guo-bo Huang, ...

  19. Hierarchical Self-Organization of AB n Dendron-like Molecules into a Supramolecular Lattice Sequence

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Xueyan [Department; Zhang, Ruimeng [Department; Li, Yiwen [College; Hong, You-lee [RIKEN CLST-JEOL; JEOL RESONANCE; Guo, Dong [Department; Lang, Kening [Department; Wu, Kuan-Yi [Department; Huang, Mingjun [Department; Mao, Jialin [Department; Wesdemiotis, Chrys [Department; Nishiyama, Yusuke [RIKEN CLST-JEOL; JEOL RESONANCE; Zhang, Wei [Department; Zhang, Wei [South; Miyoshi, Toshikazu [Department; Li, Tao [X-ray; Cheng, Stephen Z. D. [Department

    2017-08-07

    To understand the hierarchical self-organization behaviors of soft materials as well as their dependence on molecular geometry, a series of ABn dendron-type giant molecules based on polyhedral oligomeric silsesquioxane (POSS) nanoparticles were designed and synthesized. The apex of these molecules is a hydrophilic POSS cage with fourteen hydroxyl groups (denoted DPOSS). At its periphery, there are different numbers (n = 1–8) of hydrophobic POSS cages with seven isobutyl groups (denoted BPOSS), connected to the apical DPOSS via flexible dendron type linker(s). With varying the BPOSS number from one to seven, a supramolecular lattice formation sequence ranging from lamella (DPOSS-BPOSS), double gyroid (space group of Ia3d, DPOSS-BPOSS2), hexagonal cylinder (space group of P6mm, DPOSS-BPOSS3), Frank-Kasper A15 (space group of Pm3n, DPOSS-BPOSS4, DPOSS-BPOSS5, and DPOSS-BPOSS6), to Frank-Kasper sigma (space group of P42/mnm, DPOSS-BPOSS7) phases can be observed. The nanostructure formations in this series of ABn dendron-type giant molecules are mainly directed by the macromolecular geometric shapes. Furthermore, within each spherical motif, the soft spherical core is consisted of hydrophilic DPOSS cages with flexible linkages, while the hydrophobic BPOSS cages form the relative rigid shell and contact with neighbors to provide decreased interfaces among the spherical motifs for constructing final polyhedral motifs in these Frank-Kasper lattices. This study provides the design principle of macromolecules with specific geometric shapes and functional groups to achieve anticipated structures and macroscopic properties.

  20. Increased serum cartilage oligomeric matrix protein levels and decreased patellar bone mineral density in patients with chondromalacia patellae.

    Science.gov (United States)

    Murphy, E; FitzGerald, O; Saxne, T; Bresnihan, B

    2002-11-01

    Chondromalacia patellae is a potentially disabling disorder characterised by features of patellar cartilage degradation. To evaluate markers of cartilage and bone turnover in patients with chondromalacia patellae. 18 patients with chondromalacia patellae were studied. Serum cartilage oligomeric matrix protein (s-COMP) and bone sialoprotein (s-BSP) levels were measured by enzyme linked immunosorbent assay (ELISA) and compared with those of age and sex matched healthy control subjects. Periarticular bone mineral density (BMD) of both knee joints was assessed by dual energy x ray absorptiometry (DXA). s-COMP levels were significantly raised in all patients with chondromalacia patellae compared with healthy control subjects (p=0.0001). s-BSP levels did not differ significantly between the groups (p=0.41). BMD of the patella was significantly reduced in patients with chondromalacia patellae compared with the control subjects (p=0.016). In patients with bilateral chondromalacia patellae, BMD of the patella was lower in the more symptomatic knee joint (p=0.005). Changes in periarticular BMD were localised to the patella and were not present in femoral regions. Neither s-COMP (p=0.18) nor s-BSP (p=0.40) levels correlated with patellar BMD. Increased s-COMP levels, reflecting cartilage degradation, and reduced BMD localised to the patella may represent clinically useful markers in the diagnosis and monitoring of patients with chondromalacia patellae. Measures of cartilage degradation did not correlate with loss of patellar bone density, suggesting dissociated pathophysiological mechanisms.

  1. Pleiotropic benefit of monomeric and oligomeric flavanols on vascular health--a randomized controlled clinical pilot study.

    Science.gov (United States)

    Weseler, Antje R; Ruijters, Erik J B; Drittij-Reijnders, Marie-José; Reesink, Koen D; Haenen, Guido R M M; Bast, Aalt

    2011-01-01

    Cardiovascular diseases are expanding to a major social-economic burden in the Western World and undermine man's deep desire for healthy ageing. Epidemiological studies suggest that flavanol-rich foods (e.g. grapes, wine, chocolate) sustain cardiovascular health. For an evidenced-based application, however, sound clinical data on their efficacy are strongly demanded. In a double-blind, randomized, placebo-controlled intervention study we supplemented 28 male smokers with 200 mg per day of monomeric and oligomeric flavanols (MOF) from grape seeds. At baseline, after 4 and 8 weeks we measured macro- and microvascular function and a cluster of systemic biomarkers for major pathological processes occurring in the vasculature: disturbances in lipid metabolism and cellular redox balance, and activation of inflammatory cells and platelets. In the MOF group serum total cholesterol and LDL decreased significantly (P ≤ 0.05) by 5% (n = 11) and 7% (n = 9), respectively in volunteers with elevated baseline levels. Additionally, after 8 weeks the ratio of glutathione to glutathione disulphide in erythrocytes rose from baseline by 22% (n = 15, Pbenefit of an 8 weeks supplementation with 200 mg/d MOF in humans. ClinicalTrials.gov NCT00742287.

  2. Nucleotide-Binding Oligomerization Domain-1 and -2 Play No Role in Controlling Brucella abortus Infection in Mice

    Directory of Open Access Journals (Sweden)

    Fernanda S. Oliveira

    2012-01-01

    Full Text Available Nucleotide-binding oligomerization domain proteins (NODs are modular cytoplasmic proteins implicated in the recognition of peptidoglycan-derived molecules. Further, several in vivo studies have demonstrated a role for Nod1 and Nod2 in host defense against bacterial pathogens. Here, we demonstrated that macrophages from NOD1-, NOD2-, and Rip2-deficient mice produced lower levels of TNF-α following infection with live Brucella abortus compared to wild-type mice. Similar reduction on cytokine synthesis was not observed for IL-12 and IL-6. However, NOD1, NOD2, and Rip2 knockout mice were no more susceptible to infection with virulent B. abortus than wild-type mice. Additionally, spleen cells from NOD1-, NOD2-, and Rip2-deficient mice showed unaltered production of IFN-γ compared to C57BL/6 mice. Taken together, this study demonstrates that NOD1, NOD2 and Rip2 are dispensable for the control of B. abortus during in vivo infection.

  3. Glycerol-Induced Aggregation of the Oligomeric L-Asparaginase II from E. coli Monitored with ATR-FTIR

    Directory of Open Access Journals (Sweden)

    Koba Adeishvili

    2001-06-01

    Full Text Available Abstract: In this paper attenuated total reflectance Fourier transform infrared spectroscopy has been employed for the study of the structural composition of aggregates of the oligomeric L-asparaginase II from E.coli formed in the presence of glycerol after the induction of refolding of the protein. Apart from the perfect coincidence of the secondary structure composition of EcA2 as determined by FTIR and crystallography [1], it has also been shown that secondary structure of protein in asparaginase deposits is similar to that of the native conformation: 20.7% extended, 22.3% disordered, 31.4% helix and 25.6% turn/bend/β sheet. Certain structural similarities in the range of experimental error was observed for all three protein deposits presented in this paper, indicating a common structural basis for the composition of this types of aggregates. It is concluded that in the constitution of such precipitates, a partially folded (molten globule like state(s is involved, and its stabilisation is a key factor leading to the aggregation. The results presented in this paper might serve to be a good explanation and an excellent basis for the fundamental theory of protein (oligomers precipitation by osmotic substances.

  4. Functional significance of the oligomeric structure of the Na,K-pump from radiation inactivation and ligand binding

    International Nuclear Information System (INIS)

    Norby, J.G.; Jensen, J.

    1991-01-01

    The present article is concerned with the oligomeric structure and function of the Na,K-pump (Na,K-ATPase). The questions we have addressed, using radiation inactivation and target size analysis as well as ligand binding, are whether the minimal structural unit and the functional unit have more than one molecule of the catalytic subunit, alpha. The authors first discuss the fundamentals of the radiation inactivation method and emphasize the necessity for rigorous internal standardization with enzymes of known molecular mass. They then demonstrate that the radiation inactivation of Na,K-ATPase is a stepwise process which leads to intermediary fragments of the alpha-subunit with partial catalytic activity. From the target size analysis it is most likely that the membrane-bound Na,K-ATPase is structurally organized as a diprotomer containing two alpha-subunits. Determination of ADP- and ouabain-binding site stoichiometry favors a theory with one substrate site per (alpha beta) 2. 47 references

  5. Continued biological investigations of boron-rich oligomeric phosphate diesters (OPDs). Tumor-selective boron agents for BNCT

    International Nuclear Information System (INIS)

    Lee, Mark W.; Shelly, Kenneth; Kane, Robert R.; Hawthorne, M. Frederick

    2006-01-01

    Clinical success of Boron Neutron Capture Therapy will rely on the selective intracellular delivery of high concentrations of boron-10 to tumor tissue. In order for a boron agent to facilitate clinical success, the simultaneous needs of obtaining a high tumor dose, high tumor selectivity, and low systemic toxicity must be realized. Boron-rich oligomeric phosphate diesters (OPDs) are a class of highly water-soluble compounds containing up to 40% boron by weight. Previous work in our groups demonstrated that once placed in the cytoplasm of tumor cells, OPDs quickly accumulate within the cell nucleus. The objective of the current study was to determine the biodistribution of seven different free OPDs in BALB/c mice bearing EMT6 tumors. Fructose solutions containing between 1.4 and 6.4 micrograms of boron per gram of tissue were interveinously injected in mice seven to ten days after tumor implantation. At intervals during the study, animals were euthanized and samples of tumor, blood, liver, kidney, brain and skin were collected and analyzed for boron content using ICP-AES. Tumor boron concentrations of between 5 and 29 ppm were achieved and maintained over the 72-hour time course of each experiment. Several OPDs demonstrated high tumor selectivity with one oligomer exhibiting a tumor to blood ratio of 35:1. The apparent toxicity of each oligomer was assessed through animal behavior during the experiment and necropsy of each animal upon sacrifice. (author)

  6. Interplay of histidine residues of the Alzheimer’s disease Aβ peptide governs its Zn-induced oligomerization

    Science.gov (United States)

    Istrate, Andrey N.; Kozin, Sergey A.; Zhokhov, Sergey S.; Mantsyzov, Alexey B.; Kechko, Olga I.; Pastore, Annalisa; Makarov, Alexander A.; Polshakov, Vladimir I.

    2016-02-01

    Conformational changes of Aβ peptide result in its transformation from native monomeric state to the toxic soluble dimers, oligomers and insoluble aggregates that are hallmarks of Alzheimer’s disease (AD). Interactions of zinc ions with Aβ are mediated by the N-terminal Aβ1-16 domain and appear to play a key role in AD progression. There is a range of results indicating that these interactions trigger the Aβ plaque formation. We have determined structure and functional characteristics of the metal binding domains derived from several Aβ variants and found that their zinc-induced oligomerization is governed by conformational changes in the minimal zinc binding site 6HDSGYEVHH14. The residue H6 and segment 11EVHH14, which are part of this site are crucial for formation of the two zinc-mediated interaction interfaces in Aβ. These structural determinants can be considered as promising targets for rational design of the AD-modifying drugs aimed at blocking pathological Aβ aggregation.

  7. Structure of the large terminase from a hyperthermophilic virus reveals a unique mechanism for oligomerization and ATP hydrolysis.

    Science.gov (United States)

    Xu, Rui-Gang; Jenkins, Huw T; Antson, Alfred A; Greive, Sandra J

    2017-12-15

    The crystal structure of the large terminase from the Geobacillus stearothermophilus bacteriophage D6E shows a unique relative orientation of the N-terminal adenosine triphosphatase (ATPase) and C-terminal nuclease domains. This monomeric 'initiation' state with the two domains 'locked' together is stabilized via a conserved C-terminal arm, which may interact with the portal protein during motor assembly, as predicted for several bacteriophages. Further work supports the formation of an active oligomeric state: (i) AUC data demonstrate the presence of oligomers; (ii) mutational analysis reveals a trans-arginine finger, R158, indispensable for ATP hydrolysis; (iii) the location of this arginine is conserved with the HerA/FtsK ATPase superfamily; (iv) a molecular docking model of the pentamer is compatible with the location of the identified arginine finger. However, this pentameric model is structurally incompatible with the monomeric 'initiation' state and is supported by the observed increase in kcat of ATP hydrolysis, from 7.8 ± 0.1 min-1 to 457.7 ± 9.2 min-1 upon removal of the C-terminal nuclease domain. Taken together, these structural, biophysical and biochemical data suggest a model where transition from the 'initiation' state into a catalytically competent pentameric state, is accompanied by substantial domain rearrangements, triggered by the removal of the C-terminal arm from the ATPase active site. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

  8. Collagen XII and XIV, New Partners of Cartilage Oligomeric Matrix Protein in the Skin Extracellular Matrix Suprastructure*

    Science.gov (United States)

    Agarwal, Pallavi; Zwolanek, Daniela; Keene, Douglas R.; Schulz, Jan-Niklas; Blumbach, Katrin; Heinegård, Dick; Zaucke, Frank; Paulsson, Mats; Krieg, Thomas; Koch, Manuel; Eckes, Beate

    2012-01-01

    The tensile and scaffolding properties of skin rely on the complex extracellular matrix (ECM) that surrounds cells, vasculature, nerves, and adnexus structures and supports the epidermis. In the skin, collagen I fibrils are the major structural component of the dermal ECM, decorated by proteoglycans and by fibril-associated collagens with interrupted triple helices such as collagens XII and XIV. Here we show that the cartilage oligomeric matrix protein (COMP), an abundant component of cartilage ECM, is expressed in healthy human skin. COMP expression is detected in the dermal compartment of skin and in cultured fibroblasts, whereas epidermis and HaCaT cells are negative. In addition to binding collagen I, COMP binds to collagens XII and XIV via their C-terminal collagenous domains. All three proteins codistribute in a characteristic narrow zone in the superficial papillary dermis of healthy human skin. Ultrastructural analysis by immunogold labeling confirmed colocalization and further revealed the presence of COMP along with collagens XII and XIV in anchoring plaques. On the basis of these observations, we postulate that COMP functions as an adapter protein in human skin, similar to its function in cartilage ECM, by organizing collagen I fibrils into a suprastructure, mainly in the vicinity of anchoring plaques that stabilize the cohesion between the upper dermis and the basement membrane zone. PMID:22573329

  9. Collagen XII and XIV, new partners of cartilage oligomeric matrix protein in the skin extracellular matrix suprastructure.

    Science.gov (United States)

    Agarwal, Pallavi; Zwolanek, Daniela; Keene, Douglas R; Schulz, Jan-Niklas; Blumbach, Katrin; Heinegård, Dick; Zaucke, Frank; Paulsson, Mats; Krieg, Thomas; Koch, Manuel; Eckes, Beate

    2012-06-29

    The tensile and scaffolding properties of skin rely on the complex extracellular matrix (ECM) that surrounds cells, vasculature, nerves, and adnexus structures and supports the epidermis. In the skin, collagen I fibrils are the major structural component of the dermal ECM, decorated by proteoglycans and by fibril-associated collagens with interrupted triple helices such as collagens XII and XIV. Here we show that the cartilage oligomeric matrix protein (COMP), an abundant component of cartilage ECM, is expressed in healthy human skin. COMP expression is detected in the dermal compartment of skin and in cultured fibroblasts, whereas epidermis and HaCaT cells are negative. In addition to binding collagen I, COMP binds to collagens XII and XIV via their C-terminal collagenous domains. All three proteins codistribute in a characteristic narrow zone in the superficial papillary dermis of healthy human skin. Ultrastructural analysis by immunogold labeling confirmed colocalization and further revealed the presence of COMP along with collagens XII and XIV in anchoring plaques. On the basis of these observations, we postulate that COMP functions as an adapter protein in human skin, similar to its function in cartilage ECM, by organizing collagen I fibrils into a suprastructure, mainly in the vicinity of anchoring plaques that stabilize the cohesion between the upper dermis and the basement membrane zone.

  10. Supplementary Material for: A new mode of SAM domain mediated oligomerization observed in the CASKIN2 neuronal scaffolding protein

    KAUST Repository

    Smirnova, Ekaterina; Kwan, Jamie; Siu, Ryan; Gao, Xin; Zoidl, Georg; Demeler, Borries; Saridakis, Vivian; Donaldson, Logan

    2016-01-01

    Abstract Background CASKIN2 is a homolog of CASKIN1, a scaffolding protein that participates in a signaling network with CASK (calcium/calmodulin-dependent serine kinase). Despite a high level of homology between CASKIN2 and CASKIN1, CASKIN2 cannot bind CASK due to the absence of a CASK Interaction Domain and consequently, may have evolved undiscovered structural and functional distinctions. Results We demonstrate that the crystal structure of the Sterile Alpha Motif (SAM) domain tandem (SAM1-SAM2) oligomer from CASKIN2 is different than CASKIN1, with the minimal repeating unit being a dimer, rather than a monomer. Analytical ultracentrifugation sedimentation velocity methods revealed differences in monomer/dimer equilibria across a range of concentrations and ionic strengths for the wild type CASKIN2 SAM tandem and a structure-directed double mutant that could not oligomerize. Further distinguishing CASKIN2 from CASKIN1, EGFP-tagged SAM tandem proteins expressed in Neuro2a cells produced punctae that were distinct both in shape and size. Conclusions This study illustrates a new way in which neuronal SAM domains can assemble into large macromolecular assemblies that might concentrate and amplify synaptic responses.

  11. Nucleotide-binding oligomerization domain 2 (NOD2) activation induces apoptosis of human oral squamous cell carcinoma cells.

    Science.gov (United States)

    Yoon, Hyo-Eun; Ahn, Mee-Young; Kwon, Seong-Min; Kim, Dong-Jae; Lee, Jun; Yoon, Jung-Hoon

    2016-04-01

    Microbial Pattern-recognition receptors (PRRs), such as nucleotide-binding oligomerization domains (NODs), are essential for mammalian innate immune response. This study was designed to determine the effect of NOD1 and NOD2 agonist on innate immune responses and antitumor activity in oral squamous cell carcinoma (OSCC) cells. NODs expression was examined by RT-PCR, and IL-8 production by NODs agonist was examined by ELISA. Western blot analysis was performed to determine the MAPK activation in response to their agonist. Cell proliferation was determined by MTT assay. Flow cytometry and Western blot analysis were performed to determine the MDP-induced cell death. The levels of NODs were apparently expressed in OSCC cells. NODs agonist, Tri-DAP and MDP, led to the production of IL-8 and MAPK activation. NOD2 agonist, MDP, inhibited the proliferation of YD-10B cells in a dose-dependent manner. Also, the ratio of Annexin V-positive cells and cleaved PARP was increased by MDP treatment in YD-10B cells, suggesting that MDP-induced cell death in YD-10B cells may be owing to apoptosis. Our results indicate that NODs are functionally expressed in OSCC cells and can trigger innate immune responses. In addition, NOD2 agonist inhibited cell proliferation and induced apoptosis. These findings provide the potential value of MDP as novel candidates for antitumor agents of OSCC. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  12. Role of Nucleotide-Binding Oligomerization Domain-Containing (NOD 2 in Host Defense during Pneumococcal Pneumonia.

    Directory of Open Access Journals (Sweden)

    Tijmen J Hommes

    Full Text Available Streptococcus (S. pneumoniae is the most common causative pathogen in community-acquired pneumonia. Nucleotide-binding oligomerization domain-containing (NOD 2 is a pattern recognition receptor located in the cytosol of myeloid cells that is able to detect peptidoglycan fragments of S. pneumoniae. We here aimed to investigate the role of NOD2 in the host response during pneumococcal pneumonia. Phagocytosis of S. pneumoniae was studied in NOD2 deficient (Nod2-/- and wild-type (Wt alveolar macrophages and neutrophils in vitro. In subsequent in vivo experiments Nod2-/- and Wt mice were inoculated with serotype 2 S. pneumoniae (D39, an isogenic capsule locus deletion mutant (D39Δcps or serotype 3 S. pneumoniae (6303 via the airways, and bacterial growth and dissemination and the lung inflammatory response were evaluated. Nod2-/- alveolar macrophages and blood neutrophils displayed a reduced capacity to internalize pneumococci in vitro. During pneumonia caused by S. pneumoniae D39 Nod2-/- mice were indistinguishable from Wt mice with regard to bacterial loads in lungs and distant organs, lung pathology and neutrophil recruitment. While Nod2-/- and Wt mice also had similar bacterial loads after infection with the more virulent S. pneumoniae 6303 strain, Nod2-/- mice displayed a reduced bacterial clearance of the normally avirulent unencapsulated D39Δcps strain. These results suggest that NOD2 does not contribute to host defense during pneumococcal pneumonia and that the pneumococcal capsule impairs recognition of S. pneumoniae by NOD2.

  13. Non-transferrin-bound iron (NTBI uptake by T lymphocytes: evidence for the selective acquisition of oligomeric ferric citrate species.

    Directory of Open Access Journals (Sweden)

    Joao Arezes

    Full Text Available Iron is an essential nutrient in several biological processes such as oxygen transport, DNA replication and erythropoiesis. Plasma iron normally circulates bound to transferrin. In iron overload disorders, however, iron concentrations exceed transferrin binding capacity and iron appears complexed with low molecular weight molecules, known as non-transferrin-bound iron (NTBI. NTBI is responsible for the toxicity associated with iron-overload pathologies but the mechanisms leading to NTBI uptake are not fully understood. Here we show for the first time that T lymphocytes are able to take up and accumulate NTBI in a manner that resembles that of hepatocytes. Moreover, we show that both hepatocytes and T lymphocytes take up the oligomeric Fe3Cit3 preferentially to other iron-citrate species, suggesting the existence of a selective NTBI carrier. These results provide a tool for the identification of the still elusive ferric-citrate cellular carrier and may also open a new pathway towards the design of more efficient iron chelators for the treatment of iron overload disorders.

  14. Oligomerization of optineurin and its oxidative stress- or E50K mutation-driven covalent cross-linking: possible relationship with glaucoma pathology.

    Directory of Open Access Journals (Sweden)

    Jie Gao

    Full Text Available The optineurin gene, OPTN, is one of the causative genes of primary open-angle glaucoma. Although oligomerization of optineurin in cultured cells was previously observed by gel filtration analysis and blue native gel electrophoresis (BNE, little is known about the characteristics of optineurin oligomers. Here, we aimed to analyze the oligomeric state of optineurin and factors affecting oligomerization, such as environmental stimuli or mutations in OPTN. Using BNE or immunoprecipitation followed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE, we demonstrated that both endogenous and transfected optineurin exist as oligomers, rather than monomers, in NIH3T3 cells. We also applied an in situ proximity ligation assay to visualize the self-interaction of optineurin in fixed HeLaS3 cells and found that the optineurin oligomers were localized diffusely in the cytoplasm. Optineurin oligomers were usually detected as a single band of a size equal to that of the optineurin monomer upon SDS-PAGE, while an additional protein band of a larger size was observed when cells were treated with H2O2. We showed that larger protein complex is optineurin oligomers by immunoprecipitation and termed it covalent optineurin oligomers. In cells expressing OPTN bearing the most common glaucoma-associated mutation, E50K, covalent oligomers were formed even without H2O2 stimulation. Antioxidants inhibited the formation of E50K-induced covalent oligomers to various degrees. A series of truncated constructs of OPTN was used to reveal that covalent oligomers may be optineurin trimers and that the ubiquitin-binding domain is essential for formation of these trimers. Our results indicated that optineurin trimers may be the basic unit of these oligomers. The oligomeric state can be affected by many factors that induce covalent bonds, such as H2O2 or E50K, as demonstrated here; this provides novel insights into the pathogenicity of E50K. Furthermore

  15. Novel oligomeric proanthocyanidin derivatives interact with membrane androgen sites and induce regression of hormone-independent prostate cancer.

    Science.gov (United States)

    Kampa, Marilena; Theodoropoulou, Katerina; Mavromati, Fani; Pelekanou, Vassiliki; Notas, George; Lagoudaki, Eleni D; Nifli, Artemissia-Phoebe; Morel-Salmi, Cécile; Stathopoulos, Efstathios N; Vercauteren, Joseph; Castanas, Elias

    2011-04-01

    Prostate cancer is the most common malignancy among men in Western societies, and current therapeutic approaches are evolving to manage growth, recurrence, and mortality neoplasia. Membrane androgen receptors (mARs) have been characterized in human prostate cancer, being preferentially expressed in tumor rather than benign gland areas. Furthermore, mAR agonists (protein-conjugated testosterone) decrease in vitro prostate cancer cell growth and induce apoptosis, whereas in vivo they regress growth of tumor xenografts alone or in combination with taxane drugs. In this respect, targeting mARs might be a novel therapeutic approach in prostate cancer. In our search for new small-molecule ligands of mAR, we report that flavanol dimers B1-B4 (oligomeric procyanidins) decrease in vitro growth of the androgen-sensitive (LnCaP) and androgen-resistant (DU145) human prostate cancer cell lines in the following order: B3 = B4 > B2 ≫ B1 (LnCaP) and B2 ≫ B3 = B4 ≫ B1 (DU145). Some of these analogs were previously shown to trigger signaling cascades similar to testosterone-bovine serum albumin (BSA) conjugate. Galloylation does not confer an additional advantage; however, oleylation increases the dimers' antiproliferative potency by a factor of 100. In addition, we report that B2, oleylated or not, displaces testosterone from mARs with an IC(50) value at the nanomolar range and induces DU145 tumor xenograft regression by 50% (testosterone-BSA 40%). In this respect, oleylated B2 is a potent small-molecule agonist of mAR and could be a novel therapeutic agent for advanced prostate cancer, especially when taking into account the absence of androgenic actions and (liver) toxicity.

  16. Cartilage oligomeric matrix protein (COMP) in rheumatoid arthritis and its correlation with sonographic knee cartilage thickness and disease activity.

    Science.gov (United States)

    Sakthiswary, Rajalingham; Rajalingam, Shamala; Hussein, Heselynn; Sridharan, Radhika; Asrul, Abdul Wahab

    2017-12-01

    The aim of the study is to investigate the correlation of serum cartilage oligomeric matrix protein (COMP) levels with articular cartilage damage based on sonographic knee cartilage thickness (KCT) and disease activity in rheumatoid arthritis (RA). A total of 61 RA patients and 27 healthy controls were recruited in this study. Serum samples were obtained from all subjects to determine the serum COMP levels. All subjects had bilateral ultrasound scan of their knees. The KCT was based on the mean of measurements at three sites: the medial condyle, lateral condyle and intercondylar notch. Besides, the RA patients were assessed for their disease activity based on 28-joint-based Disease Activity Score (DAS 28). Serum COMP concentrations were significantly elevated in the RA patients compared to the controls (p = 0.001). The serum COMP levels had an inverse relationship with bilateral KCT in RA subjects and the healthy controls. COMP correlated significantly with disease activity based on DAS 28 (r = 0.299, p = 0.010), disease duration (r = 0.439, p = correlation between serum COMP and DAS 28 scores was comparable to the traditional markers of inflammation: erythrocyte sedimentation rate (ESR) (r = 0.372, p = 0.003) and C-reactive protein (CRP) (r = 0.305, p = 0.017). The serum COMP is a promising biomarker in RA which reflects disease activity and damage to the articular cartilage.

  17. Multicore Magnetic Nanoparticles Coated with Oligomeric Micelles: Characterization and Potential for the Extraction of Contaminants over a Wide Polarity Range.

    Science.gov (United States)

    Naous, Mohamed; García-Gómez, Diego; López-Jiménez, Francisco José; Bouanani, Farida; Lunar, María Loreto; Rubio, Soledad

    2017-01-17

    Oligomeric micelles from sodium undecylenate (oSUD) were chemisorbed to magnetic iron oxide nanoparticles (MNPs) through a single-step synthetic route involving the simultaneous nanoparticle formation and functionalization in an aqueous medium. The resulting spherical nanoparticles (MNPs-oSUD) consisted of a concatenation of iron oxide cores, with an average size of 7.7 nm, bound by oSUD micelles (particle average diameter of ca. 200 nm). Micellar coverage was ∼50% of the MNP-oSUD (by weight) and offered multiple retention mechanisms (e.g., dispersion, hydrogen bonding, polar, and ionic) for solute solubilization while keeping it intact during analyte elution. The high density of micelles and variety of interactions provided by this sorbent rendered it highly efficient for the extraction of aromatic amines in a wide polarity range (log K ow values from -0.80 to 4.05) from textiles, urine, and wastewater. Extraction took 5 min, no cleanup or evaporation of the extracts was needed and the method, based on LC-MS/MS quantitation, proved matrix-independent. Recoveries for 17 aromatic amines in samples were in the range of 93%-123% while those with negative log K ow values were in the range of 69%-87%. Detection limits for aromatic amines in textiles (0.007-2 mg kg -1 ) were well below the limits legislated by the European Union (EU) (30 mg kg -1 ) and those in urine and wastewater (0.004-1.5 μg L -1 ) were at the level usually found in real-world applications. All the analyzed samples were positive in aromatic amines. The easy synthesis and excellent extraction properties of MNPs-oSUD anticipate their high potential not only for multiresidue analysis but also in other fields such as water remediation.

  18. Pleiotropic benefit of monomeric and oligomeric flavanols on vascular health--a randomized controlled clinical pilot study.

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    Antje R Weseler

    Full Text Available BACKGROUND: Cardiovascular diseases are expanding to a major social-economic burden in the Western World and undermine man's deep desire for healthy ageing. Epidemiological studies suggest that flavanol-rich foods (e.g. grapes, wine, chocolate sustain cardiovascular health. For an evidenced-based application, however, sound clinical data on their efficacy are strongly demanded. METHODS: In a double-blind, randomized, placebo-controlled intervention study we supplemented 28 male smokers with 200 mg per day of monomeric and oligomeric flavanols (MOF from grape seeds. At baseline, after 4 and 8 weeks we measured macro- and microvascular function and a cluster of systemic biomarkers for major pathological processes occurring in the vasculature: disturbances in lipid metabolism and cellular redox balance, and activation of inflammatory cells and platelets. RESULTS: In the MOF group serum total cholesterol and LDL decreased significantly (P ≤ 0.05 by 5% (n = 11 and 7% (n = 9, respectively in volunteers with elevated baseline levels. Additionally, after 8 weeks the ratio of glutathione to glutathione disulphide in erythrocytes rose from baseline by 22% (n = 15, P<0.05 in MOF supplemented subjects. We also observed that MOF supplementation exerts anti-inflammatory effects in blood towards ex vivo added bacterial endotoxin and significantly reduces expression of inflammatory genes in leukocytes. Conversely, alterations in macro- and microvascular function, platelet aggregation, plasma levels of nitric oxide surrogates, endothelin-1, C-reactive protein, fibrinogen, prostaglandin F2alpha, plasma antioxidant capacity and gene expression levels of antioxidant defense enzymes did not reach statistical significance after 8 weeks MOF supplementation. However, integrating all measured effects into a global, so-called vascular health index revealed a significant improvement of overall vascular health by MOF compared to placebo (P ≤ 0.05. CONCLUSION: Our

  19. Insights into Basal Signaling Regulation, Oligomerization, and Structural Organization of the Human G-Protein Coupled Receptor 83.

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    Anne Müller

    Full Text Available The murine G-protein coupled receptor 83 (mGPR83 is expressed in the hypothalamus and was previously suggested to be involved in the regulation of metabolism. The neuropeptide PEN has been recently identified as a potent GPR83 ligand. Moreover, GPR83 constitutes functionally relevant hetero-oligomers with other G-protein coupled receptors (GPCR such as the ghrelin receptor (GHSR or GPR171. Previous deletion studies also revealed that the long N-terminal extracellular receptor domain (eNDo of mGPR83 may act as an intra-molecular ligand, which participates in the regulation of basal signaling activity, which is a key feature of GPCR function. Here, we investigated particular amino acids at the eNDo of human GPR83 (hGPR83 by side-directed mutagenesis to identify determinants of the internal ligand. These studies were accompanied by structure homology modeling to combine functional insights with structural information. The capacity for hetero-oligomer formation of hGPR83 with diverse family A GPCRs such as the melanocortin-4 receptor (MC4R was also investigated, with a specific emphasis on the impact of the eNDo on oligomerization and basal signaling properties. Finally, we demonstrate that hGPR83 exhibits an unusual basal signaling for different effectors, which also supports signaling promiscuity. hGPR83 interacts with a variety of hypothalamic GPCRs such as the MC4R or GHSR. These interactions are not dependent on the ectodomain and most likely occur at interfaces constituted in the transmembrane regions. Moreover, several amino acids at the transition between the eNDo and transmembrane helix 1 were identified, where mutations lead also to biased basal signaling modulation.

  20. Nucleotide-oligomerizing domain-1 (NOD1) receptor activation induces pro-inflammatory responses and autophagy in human alveolar macrophages.

    Science.gov (United States)

    Juárez, Esmeralda; Carranza, Claudia; Hernández-Sánchez, Fernando; Loyola, Elva; Escobedo, Dante; León-Contreras, Juan Carlos; Hernández-Pando, Rogelio; Torres, Martha; Sada, Eduardo

    2014-09-25

    Nucleotide-binding oligomerizing domain-1 (NOD1) is a cytoplasmic receptor involved in recognizing bacterial peptidoglycan fragments that localize to the cytosol. NOD1 activation triggers inflammation, antimicrobial mechanisms and autophagy in both epithelial cells and murine macrophages. NOD1 mediates intracellular pathogen clearance in the lungs of mice; however, little is known about NOD1's role in human alveolar macrophages (AMs) or its involvement in Mycobacterium tuberculosis (Mtb) infection. AMs, monocytes (MNs), and monocyte-derived macrophages (MDMs) from healthy subjects were assayed for NOD1 expression. Cells were stimulated with the NOD1 ligand Tri-DAP and cytokine production and autophagy were assessed. Cells were infected with Mtb and treated with Tri-DAP post-infection. CFUs counting determined growth control, and autophagy protein recruitment to pathogen localization sites was analyzed by immunoelectron microscopy. NOD1 was expressed in AMs, MDMs and to a lesser extent MNs. Tri-DAP stimulation induced NOD1 up-regulation and a significant production of IL1β, IL6, IL8, and TNFα in AMs and MDMs; however, the level of NOD1-dependent response in MNs was limited. Autophagy activity determined by expression of proteins Atg9, LC3, IRGM and p62 degradation was induced in a NOD1-dependent manner in AMs and MDMs but not in MNs. Infected AMs could be activated by stimulation with Tri-DAP to control the intracellular growth of Mtb. In addition, recruitment of NOD1 and the autophagy proteins IRGM and LC3 to the Mtb localization site was observed in infected AMs after treatment with Tri-DAP. NOD1 is involved in AM and MDM innate responses, which include proinflammatory cytokines and autophagy, with potential implications in the killing of Mtb in humans.

  1. Activation of nucleotide oligomerization domain 2 (NOD2 by human cytomegalovirus initiates innate immune responses and restricts virus replication.

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    Arun Kapoor

    Full Text Available Nucleotide-binding oligomerization domain 2 (NOD2 is an important innate immune sensor of bacterial pathogens. Its induction results in activation of the classic NF-κB pathway and alternative pathways including type I IFN and autophagy. Although the importance of NOD2 in recognizing RNA viruses has recently been identified, its role in sensing DNA viruses has not been studied. We report that infection with human cytomegalovirus (HCMV results in significant induction of NOD2 expression, beginning as early as 2 hours post infection and increasing steadily 24 hours post infection and afterwards. Infection with human herpesvirus 1 and 2 does not induce NOD2 expression. While the HCMV-encoded glycoprotein B is not required for NOD2 induction, a replication competent virion is necessary. Lentivirus-based NOD2 knockdown in human foreskin fibroblasts (HFFs and U373 glioma cells leads to enhanced HCMV replication along with decreased levels of interferon beta (IFN-β and the pro-inflammatory cytokine, IL8. NOD2 induction in HCMV-infected cells activates downstream NF-κB and interferon pathways supported by reduced nuclear localization of NF-κB and pIRF3 in NOD2 knockdown HFFs. Stable overexpression of NOD2 in HFFs restricts HCMV replication in association with increased levels of IFN-β and IL8. Similarly, transient overexpression of NOD2 in U373 cells or its downstream kinase, RIPK2, results in decreased HCMV replication and enhanced cytokine responses. However, overexpression of a mutant NOD2, 3020insC, associated with severe Crohn's disease, results in enhanced HCMV replication and decreased levels of IFN-β in U373 cells. These results show for the first time that NOD2 plays a significant role in HCMV replication and may provide a model for studies of HCMV recognition by the host cell and HCMV colitis in Crohn's disease.

  2. Oligomeric proanthocyanidins (OPCs) modulating radiation-induced oxidative stress on functional and structural performance of eye in male rats

    International Nuclear Information System (INIS)

    Said, U.Z.; Soliman, S.M.; Azab, Kh.Sh.; El-Tahawy, N.A.

    2005-01-01

    Eye oxidative stress may play a major role in the etiology and pathogenesis of eye disorders such as macular degeneration and photic injury of retinal degeneration that lead to vision loss. Proanthocyanidins derived from pine bark and from grape seeds have various anti pathophysiological functions. This study was performed to evaluate the role of oligomeric proanthocyanidins (OPCs) on the radiation-induced changes in rat eye tissues. OPCs were supplemented to rats (100 mg /kg body weight/ day) for 14 successive days before and 7 successive days after exposure to 7 Gy (single dose) of whole body gamma irradiation. The results revealed radiation-induced depletion in the activities of eye endogenous antioxidant enzymes and rise in pro-oxidant levels. Supplementation of OPCs pre- and post-irradiation has significantly reduced the levels of thiobarbituric acid reactive substances, xanthine oxidase, and significantly ameliorated the activities of xanthine dehydrogenase and reactive oxygen scavenging enzymes such as superoxide dismutase, glutathione peroxidase and catalase activities in eye tissues. OPCs significantly ameliorated the radiation-induced changes in levels of insulin and glucose in the serum. The oxidative stress induced cellular damage as indicated by retardation in the responses of eye to photo stimulation as well as histopathological changes in the eye tissues. Severe intra-retinal hemorrhages, cornea swelling, disruption of photoreceptor layer of the retina and epithelial necrosis were seen. The eye tissues of rats that received OPCs supplement showed significant less severe histological damage and remarkable improvement in photo stimulation responses when compared to irradiated rats on the 7 T h and 21 s t days after exposure to gamma irradiation. According to the results obtained, it could be concluded that OPCs might protect the eye tissues from the oxidative stress possibly by virtue of its anti oxidative activity through augmentation of antioxidant

  3. A Free Energy Barrier Caused by the Refolding of an Oligomeric Intermediate Controls the Lag Time of Amyloid Formation by hIAPP.

    Science.gov (United States)

    Serrano, Arnaldo L; Lomont, Justin P; Tu, Ling-Hsien; Raleigh, Daniel P; Zanni, Martin T

    2017-11-22

    Transiently populated oligomers formed en route to amyloid fibrils may constitute the most toxic aggregates associated with many amyloid-associated diseases. Most nucleation theories used to describe amyloid aggregation predict low oligomer concentrations and do not take into account free energy costs that may be associated with structural rearrangements between the oligomer and fiber states. We have used isotope labeling and two-dimensional infrared spectroscopy to spectrally resolve an oligomeric intermediate during the aggregation of the human islet amyloid protein (hIAPP or amylin), the protein associated with type II diabetes. A structural rearrangement includes the F 23 G 24 A 25 I 26 L 27 region of hIAPP, which starts from a random coil structure, evolves into ordered β-sheet oligomers containing at least 5 strands, and then partially disorders in the fibril structure. The supercritical concentration is measured to be between 150 and 250 μM, which is the thermodynamic parameter that sets the free energy of the oligomers. A 3-state kinetic model fits the experimental data, but only if it includes a concentration independent free energy barrier >3 kcal/mol that represents the free energy cost of refolding the oligomeric intermediate into the structure of the amyloid fibril; i.e., "oligomer activation" is required. The barrier creates a transition state in the free energy landscape that slows fibril formation and creates a stable population of oligomers during the lag phase, even at concentrations below the supercritical concentration. Largely missing in current kinetic models is a link between structure and kinetics. Our experiments and modeling provide evidence that protein structural rearrangements during aggregation impact the populations and kinetics of toxic oligomeric species.

  4. The long N-terminus of the human monocarboxylate transporter 8 is a target of ubiquitin-dependent proteasomal degradation which regulates protein expression and oligomerization capacity.

    Science.gov (United States)

    Zwanziger, Denise; Schmidt, Mathias; Fischer, Jana; Kleinau, Gunnar; Braun, Doreen; Schweizer, Ulrich; Moeller, Lars Christian; Biebermann, Heike; Fuehrer, Dagmar

    2016-10-15

    Monocarboxylate transporter 8 (MCT8) equilibrates thyroid hormones between the extra- and the intracellular sides. MCT8 exists either with a short or a long N-terminus, but potential functional differences between both variants are yet not known. We, therefore, generated MCT8 constructs which are different in N-terminal length: MCT8(1-613), MCT8(25-613), MCT8(49-613) and MCT8(75-613). The M75G substitution prevents translation of MCT8(75-613) and ensures expression of full-length MCT8 protein. The K56G substitution was made to prevent ubiquitinylation. Cell-surface expression, localization and proteasomal degradation were investigated using C-terminally GFP-tagged MCT8 constructs (HEK293 and MDCK1 cells) and oligomerization capacity was determined using N-terminally HA- and C-terminally FLAG-tagged MCT8 constructs (COS7 cells). MCT8(1-613)-GFP showed a lower protein expression than the shorter MCT8(75-613)-GFP protein. The proteasome inhibitor lactacystin increased MCT8(1-613)-GFP protein amount, suggesting proteasomal degradation of MCT8 with the long N-terminus. Ubiquitin conjugation of MCT8(1-613)-GFP was found by immuno-precipitation. A diminished ubiquitin conjugation caused by K56G substitution resulted in increased MCT8(1-613)-GFP protein expression. Sandwich ELISA was performed to investigate if the bands at higher molecular weight observed in Western blot analysis are due to MCT8 oligomerization, which was indeed shown. Our data imply a role of the long N-terminus of MCT8 as target of ubiquitin-dependent proteasomal degradation affecting MCT8 amount and subsequently oligomerization capacity. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  5. Hydrolyzable Tannins of Tamaricaceous Plants. 7.1 Structures and Cytotoxic Properties of Oligomeric Ellagitannins from Leaves of Tamarix nilotica and Cultured Tissues of Tamarix tetrandra.

    Science.gov (United States)

    Orabi, Mohamed A A; Taniguchi, Shoko; Sakagami, Hiroshi; Yoshimura, Morio; Amakura, Yoshiaki; Hatano, Tsutomu

    2016-04-22

    Partially unacylated new oligomeric hydrolyzable tannins, nilotinin T2 (1, trimer) and nilotinin Q1 (2, tetramer), together with four known trimers, nilotinin T1 (3) and hirtellins T1-T3 (4-6), and a dimer, tamarixinin B (7), were isolated from the aqueous acetone extracts of leaves of Tamarix nilotica. Among them, the new trimer 1 and the known trimers 4 and 6, in addition to the partially unacylated new trimer nilotinin T3 (8), the known dimers nilotinin D3 (9) and tamarixinin C (10), and the monomer tellimagrandin I (11), were isolated from the cultured shoots of Tamarix tetrandra. The structures of the new hydrolyzable tannins were established by chromatographic analyses and extensive 1D and 2D NMR, HRESI-TOFMS, and ECD spectroscopic experiments. Among the new oligomeric tannins, the particular unacylated position of a glucose core is attributed to a possible biosynthetic route. Isolation of the same oligomeric tannins from cultured shoots of T. tetrandra emphasizes the unique biogenetic ability of the obtained cultures on production of the structurally and biologically characteristic tamaricaceous tannins commonly produced by the intact Tamarix plants. Additionally, tannins obtained in the present study together with gemin D (12) and 1,3-di-O-galloyl-4,6-O-(aS)-hexahydroxydiphenoyl-β-d-glucose (13), from our previous investigation of the leaves of T. nilotica, exhibited variable tumor-specific cytotoxic effects. The ellagitannin trimers 4, 6, and 8 and the dimer 9 exerted predominant tumor-selective cytotoxic effects with high specificity toward human promyelocytic leukemia cells.

  6. Insight into the template effect of vesicles on the laccase-catalyzed oligomerization of N-phenyl-1,4-phenylenediamine from Raman spectroscopy and cyclic voltammetry measurements

    Science.gov (United States)

    Ležaić, Aleksandra Janoševic; Luginbühl, Sandra; Bajuk-Bogdanović, Danica; Pašti, Igor; Kissner, Reinhard; Rakvin, Boris; Walde, Peter; Ćirić-Marjanović, Gordana

    2016-08-01

    We report about the first Raman spectroscopy study of a vesicle-assisted enzyme-catalyzed oligomerization reaction. The aniline dimer N-phenyl-1,4-phenylenediamine (= p-aminodiphenylamine, PADPA) was oxidized and oligomerized with Trametes versicolor laccase and dissolved O2 in the presence of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) vesicles (80-100 nm diameter) as templates. The conversion of PADPA into oligomeric products, poly(PADPA), was monitored during the reaction by in situ Raman spectroscopy. The results obtained are compared with UV/vis/NIR and EPR measurements. All three complementary methods indicate that at least some of the poly(PADPA) products, formed in the presence of AOT vesicles, resemble the conductive emeraldine salt form of polyaniline (PANI-ES). The Raman measurements also show that structural units different from those of “ordinary” PANI-ES are present too. Without vesicles PANI-ES-like products are not obtained. For the first time, the as-prepared stable poly(PADPA)-AOT vesicle suspension was used directly to coat electrodes (without product isolation) for investigating redox activities of poly(PADPA) by cyclic voltammetry (CV). CV showed that poly(PADPA) produced with vesicles is redox active not only at pH 1.1-as expected for PANI-ES-but also at pH 6.0, unlike PANI-ES and poly(PADPA) synthesized without vesicles. This extended pH range of the redox activity of poly(PADPA) is important for applications.

  7. Structure-based design of a disulfide-linked oligomeric form of the simian virus 40 (SV40) large T antigen DNA-binding domain

    International Nuclear Information System (INIS)

    Meinke, Gretchen; Phelan, Paul; Fradet-Turcotte, Amélie; Archambault, Jacques; Bullock, Peter A.

    2011-01-01

    With the aim of forming the ‘lock-washer’ conformation of the origin-binding domain of SV40 large T antigen in solution, using structure-based analysis an intermolecular disulfide bridge was engineered into the origin-binding domain to generate higher order oligomers in solution. The 1.7 Å resolution structure shows that the mutant forms a spiral in the crystal and has the de novo disulfide bond at the protein interface, although structural rearrangements at the interface are observed relative to the wild type. The modular multifunctional protein large T antigen (T-ag) from simian virus 40 orchestrates many of the events needed for replication of the viral double-stranded DNA genome. This protein assembles into single and double hexamers on specific DNA sequences located at the origin of replication. This complicated process begins when the origin-binding domain of large T antigen (T-ag ODB) binds the GAGGC sequences in the central region (site II) of the viral origin of replication. While many of the functions of purified T-ag OBD can be studied in isolation, it is primarily monomeric in solution and cannot assemble into hexamers. To overcome this limitation, the possibility of engineering intermolecular disulfide bonds in the origin-binding domain which could oligomerize in solution was investigated. A recent crystal structure of the wild-type T-ag OBD showed that this domain forms a left-handed spiral in the crystal with six subunits per turn. Therefore, we analyzed the protein interface of this structure and identified two residues that could potentially support an intermolecular disulfide bond if changed to cysteines. SDS–PAGE analysis established that the mutant T-ag OBD formed higher oligomeric products in a redox-dependent manner. In addition, the 1.7 Å resolution crystal structure of the engineered disulfide-linked T-ag OBD is reported, which establishes that oligomerization took place in the expected manner

  8. A S52P mutation in the 'α-crystallin domain' of Mycobacterium leprae HSP18 reduces its oligomeric size and chaperone function.

    Science.gov (United States)

    Nandi, Sandip K; Rehna, Elengikal A A; Panda, Alok K; Shiburaj, Sugathan; Dharmalingam, Kuppamuthu; Biswas, Ashis

    2013-12-01

    Mycobacterium leprae HSP18 is a small heat shock protein (sHSP). It is a major immunodominant antigen of M. leprae pathogen. Previously, we have reported the existence of two M. leprae HSP18 variants in various leprotic patients. One of the variants has serine at position 52, whereas the other one has proline at the same position. We have also reported that HSP18 having proline at position 52 (HSP18P(52)) is a nonameric protein and exhibits chaperone function. However, the structural and functional characterization of wild-type HSP18 having serine at position 52 (HSP18S(52)) is yet to be explored. Furthermore, the implications of the S52P mutation on the structure and chaperone function of HSP18 are not well understood. Therefore, we cloned and purified these two HSP18 variants. We found that HSP18S(52) is also a molecular chaperone and an oligomeric protein. Intrinsic tryptophan fluorescence and far-UV CD measurements revealed that the S52P mutation altered the tertiary and secondary structure of HSP18. This point mutation also reduced the oligomeric assembly and decreased the surface hydrophobicity of HSP18, as revealed by HPLC and 4,4'-dianilino-1,1'-binaphthyl-5,5'-disulfonic acid binding studies, respectively. Mutant protein was less stable against thermal and chemical denaturation and was more susceptible towards tryptic cleavage than wild-type HSP18. HSP18P(52) had lower chaperone function and was less effective in protecting thermal killing of Escherichia coli than HSP18S(52). Taken together, our data suggest that serine 52 is important for the larger oligomerization and chaperone function of HSP18. Because both variants differ in stability and function, they may have different roles in the survival of M. leprae in infected hosts. © 2013 FEBS.

  9. Facile hydrothermal synthesis of polyhedral Fe{sub 3}O{sub 4} nanocrystals, influencing factors and application in the electrochemical detection of H{sub 2}O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Yuan Kefeng [College of Chemistry and Materials Science, Anhui Key Laboratory of Functional Molecular Solids, Anhui Normal University, Wuhu 241000 (China); Ni Yonghong, E-mail: niyh@mail.ahnu.edu.cn [College of Chemistry and Materials Science, Anhui Key Laboratory of Functional Molecular Solids, Anhui Normal University, Wuhu 241000 (China); Zhang Li [College of Chemistry and Materials Science, Anhui Key Laboratory of Functional Molecular Solids, Anhui Normal University, Wuhu 241000 (China)

    2012-08-15

    Highlights: Black-Right-Pointing-Pointer Fe{sub 3}O{sub 4} polyhedra had been successfully synthesized by a facile hydrothermal technology. Black-Right-Pointing-Pointer The as-obtained product exhibited the room-temperature ferrimagnetic property. Black-Right-Pointing-Pointer The final product could be prepared into an electrochemical sensor for the detection of H{sub 2}O{sub 2}. - Abstract: Polyhedral Fe{sub 3}O{sub 4} nanocrystals have been successfully synthesized by a facile hydrothermal technique, employing FeSO{sub 4}{center_dot}7H{sub 2}O, N{sub 2}H{sub 4} and NH{sub 3}{center_dot}H{sub 2}O as the reactants without the assistance of any surfactant. The phase of the as-obtained Fe{sub 3}O{sub 4} was characterized by X-ray powder diffraction (XRD) and further proved by Rietveld refinement of XRD data. Energy dispersive spectrometry (EDS) and scanning electron microscopy (SEM) were used for the composition and morphology analyses of the final product. Some factors influencing the formation of polyhedral Fe{sub 3}O{sub 4} nanocrystals were systematically investigated, including the reaction temperature and time, and the original volume ratio of NH{sub 3}{center_dot}H{sub 2}O/N{sub 2}H{sub 4}{center_dot}H{sub 2}O. It was found that the as-prepared Fe{sub 3}O{sub 4} polyhedra exhibited a good electrochemical property in 0.1 M phosphate buffer solution (PBS) with pH 7.0 and could be prepared into an electrochemical sensor for the detection of H{sub 2}O{sub 2}. The linear response range of the sensor was 10.0 Multiplication-Sign 10{sup -6} to 140.0 Multiplication-Sign 10{sup -6} M and a sensitivity was 11.05 {mu}A/mM. Furthermore, the room-temperature magnetic property of the product was also investigated.

  10. Biodegradable and adjustable sol-gel glass based hybrid scaffolds from multi-armed oligomeric building blocks.

    Science.gov (United States)

    Kascholke, Christian; Hendrikx, Stephan; Flath, Tobias; Kuzmenka, Dzmitry; Dörfler, Hans-Martin; Schumann, Dirk; Gressenbuch, Mathias; Schulze, F Peter; Schulz-Siegmund, Michaela; Hacker, Michael C

    2017-11-01

    Biodegradability is a crucial characteristic to improve the clinical potential of sol-gel-derived glass materials. To this end, a set of degradable organic/inorganic class II hybrids from a tetraethoxysilane(TEOS)-derived silica sol and oligovalent cross-linker oligomers containing oligo(d,l-lactide) domains was developed and characterized. A series of 18 oligomers (Mn: 1100-3200Da) with different degrees of ethoxylation and varying length of oligoester units was established and chemical composition was determined. Applicability of an established indirect rapid prototyping method enabled fabrication of a total of 85 different hybrid scaffold formulations from 3-isocyanatopropyltriethoxysilane-functionalized macromers. In vitro degradation was analyzed over 12months and a continuous linear weight loss (0.2-0.5wt%/d) combined with only moderate material swelling was detected which was controlled by oligo(lactide) content and matrix hydrophilicity. Compressive strength (2-30MPa) and compressive modulus (44-716MPa) were determined and total content, oligo(ethylene oxide) content, oligo(lactide) content and molecular weight of the oligomeric cross-linkers as well as material porosity were identified as the main factors determining hybrid mechanics. Cytocompatibility was assessed by cell culture experiments with human adipose tissue-derived stem cells (hASC). Cell migration into the entire scaffold pore network was indicated and continuous proliferation over 14days was found. ALP activity linearly increased over 2weeks indicating osteogenic differentiation. The presented glass-based hybrid concept with precisely adjustable material properties holds promise for regenerative purposes. Adaption of degradation kinetics toward physiological relevance is still an unmet challenge of (bio-)glass engineering. We therefore present a glass-derived hybrid material with adjustable degradation. A flexible design concept based on degradable multi-armed oligomers was combined with an

  11. Carbon Domains on MoS2/TiO2 System via Catalytic Acetylene Oligomerization: Synthesis, Structure, and Surface Properties

    Directory of Open Access Journals (Sweden)

    Sara Cravanzola

    2017-11-01

    Full Text Available Carbon domains have been obtained at the surface of a MoS2/TiO2 (Evonik, P25 system via oligomerization and cyclotrimerization reactions involved in the interaction of the photoactive material with acetylene. Firstly, MoS2 nanosheets have been synthesized at the surface of TiO2, via sulfidation of a molybdenum oxide precursor with H2S (bottom-up method. Secondly, the morphology and the structure, the optical and the vibrational properties of the obtained materials, for each step of the synthesis procedure, have been investigated by microscopy and spectroscopy methods. In particular, transmission electron microscopy images provide a simple tool to highlight the effectiveness of the sulfidation process, thus showing 1L, 2L, and stacked MoS2 nanosheets anchored to the surface of TiO2 nanoparticles. Lastly, in-situ FTIR spectroscopy investigation gives insights into the nature of the oligomerized species, showing that the formation of both polyenic and aromatic systems can be taken into account, being their formation promoted by both Ti and Mo catalytic sites. This finding gives an opportunity for the assembly of extended polyenic, polyaromatic, or mixed domains firmly attached at the surface of photoactive materials. The presented approach, somehow different from the carbon adding or doping processes of TiO2, is of potential interest for the advanced green chemistry and energy conversion/transport applications.

  12. Simultaneous separation and identification of oligomeric procyanidins and anthocyanin-derived pigments in raw red wine by HPLC-UV-ESI-MSn.

    Science.gov (United States)

    Pati, S; Losito, I; Gambacorta, G; La Notte, E; Palmisano, F; Zambonin, P G

    2006-07-01

    Samples of raw red wine (Primitivo di Manduria, Apulia, Southern Italy) were analysed without any pre-treatment (except 1:2 dilution with water) using HPLC with detection based on UV absorbance and Electrospray Ionisation Sequential Mass Spectrometry (ESI-MSn, with n = 1-3) in a series configuration. In particular, absorbance at 520 nm was monitored for UV detection in order to identify pigments responsible for wine colour. On the other hand, two subsequent stages of MS detection based on positive ions were adopted. The first consisted of an explorative MS acquisition, aimed at the individuation of the m/z ratios for positively charged compounds; the second was based on fragmentation of the detected ions within an ion trap analyser, followed by MS/MS and, if required, MS3 acquisitions. The synergy between UV detection and MSn analysis led to the identification of 41 pigments, which can be classified into five groups: grape anthocyanins, pyranoanthocyanins, vinyl-linked anthocyanin-flavanol pigments, ethyl-bridged anthocyanin-flavanol pigments and flavanol-anthocyanin compounds. Many isomeric and oligomeric structures were found within each group. A further class of compounds, not absorbing in the visible spectrum, could be also characterised by ESI-MSn and corresponded to B-type procyanidins, i.e. proanthocyanidins arising from C4-->C8/C4-->C6 couplings between catechin or epicatechin units. In particular, oligomeric structures (from dimers to pentamers), often present with several isomers, were identified and their fragmentation patterns clarified.

  13. Eicosanoyl-5-hydroxytryptamide (EHT prevents Alzheimer's disease-related cognitive and electrophysiological impairments in mice exposed to elevated concentrations of oligomeric beta-amyloid.

    Directory of Open Access Journals (Sweden)

    Kesava Asam

    Full Text Available Soluble forms of oligomeric beta-amyloid (Aβ are thought to play a central role in Alzheimer's disease (AD. Transgenic manipulation of methylation of the serine/threonine protein phosphatase, PP2A, was recently shown to alter the sensitivity of mice to AD-related impairments resulting from acute exposure to elevated levels of Aβ. In addition, eicosanoyl-5-hydroxytryptamide (EHT, a naturally occurring component from coffee beans that modulates PP2A methylation, was shown to confer therapeutic benefits in rodent models of AD and Parkinson's disease. Here, we tested the hypothesis that EHT protects animals from the pathological effects of exposure to elevated levels of soluble oligomeric Aβ. We treated mice with EHT-containing food at two different doses and assessed the sensitivity of these animals to Aβ-induced behavioral and electrophysiological impairments. We found that EHT administration protected animals from Aβ-induced cognitive impairments in both a radial-arm water maze and contextual fear conditioning task. We also found that both chronic and acute EHT administration prevented Aβ-induced impairments in long-term potentiation. These data add to the accumulating evidence suggesting that interventions with pharmacological agents, such as EHT, that target PP2A activity may be therapeutically beneficial for AD and other neurological conditions.

  14. Data in support of the identification of neuronal and astrocyte proteins interacting with extracellularly applied oligomeric and fibrillar α-synuclein assemblies by mass spectrometry.

    Science.gov (United States)

    Shrivastava, Amulya Nidhi; Redeker, Virginie; Fritz, Nicolas; Pieri, Laura; Almeida, Leandro G; Spolidoro, Maria; Liebmann, Thomas; Bousset, Luc; Renner, Marianne; Léna, Clément; Aperia, Anita; Melki, Ronald; Triller, Antoine

    2016-06-01

    α-Synuclein (α-syn) is the principal component of Lewy bodies, the pathophysiological hallmark of individuals affected by Parkinson disease (PD). This neuropathologic form of α-syn contributes to PD progression and propagation of α-syn assemblies between neurons. The data we present here support the proteomic analysis used to identify neuronal proteins that specifically interact with extracellularly applied oligomeric or fibrillar α-syn assemblies (conditions 1 and 2, respectively) (doi: 10.15252/embj.201591397[1]). α-syn assemblies and their cellular partner proteins were pulled down from neuronal cell lysed shortly after exposure to exogenous α-syn assemblies and the associated proteins were identified by mass spectrometry using a shotgun proteomic-based approach. We also performed experiments on pure cultures of astrocytes to identify astrocyte-specific proteins interacting with oligomeric or fibrillar α-syn (conditions 3 and 4, respectively). For each condition, proteins interacting selectively with α-syn assemblies were identified by comparison to proteins pulled-down from untreated cells used as controls. The mass spectrometry data, the database search and the peak lists have been deposited to the ProteomeXchange Consortium database via the PRIDE partner repository with the dataset identifiers PRIDE: PXD002256 to PRIDE: PXD002263 and doi: 10.6019/PXD002256 to 10.6019/PXD002263.

  15. Inside-out signaling promotes dynamic changes in the carcinoembryonic antigen-related cellular adhesion molecule 1 (CEACAM1) oligomeric state to control its cell adhesion properties.

    Science.gov (United States)

    Patel, Prerna C; Lee, Hannah S W; Ming, Aaron Y K; Rath, Arianna; Deber, Charles M; Yip, Christopher M; Rocheleau, Jonathan V; Gray-Owen, Scott D

    2013-10-11

    Cell-cell contacts are fundamental to multicellular organisms and are subject to exquisite levels of control. The carcinoembryonic antigen-related cell adhesion molecule 1 (CEACAM1) can engage in both cis-homophilic (parallel) oligomerization and trans-homophilic (anti-parallel) binding. In this study, we establish that the CEACAM1 transmembrane domain has a propensity to form cis-dimers via the transmembrane-embedded (432)GXXXG(436) motif and that this basal state is overcome when activated calmodulin binds to the CEACAM1 cytoplasmic domain. Although mutation of the (432)GXXXG(436) motif reduced CEACAM1 oligomerization, it did not affect surface localization of the receptor or influence CEACAM1-dependent cellular invasion by the pathogenic Neisseria. The mutation did, however, have a striking effect on CEACAM1-dependent cellular aggregation, increasing both the kinetics of cell-cell association and the size of cellular aggregates formed. CEACAM1 association with tyrosine kinase c-Src and tyrosine phosphatases SHP-1 and SHP-2 was not affected by the (432)GXXXG(436) mutation, consistent with their association with the monomeric form of wild type CEACAM1. Collectively, our results establish that a dynamic oligomer-to-monomer shift in surface-expressed CEACAM1 facilitates trans-homophilic binding and downstream effector signaling.

  16. Changes in the oligomerization potential of the division inhibitor UgtP co-ordinate Bacillus subtilis cell size with nutrient availability.

    Science.gov (United States)

    Chien, An-Chun; Zareh, Shannon Kian Gharabiklou; Wang, Yan Mei; Levin, Petra Anne

    2012-11-01

    How cells co-ordinate size with growth and development is a major, unresolved question in cell biology. In previous work we identified the glucosyltransferase UgtP as a division inhibitor responsible for increasing the size of Bacillus subtilis cells under nutrient-rich conditions. In nutrient-rich medium, UgtP is distributed more or less uniformly throughout the cytoplasm and concentrated at the cell poles and/or the cytokinetic ring. Under these conditions, UgtP interacts directly with FtsZ to inhibit division and increase cell size. Conversely, under nutrient-poor conditions, UgtP is sequestered away from FtsZ in punctate foci, and division proceeds unimpeded resulting in a reduction in average cell size. Here we report that nutrient-dependent changes in UgtP's oligomerization potential serve as a molecular rheostat to precisely co-ordinate B. subtilis cell size with nutrient availability. Our data indicate UgtP interacts with itself and the essential cell division protein FtsZ in a high-affinity manner influenced in part by UDP glucose, an intracellular proxy for nutrient availability. These findings support a model in which UDP-glc-dependent changes in UgtP's oligomerization potential shift the equilibrium between UgtP•UgtP and UgtP•FtsZ, fine-tuning the amount of FtsZ available for assembly into the cytokinetic ring and with it cell size. © 2012 Blackwell Publishing Ltd.

  17. Microglial phagocytosis induced by fibrillar β-amyloid is attenuated by oligomeric β-amyloid: implications for Alzheimer's disease

    Directory of Open Access Journals (Sweden)

    Lin Nan

    2011-06-01

    Full Text Available Abstract Background Reactive microglia are associated with β-amyloid (Aβ deposit and clearance in Alzhiemer's Disease (AD. Paradoxically, entocranial resident microglia fail to trigger an effective phagocytic response to clear Aβ deposits although they mainly exist in an "activated" state. Oligomeric Aβ (oAβ, a recent target in the pathogenesis of AD, can induce more potent neurotoxicity when compared with fibrillar Aβ (fAβ. However, the role of the different Aβ forms in microglial phagocytosis, induction of inflammation and oxidation, and subsequent regulation of phagocytic receptor system, remain unclear. Results We demonstrated that Aβ(1-42 fibrils, not Aβ(1-42 oligomers, increased the microglial phagocytosis. Intriguingly, the pretreatment of microglia with oAβ(1-42 not only attenuated fAβ(1-42-triggered classical phagocytic response to fluorescent microspheres but also significantly inhibited phagocytosis of fluorescent labeled fAβ(1-42. Compared with the fAβ(1-42 treatment, the oAβ(1-42 treatment resulted in a rapid and transient increase in interleukin 1β (IL-1β level and produced higher levels of tumor necrosis factor-α (TNF-α, nitric oxide (NO, prostaglandin E2 (PGE2 and intracellular superoxide anion (SOA. The further results demonstrated that microglial phagocytosis was negatively correlated with inflammatory mediators in this process and that the capacity of phagocytosis in fAβ(1-42-induced microglia was decreased by IL-1β, lippolysaccharide (LPS and tert-butyl hydroperoxide (t-BHP. The decreased phagocytosis could be relieved by pyrrolidone dithiocarbamate (PDTC, a nuclear factor-κB (NF-κB inhibitor, and N-acetyl-L-cysteine (NAC, a free radical scavenger. These results suggest that the oAβ-impaired phagocytosis is mediated through inflammation and oxidative stress-mediated mechanism in microglial cells. Furthermore, oAβ(1-42 stimulation reduced the mRNA expression of CD36, integrin β1 (Itgb1, and Ig

  18. Mutations increasing exposure of a receptor binding site epitope in the soluble and oligomeric forms of the caprine arthritis-encephalitis lentivirus envelope glycoprotein

    International Nuclear Information System (INIS)

    Hoetzel, Isidro; Cheevers, William P.

    2005-01-01

    The caprine arthritis-encephalitis (CAEV) and ovine maedi-visna (MVV) viruses are resistant to antibody neutralization, a feature shared with all other lentiviruses. Whether the CAEV gp135 receptor binding site(s) (RBS) in the functional surface envelope glycoprotein (Env) is protected from antibody binding, allowing the virus to resist neutralization, is not known. Two CAEV gp135 regions were identified by extrapolating a gp135 structural model that could affect binding of antibodies to the RBS: the V1 region and a short sequence analogous in position to the human immunodeficiency virus type 1 gp120 loop B postulated to be located between two major domains of CAEV gp135. Mutation of isoleucine-166 to alanine in the putative loop B of gp135 increased the affinity of soluble gp135 for the CAEV receptor(s) and goat monoclonal antibody (Mab) F7-299 which recognizes an epitope overlapping the gp135 RBS. The I166A mutation also stabilized or exposed the F7-299 epitope in anionic detergent buffers, indicating that the I166A mutation induces conformational changes and stabilizes the RBS of soluble gp135 and enhances Mab F7-299 binding. In contrast, the affinity of a V1 deletion mutant of gp135 for the receptor and Mab F7-299 and its structural stability did not differ from that of the wild-type gp135. However, both the I166A mutation and the V1 deletion of gp135 increased cell-to-cell fusion activity and binding of Mab F7-299 to the oligomeric Env. Therefore, the CAEV gp135 RBS is protected from antibody binding by mechanisms both dependent and independent of Env oligomerization which are disrupted by the V1 deletion and the I166A mutation, respectively. In addition, we found a correlation between side-chain β-branching at amino acid position 166 and binding of Mab F7-299 to oligomeric Env and cell-to-cell fusion, suggesting local secondary structure constraints in the region around isoleucine-166 as one determinant of gp135 RBS exposure and antibody binding

  19. Single Site Silica Supported Tetramethyl Niobium by the SOMC Strategy: Synthesis, Characterization and Structure-Activity Relationship in Ethylene Oligomerization Reaction

    KAUST Repository

    Hamieh, Ali Imad Ali

    2017-06-06

    Silica supported Tetramethyl niobium complex [(≡SiO)NbMe4] 2 has been isolated by surface alkylation of [(≡SiO-)NbCl3Me] 1 with dimethyl zinc in pentane. 1 can be easily synthesized by grafting of NbCl3Me2 on to the surface of partially dehydroxylated silica by the SOMC strategy. Precise structural analysis was carried out by the FTIR, advance solid state NMR, elemental analysis and mass balance techniques (gas quantification after treating 2 with degassed water) . Complex 1 was found to be active in the ethylene oligomerization to produce up to C30, whereas to our surprise complex 2 selectively dimerizes ethylene into 1-butene in the absence of a co-catalyst at the same conversion levels.

  20. (Pressure + volume + temperature) properties for binary oligomeric solutions of poly(ethylene glycol mono-4-octylphenyl ether) with 1-octanol or acetophenone at pressures up to 50 MPa

    International Nuclear Information System (INIS)

    Lee, M.-J.; Ku, T.-J.; Lin Homu

    2009-01-01

    Densities were measured with a high-pressure densitometer for two binary oligomeric systems of poly(ethylene glycol mono-4-octylphenyl ether) (PEGOPE) with 1-octanol or acetophenone at temperatures from 298.15 K to 348.15 K and pressures up to 50 MPa. While the excess volumes are negative in (acetophenone + PEGOPE) over the entire composition range, those are found to change from positive to negative with increasing mole fraction of the solvent in (1-octanol + PEGOPE). The pressure-effect on the liquid densities can be represented accurately by the Tait equation. Moreover, an empirical equation with two characteristic parameters correlates well the PVT data over the entire experimental conditions for each binary system. The experimental specific volumes were also correlated with the Flory-Orwoll-Vrij (FOV) and the Schotte equations of state to within the experimental uncertainty.