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Sample records for 3-n-propyl methylpyridinium silsesquioxane

  1. Structure of 4-methylpyridinium Hydrogen Sulfide

    NASA Technical Reports Server (NTRS)

    Andras, Maria T.; Hepp, Aloysius F.; Fanwick, Phillip E.; Martuch, Robert A.; Duraj, Stan A.; Gordon, Edward M.

    1994-01-01

    4-Methylpyridinium hydrogen sulfide, (C6H7NH)HS, M(sub r) = 127.21, consists of C6H7NH(+) cations and HS(-) anions. Z = 2 for the crystal with monoclinic space group Cm (#8), dimensions of a = 8.679(2) A, b = 7.964(1) A, and c = 4.860(2) A, an angle beta of 101.10(2) degrees, and a volume of V = 329.6(3) A(exp 3). R = 0.039 and R(sub w) = 0.048 for 385 reflections with F(sub o)(exp 2) greater than 3 sigma(F(sub o)(exp 2)) and 59 variables. Both the C6H7NH(+) cation and the HS(-) anion lie on crystallographic mirror planes with the N,S, two carbon atoms, and two hydrogen atoms positioned in the planes. The hydrogen atom of the HS(-) anion was not located.

  2. Troponin T immunosensor based on liquid crystal and silsesquioxane-supported gold nanoparticles.

    PubMed

    Zapp, Eduardo; da Silva, Paulo Sérgio; Westphal, Eduard; Gallardo, Hugo; Spinelli, Almir; Vieira, Iolanda Cruz

    2014-09-17

    A nanostructured immunosensor based on the liquid crystal (E)-1-decyl-4-[(4-decyloxyphenyl)diazenyl]pyridinium bromide (Br-Py) and gold nanoparticles supported by the water-soluble hybrid material 3-n-propyl-4-picolinium silsesquioxane chloride (AuNP-Si4Pic(+)Cl(-)) was built for the detection of troponin T (cTnT), a cardiac marker for acute myocardial infarction (AMI). The functionalized nanostructured surface was used to bind anti-cTnT monoclonal antibodies through electrostatic interaction. The immunosensor (ab-cTnT/AuNP-Si4Pic(+)Cl(-)/Br-Py/GCE) surface was characterized by microscopy techniques. The electrochemical behavior of the immunosensor was studied by cyclic voltammetry and electrochemical impedance spectroscopy. A calibration curve was obtained by square-wave voltammetry. The immnunosensor provided a limit of detection of 0.076 ng mL(-1) and a linear range between 0.1 and 0.9 ng mL(-1) (appropriate for AMI diagnosis).

  3. Silsesquioxane-derived ceramic fibres

    NASA Technical Reports Server (NTRS)

    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.

  4. Silsesquioxane-derived ceramic fibres

    NASA Technical Reports Server (NTRS)

    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.

  5. Polyhedral Oligomeric Silsesquioxanes in Plastics

    NASA Astrophysics Data System (ADS)

    Dearmitt, Chris

    Polyhedral oligomeric silsesquioxanes (POS or POSS®) were fi rst synthesized as long ago as the 1960s. Since that time, global interest has grown considerably as indicated by the many articles and patents in the fi eld [1,2,3,4,5]. The reason being that POS, with a unique three dimensional cage structure composed of silicon and oxygen (Fig. 5.1), is an unusual type of molecule with correspondingly unusual properties. The discovery of the cage form of carbon, called buckminsterfullerene (Fig. 5.1), was awarded the 1996 Nobel Prize for Chemistry, and other cage structure hydrocarbons such as adamantane and other diamondoids have attracted considerable interest. However, time has shown that POS is far more commercially important for several reasons. Firstly, POS is extremely versatile.

  6. Gold nanoparticles hosted in a water-soluble silsesquioxane polymer applied as a catalytic material onto an electrochemical sensor for detection of nitrophenol isomers.

    PubMed

    Silva, Paulo Sérgio da; Gasparini, Bianca C; Magosso, Hérica A; Spinelli, Almir

    2014-05-30

    The water-soluble 3-n-propyl-4-picolinium silsesquioxane chloride (Si4Pic(+)Cl(-)) polymer was prepared, characterized and used as a stabilizing agent for the synthesis of gold nanoparticles (nAu). The ability of Si4Pic(+)Cl(-) to adsorb anionic metal complexes such as AuCl4(-) ions allowed well-dispersed nAu to be obtained with an average particle size of 4.5nm. The liquid suspension of nAu-Si4Pic(+)Cl(-) was deposited by the drop coating method onto a glassy carbon electrode (GCE) surface to build a sensor (nAu-Si4Pic(+)Cl(-)/GCE) which was used for the detection of o-nitrophenol (o-NP) and p-nitrophenol (p-NP). Under optimized experimental conditions the reduction peak current increased with increasing concentrations of both nitrophenol isomers in the range of 0.1-1.5μmolL(-1). The detection limits were 46nmolL(-1) and 55nmolL(-1) for o-NP and p-NP, respectively. These findings indicate that the nAu-Si4Pic(+)Cl(-) material is a very promising candidate to assemble electrochemical sensors for practical applications in the field of analytical chemistry.

  7. Vibrational analysis of 1-methyl-pyridinium-2-aldoxime and 1-methyl-pyridinium-4-aldoxime cations

    NASA Astrophysics Data System (ADS)

    Grošev, Vlasta Mohaček; Foretić, Blaženka; Gamulin, Ozren

    2011-05-01

    Pyrimidinium aldoximes are administered intravenously in cases of acute organophosphate poisoning. Since questions regarding their morphology and active conformation in the solution are still open, an effort was made to establish correspondence between their crystal state conformers and vibrational spectra, thus facilitating the future work on the assignment of bands in solution. Normal coordinate analysis including the potential energy distribution for all modes was performed for 1-methyl-pyridinium-2-aldoxime (PAM2AN) and 1-methyl-pyridinium-4-aldoxime (PAM4AN) cations (charge = +e, spin = 0). Positions of infrared and Raman bands of corresponding chloride salts agree rather well with predicted values, except for modes taking part in hydrogen bonding to anions. The strength of hydrogen bonding is estimated to be of medium strength in both salts, the bonding in PAM2AN being stronger. The calculated and observed values of the characteristic stretching modes for the aldoxime moiety have been in accordance with the stronger acidity of PAM2AN structural isomer.

  8. Silsesquioxanes as precursors to ceramic composites

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Hyatt, Lizbeth H.; Gorecki, Joy; Damore, Lisa

    1987-01-01

    Silsesquioxanes having the general structure RSiO sub 1.5, where R = methyl, propyl, or phenyl, melt flow at 70 to 100 C. Above 100 C, free -OH groups condense. At 225 C further crosslinking occurs, and the materials form thermosets. Pyrolysis, with accompanying loss of volatiles, takes place at nominally 525 C. At higher temperatures, the R group serves as an internal carbon soruce for carbo-thermal reduction to SiC accompanied by the evolution of CO. By blending silsesquioxanes with varying R groups, both the melt rheology and composition of the fired ceramic can be controlled. Fibers can be spun from the melt which are stable in argon in 1400 C. The silsesquioxanes also were used as matrix precursors for Nicalon and alpha-SiC platelet reinforced composites.

  9. Oxovanadium(IV) silsesquioxane complexes.

    PubMed

    Ohde, Christian; Limberg, Christian; Stösser, Reinhard; Demeshko, Serhiy

    2010-03-01

    In the context of a potential modeling of reduced oxovanadium species occurring on the surfaces of silica-supported vanadia catalysts in the course of its turnover, the incompletely condensed silsesquioxane H(3)(c-pentyl)T(7) was reacted with Cl(4)V(THF)(2) (where THF = tetrahydrofuran) in the presence of triethylamine. Precipitation of 3 equiv of HNEt(3)Cl seemed to point to the clean formation of [((c-pentyl)T(7))(V(IV)Cl)] (1), which was supported by electron paramagnetic resonance studies performed for the resulting solutions, but further analytical and spectroscopic investigations showed that the processes occurring at that stage are more complex than that and even include the formation of [((c-pentyl)T(7))(V(V)O)](2) as a side product. Storage of a red-brown hexane solution of this product mixture reproducibly led to the precipitation of blue crystals belonging to the chloride-free compound [((c-pentyl)T(7))(2)(V(IV)=O)(3)(THF)(2)] (2), as revealed by single-crystal X-ray diffraction. Performing the same reaction in the presence of 2 equiv of pyridine leads to an analogous product, where the THF ligands are replaced by pyridine. Subsequent investigations showed that the terminal oxo ligands at the vanadium centers are, on the one hand, due to the presence of adventitious water; on the other hand, the [(c-pentyl)T(7)](3-) ligand also acted as a source of O(2-). The results of SQUID measurements performed for 2 can be interpreted in terms of a ferromagnetic coupling between the vanadyl units. Exposing 2 to a dioxygen atmosphere resulted in its immediate oxidation to yield the V(V) complex [((c-pentyl)T(7))(V(V)O)](2), which may model a fast reoxidation reaction of oxovanadium(IV) trimers on silica surfaces.

  10. Hydrophobic Silsesquioxane Nanoparticles and Nanocomposite Surfaces (POSTPRINT)

    DTIC Science & Technology

    2006-05-04

    Fluorinated Polyhedral Oligomeric Silsesquioxanes are hydrophobic nanoparticles. One compound, FD8T8, is ultrahydrophobic, possessing a water contact ... angle of 154 deg. This is believed to be the most hydrophobic and lowest surface tension crystalline substance known. Analysis of the x-ray crystal

  11. Pysico-chemical properties of hydrophobic ionic liquids containing1-octylpyridinium, 1-octyl-2-methylpyridinium or1-octyl-4-methylpyridinium cations

    SciTech Connect

    Papaiconomou, Nicolas; Salminen, Justin; Lee, Jong-Min; Prausnitz, John M.

    2006-09-15

    This paper reports synthesis of some ionic liquids based on cations 1-octylpyridinium, 1-octyl-2-methylpyridinium or 1-octyl-4-methylpyridinium and anions dicyanamide [N(CN)2]-, bis(trifluoromethylsulfonyl)imide [Tf2N]-, bis(pentafluoroethylsulfonyl)imide [BETI]-, trifluoromethyl sulfonate [TfO]-, nonafluorobutyl sulfonate [NfO]-, tetrafluoroborate [BF4]-, trifluorophenylborate [BF3Ph]- or hexafluoroarsenate [AsF6]-. Melting points, decomposition temperatures, densities, mutual solubilities with water, and viscosities have been measured. Unlike similar ionic liquids containing imidazolium cations, pyridinium ionic liquids studied here are nearly immiscible in water. Viscosities are similar and water content is slightly lower than those for ionic liquids containing imidazolium cations.

  12. Synthesis and Characterization of Polyfunctional Polyhedral Silsesquioxane Cages

    NASA Astrophysics Data System (ADS)

    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

  13. Silsesquioxane nanoparticles with reactive internal functional groups

    NASA Astrophysics Data System (ADS)

    Brozek, Eric M.; Washton, Nancy M.; Mueller, Karl T.; Zharov, Ilya

    2017-02-01

    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.

  14. Characterization of isomeric 1,2,4-oxadiazolyl-N-methylpyridinium salts by electrospray ionization tandem mass spectrometry.

    PubMed

    Avellone, Guiseppe; Bongiorno, David; Buscemi, Silvestre; Ceraulo, Leopoldo; Indelicato, Serena; Pace, Andrea; Pibiri, Ivana; Vivona, Nicolò

    2007-01-01

    The mass spectrometry behavior of 1,2,4-oxadiazolyl-N-methylpyridinium salts has been investigated. These substances are of current interest as perspective ionic liquids, compounds used as green solvents for synthesis, and for their catalytic properties. The studies have been developed through ESI-MS/MS experiments. The obtained results demonstrate that a readily distinction between the two isomeric classes, 3- N-methylpyridinium- and 5-N-methylpyridinium-1,2,4-oxadiazoles, is possible through ESI-MS/MS experiments. A deeper investigation on the principal fragmentation pathways of characteristic ions has been also developed.

  15. Structural Evolution of Silica Gel and Silsesquioxane Using Thermal Curing.

    PubMed

    Hu, Nan; Rao, YuanQiao; Sun, Shengtong; Hou, Lei; Wu, Peiyi; Fan, Shaojuan; Ye, Bangjiao

    2016-08-01

    The curing of coatings of two types of siloxane containing materials, silica gel and silsesquioxane, at a modest temperature (<280℃) was studied with in situ heating Fourier transform infrared spectroscopy (FT-IR) in combination with perturbation correlation moving window (PCMW) and two-dimensional correlation spectroscopy (2D-COS) analyses. The result revealed detailed structural evolution of these two different gels. When the silica gel was heated, (Si-O)6 rings appeared from the random Si-O-Si network formed after sol gel reaction, followed by condensation of silanol groups. Upon further heating, the existing (Si-O)4 rings were broken down and converted into (Si-O)6 structures, and finally isolated silanols appeared. The transition from (Si-O)4 rings to (Si-O)6 rings was observed by IR and further confirmed with positron annihilation lifetime spectroscopy (PALS). In comparison, during the curing of hybrid silsesquioxane, the condensation of silanols happens immediately upon heating without the rearrangement of Si-O-Si network. Afterwards, the fraction of (Si-O)6 ring structure increased. (Si-O)4 structures exhibited higher stability in hybrid silsesquioxanes. In addition, the amount of silanols in silsesquioxane continued to reduce without the generation of isolated silanol in the end. The different curing behavior of silsesquioxanes from silica gel originates from the organic groups in silsesquioxanes, which lowers the cross-linking density and reduces the rigidity of siloxane network.

  16. Thermosetting Poly(imide silsesquioxane)s Featuring Reduced Moisture Affinity and Improved Processability (Post-print)

    DTIC Science & Technology

    2013-09-11

    Journal Article 3. DATES COVERED (From - To) August 2013- October 2013 4. TITLE AND SUBTITLE Thermosetting Poly(imide silsesquioxane)s Featuring Reduced... Journal article published in the ACS Macromolecules Vol. #46, Issue #18 September 2013. PA Case Number: #13496; Clearance Date: 10 Oct 2013...from oligoamic acid to oligoimide is attributed to a lower degree of rotational freedom and thus more chemical environments. Rheology . Figure 5

  17. Incompletely-Condensed Fluorinated Silsesquioxane: Synthesis and Crystal Structure

    DTIC Science & Technology

    2011-11-29

    other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a ...ABSTRACT A recently developed sub-class of POSS, fluorinated polyhedral oligomeric silsesquioxane (F-POSS), consists of a Si-O core with a periphery of...incompletely-condensed silsesquioxane, (CF3(CF2)7CH2CH2)8Si8O11(OH)2, has been synthesized via a multi-step synthesis (52% yield). The structure was

  18. Photoinduced electron transfer in rigidly linked dimethoxynapthalene-N-methylpyridinium donor-acceptor molecules

    NASA Astrophysics Data System (ADS)

    Clayton, Andrew H. A.; Ghiggino, Kenneth P.; Wilson, Gerard J.; Keyte, Peter J.; Paddon-Row, Michael N.

    1992-07-01

    Photoinduced electron transfer (ET) is studied in a series of novel molecules containing a dimethoxynaphthalene (DMN) donor and either a pyridine (P) or N-methylpyridinium (P-Me +) acceptor covalently linked via a rigid nonbornalogous bridge ( n sigma bonds in length). ET rates of the order of 10 10 s -1 were measured for the DMN- n-P-Me + series ( n = 4, 6), while no appreciable ET was observed for the DMN- n-P compounds. Electronic and nuclear factors are discussed and the results rationalized in terms of Marcus—Hush and non-adiabatic ET theories.

  19. Mitochondrial uptake of bridged bis-methylpyridinium aldoximes and induction of the "petite" phenotype in yeast.

    PubMed

    Dodin, G; Averbeck, D; Demerseman, P; Nocentini, S; Dupont, J

    1991-09-16

    The 3,3'-[omega,omega'-alkanediylbis(oxy)]bis[2- (hydroxyimino)methyl]-1-methylpyridinium derivatives bearing a linking chain of 4, 5 and 6 methylene groups are accumulated in mitochondria with increasing efficiency under the effect of the electrical potential. Accumulation does not take place with derivatives carrying a 2 and 3 methylene-long linking chain. The uptake process is saturable. The efficiency of the various derivatives to induce the "petite" phenotype in yeast reflects the uptake rate observed with purified mitochondria.

  20. Polyhedral oligomeric silsesquioxane grafted polymer in polymeric foam

    DOEpatents

    King, Bruce A.; Patankar, Kshitish A.; Costeux, Stephane; Jeon, Hyun K.

    2017-01-17

    A polymeric foam article with a polymer matrix defining multiple cells therein has a polymer component with a first polymer that is a polyhedral oligomeric silsesquioxane grafted polymer that has a weight-average molecular weight of two kilograms per mole or higher and 200 kilograms per mole or lower.

  1. Hydrophobic and Oleophobic Fluoroalkyl Functionalized Silsesquioxane Nanostructures (Preprint)

    DTIC Science & Technology

    2007-01-25

    data for 2 was been submitted to the Cambridge Crystallographic Data Center with publication number CCDC 629369. Copies can be obtained free of...charge from CCDC , 12 Union Road, Cambridge, CB2 1EZ, UK (e-mail: deposit@ccdc.cam.ac.uk). Octa(3,3,3-trifluropropyl)-T8-Silsesquioxane (2). Compound 2

  2. Crystal structure of a second triclinic polymorph of 2-methyl-pyridinium picrate.

    PubMed

    Gomathi, Jeganathan; Kalaivani, Doraisamyraja

    2015-11-01

    The title mol-ecular salt, C6H8N(+)·C6H2N3O7 (-) (systematic name: 2-methyl-pyridinium 2,4,6-tri-nitro-phenolate), crystallizes with two cations and two anions in the asymmetric unit. In the crystal, the cations are linked to the anions via bifurcated N-H⋯(O,O) hydrogen bonds, generating R 1 (2)(6) graph-set motifs. Numerous C-H⋯O hydrogen bonds are observed between these cation-anion pairs, which result in a three-dimensional network. In addition, weak aromatic π-π stacking between the 2-methyl-pyridinium rings [inter-centroid distance = 3.8334 (19) Å] and very weak stacking [inter-centroid distance = 4.0281 (16) Å] between inversion-related pairs of picrate anions is observed. The title salt is a second triclinic polymorph of the structure (also with Z' = 2) reported earlier [Anita et al. (2006). Acta Cryst. C62, o567-o570; Chan et al. (2014 ▸). CrystEngComm, 16, 4508-4538]. In the title compound, the cations and anions display a chequerboard arrangement when viewed down [100], whereas in the first polymorph, (010) layers of alternating cations and anions are apparent in a [100] view. It is inter-esting that the unit-cell lengths are almost identical for the two polymorphs, although the inter-axial angles are quite different.

  3. Identification of metabolites involved in the biodegradation of the ionic liquid 1-butyl-3-methylpyridinium bromide by activated sludge microorganisms.

    PubMed

    Pham, Thi Phuong Thuy; Cho, Chul-Woong; Jeon, Che-Ok; Chung, Yun-Jo; Lee, Min-Woo; Yun, Yeoung-Sang

    2009-01-15

    Ionic liquids (ILs) are low melting organic salts that potentially comprise wide application due to their fascinating properties and have emerged as promising "green" replacements for volatile organic solvents. Despite their nonmeasurable vapor pressure, some quantities of ILs will soon be present in effluent discharges since they do have significant solubility in water. Recently, the toxic effects of ILs toward aquatic communities have been intensively investigated, but little information is available concerning the biodegradable properties of these compounds. The objective of this study was to identify the metabolites generated during the biotransformation of 1-butyl-3-methylpyridinium by microorganisms in aerobic activated sludge. The obtained results revealed that the alkylpyridinium salt was metabolized through the sequential oxidization in different positions of the alkyl side chains. High-performance liquid chromatography and mass-spectrometry analyses demonstrated that this biodegradation led to the formation of 1-hydroxybutyl-3-methylpyridinium, 1-(2-hydroxybutal)-3-methylpyridinium, 1-(2-hydroxyethyl)-3-methylpyridinium, and methylpyridine. On the basis of these intermediate products, biodegradation pathways were also suggested. These findings provide the basic information that might be useful for assessing the factors related to the environmental fate and behavior of this commonly used pyridinium IL.

  4. Polyhedral Oligomeric Silsesquioxanes - Based Hybrid Electrolytes with Controlled Network Structure

    NASA Astrophysics Data System (ADS)

    Pan, Qiwei; Li, Christopher; Department of Materials Science; Engineering, South China University of Technology Team; Department of Materials Science; Engineering, Drexel University Team

    2015-03-01

    High ion conductivity and mechanical integrity are the most important properties in the application of solid polymer electrolytes (SPEs). We herein report synthesis and characterization of hybrid electrolytes with inorganic polyhedral oligomeric silsesquioxanes (POSS) as the crosslinker. The SPEs were prepared by a facile one-pot reactions between octakis[3-(glycidyloxy)propyldimethylsiloxy]silsesquioxane and bis(3-aminopropyl) terminated poly(ethylene glycol) (PEG) in the present of bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Uniform distribution of POSS and LiTFSI in the SPEs were confirmed by SEM-BSD and SEM-EDX. We show that both ionic conductivity and mechanical properties of the SPE can be easily tuned by varying POSS contents. Correlation between the SPE network structure and the ionic conductivity and mechanical properties will be discussed.

  5. Crystal structure of 3-methyl-pyridinium picrate: a triclinic polymorph.

    PubMed

    Gomathi, Jeganathan; Kalaivani, Doraisamyraja

    2015-10-01

    The title mol-ecular salt, C6H8N(+)·C6H2N3O7 (-) (systematic name: 3-methyl-pyridinium 2,4,6-tri-nitro-phenolate), crystallizes in the triclinic space group P-1. The crystal structure of the monoclinic polymorph (space group P21/n) has been reported [Stilinovic & Kaitner (2011 ▸). Cryst. Growth Des. 11, 4110-4119]. In the crystal, the anion and cation are linked via bifurcated N-H⋯(O,O) hydrogen bonds, enclosing an R 1 (2)(6) graph-set motif. These units are linked via C-H⋯O hydrogen bonds, forming a three-dimensional framework. Within the framework there are π-π inter-actions present, involving inversion-related picrate anions and inversion-related pyridinium cations, with inter-centroid distances of 3.7389 (14) and 3.560 (2) Å, respectively.

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

    PubMed

    Croissant, Jonas G; Cattoën, Xavier; Durand, Jean-Olivier; Wong Chi Man, Michel; Khashab, Niveen M

    2016-12-08

    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-SiO1.5, with R organic groups) and bridged silsesquioxanes (O1.5Si-R-SiO1.5) 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-SiO1.5) stand between silicas (SiO2) and silicones (R2SiO), 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.

  7. Novel silsesquioxane mixture-modified high elongation polyurethane with reduced platelet adhesion

    NASA Astrophysics Data System (ADS)

    Tao, William; Zhou, Hongyang; Zhang, Yan; Li, Gang

    2008-02-01

    We have successfully synthesized a kind of novel silsesquioxane mixture that can be used to modify the surface of biomaterial polyurethane (PU) for the purpose of making silsesquioxane/PU as low-price and high-quality biomaterial. HPLC, FTIR and 29Si NMR are used to characterize as-synthesized silsesquioxane mixture. XPS figure and SEM images show the silsesquioxane particles really self-assemble on the PU surface. Contact angle measurements verify that there is a large hysteresis loop, which relates to low- and high-surface free energy component on the surface. Platelet adsorption at 90 min of PU/silsesquioxane mixture is lower than that of poly(tetrafluoroethylene) (PTFE) and PU (two-way ANOVA, p < 0.05). Furthermore, SEM images show "island" morphologic pattern with Cooper grades I platelet adsorption morphology on the smooth PU/silsesquioxane surface, and mechanic test shows that the samples with silsesquioxane mixture can increase mechanic property of PU. On the basis of these results, we conclude that this kind of nanocomposite has promise for application in biomaterials.

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

    PubMed Central

    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

  9. Developments in Nanoscience: Polyhedral Oligomeric Silsesquioxane (POSS) - Polymers

    DTIC Science & Technology

    2006-05-31

    wt% POSS. a b 0 5 10 15 20 25 30 0.01 0.1 1 00 5 10 15 20 25 30 0 2 4 6 8 10 Approved for public release; distribution is unlimited 37 TABLES Air...DATE 08 MAR 2004 2 . REPORT TYPE 3. DATES COVERED - 4. TITLE AND SUBTITLE Developments in Nanoscience: Polyhedral Oligomeric Silsesquioxane (POSS...distribution is unlimited 2 Abstract This review is intended to cover the more recent advances in both structure-property relationships of polymers

  10. Siloxane and silsesquioxane molecules—Precursors for silicate materials

    NASA Astrophysics Data System (ADS)

    Handke, M.; Kowalewska, A.

    2011-08-01

    Preparation of ceramics by sol-gel method has been known for many years, but recently it has been developed as a method for the synthesis of nanostructural ceramic materials. Hydrolytic polycondensation of simple molecules [e.g. most widely used tetraethoxysilane (TEOS)] leads to xerogel materials that can contain macromolecules of distinct random, ladder and cage or partial cage structure. In order to obtain well-defined silsesquioxanes it is preferred to start the process with more complex molecules, bringing in a specific framework that can govern the structure of the product. In the presented work alkoxy derivatives of cyclosiloxanes and polysiloxanes as well as a hydride derivative of octahedral silsequioxane (T 8H) were applied as precursors in the process of hydrolytic polycondensation. Depending on the reaction conditions, silsesquioxane macromolecules or silica material of ordered structure were obtained. We have prepared mesoporous organiosilica materials without using any template or surfactant whatsoever. The meso-pores are created due to the unique structure of initial oligosiloxane or silsequioxane molecules and the specific interactions in the used catalyst/solvent system. In the case of octasilsesquioxane precursor, the condensation process gives directly mesoporous silica material. Dried polysilsesquioxanes were heated at the temperature of 600 °C in argon or air atmosphere (pyrolysis or ceramization). In the atmosphere of argon SiC xO y glass materials were obtained.

  11. Improvement in Char Strength with an Open Cage Silsesquioxane Flame Retardant.

    PubMed

    Bautista, Yolanda; Gozalbo, Ana; Mestre, Sergio; Sanz, Vicente

    2017-05-23

    Different characterization techniques were used to study the hydrolysis and condensation reaction kinetics of 3-methacryloxypropyltrimethoxysilane (MAPTMS) to obtain open cage silsesquioxane oligomers. The formation of hydrogen bonds, which condition the chemical structures of the resulting products, was identified. Improved thermal and fire resistant behavior of unsaturated polyester (UP) composites prepared with aluminium trihydroxide (ATH) and the synthesized oligomer were registered. Opened silsesquioxane structures also showed an improvement in the mechanical properties of the char formed after firing.

  12. Improvement in Char Strength with an Open Cage Silsesquioxane Flame Retardant

    PubMed Central

    Bautista, Yolanda; Gozalbo, Ana; Mestre, Sergio; Sanz, Vicente

    2017-01-01

    Different characterization techniques were used to study the hydrolysis and condensation reaction kinetics of 3-methacryloxypropyltrimethoxysilane (MAPTMS) to obtain open cage silsesquioxane oligomers. The formation of hydrogen bonds, which condition the chemical structures of the resulting products, was identified. Improved thermal and fire resistant behavior of unsaturated polyester (UP) composites prepared with aluminium trihydroxide (ATH) and the synthesized oligomer were registered. Opened silsesquioxane structures also showed an improvement in the mechanical properties of the char formed after firing. PMID:28772928

  13. Layered hybrid perovskites with micropores created by alkylammonium functional silsesquioxane interlayers.

    PubMed

    Kataoka, Sho; Banerjee, Subhabrata; Kawai, Akiko; Kamimura, Yoshihiro; Choi, Jun-Chul; Kodaira, Tetsuya; Sato, Kazuhiko; Endo, Akira

    2015-04-01

    Layered organic-inorganic hybrid perovskites that consist of metal halides and organic interlayers are a class of low-dimensional materials. Here, we report the fabrication of layered hybrid perovskites using metal halides and silsesquioxane with a cage-like structure. We used a silsesquioxane as an interlayer to produce a rigid structure and improve the functionality of perovskite layers. Propylammonium-functionalized silsesquioxane and metal halide salts (CuCl2, PdCl2, PbCl2, and MnCl2) were self-assembled to form rigid layered perovskite structures with high crystallinity. The rigid silsesquioxane structure produces micropores between the perovskite layers that can potentially be filled with different molecules to tune the dielectric constants of the interlayers. The obtained silsesquioxane-metal halide hybrid perovskites exhibit some characteristic properties of layered perovskites including magnetic ordering (CuCl4(2-) and MnCl4(2-)) and excitonic absorption/emission (PbCl4(2-)). Our results indicate that inserting silsesquioxane interlayers into hybrid perovskites retains and enhances the low-dimensional properties of the materials.

  14. Polyhedral oligomeric silsesquioxanes as modifiers of polyoxymethylene structure

    NASA Astrophysics Data System (ADS)

    Czarnecka-Komorowska, Dorota; Sterzynski, Tomasz; Dutkiewicz, Michal

    2015-12-01

    In this paper the influence of silsesquioxanes (POSS) on crystallization behaviour of polyoxymethylene (POM) during non-isothermal crystallization was investigated by polarized light microscope (PLM) and differential scanning calorimetry (DSC). The study concerns polyoxymethylene (POM) and nanocomposites containing POSS's with different organic functional groups ePOSS, vPOSS and hPOSS (0.5% and 1% by weight). The nucleation effectiveness was assessed by DSC determination of crystallization temperature and by optical measurement of nucleation density and spherulites dimensions. An increase of crystallization temperature alone with a decrease of the average spherulites dimension deliver a proof of a nucleation - like activity of hPOSS. An additionally effect observed for POPSS modified POM was a higher homogeneity of the morphology.

  15. Thermoplastic starch-nanohybrid films with polyhedral oligomeric silsesquioxane.

    PubMed

    Martinez-Pardo, I; Shanks, Robert A; Adhikari, Benu; Adhikari, Raju

    2017-10-01

    Thermoplastic starch forms packaging films that have low gas permeability, but they are more permeable to water vapour and they are attacked by water. Our approach was to create surface and internal localised hydrophobicity using added reactive nano-materials to form nano-silica hybrids with emphasis on enhancing surface water resistance. Functionalization was via epoxy-POS, that were further linked to hydrophobic erucamide or an amphiphilic poly(oxyethylene-co-oxypropylene) mono-amine. High amylose thermoplastic starch was combined with mono-functionalised hepta-isobutyl polyhedral oligomeric silsesquioxane (POS). POS modified thermoplastic starch increased water resistance of TPS film. Wettability kinetics was a function of two distinct mechanisms each with independent linear behaviour. Surface water resistance increased and is proposed to be due to preferential location of the POS derivatives at the surface with associated increase of hydrophobicity due a surface change. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Maxillofacial Materials Reinforced with Various Concentrations of Polyhedral Silsesquioxanes

    PubMed Central

    Mohammad, Sharif A.; Wee, Alvin G.; Rumsey, Deborah J.; Schricker, Scott R.

    2010-01-01

    This study evaluates two mechanical properties, tensile strength and tear strength, of maxillofacial materials reinforced with functional polyhedral silsesquioxane (POSS) nanoparticles at 0.0, 0.5, 1.0, 2.0, and 5.0% (mass/mass) loading. Adding POSS was found to significantly affect the overall tensile strength and extensibility of the maxillofacial material. Significant differences were found in mean peak load (p = .050) and extension before failure (p = .050), respectively, between concentrations of 0% and 5%. For tear resistance, a significant difference was observed in mean load (p = .002) between concentrations of 1% and 5%. Significant differences were also observed in extension before failure between concentrations of 0% and 1% (p = .002) and between 0% and 2% (p = .002). Increased resistance to tensile or shearing stresses could lead to greater clinical longevity. The following results suggest that functional nanoparticles can be used to improve properties without compromising clinical handling. PMID:20981354

  17. Tunable Gravimetric and Volumetric Hydrogen Storage Capacities in Polyhedral Oligomeric Silsesquioxane Frameworks.

    PubMed

    Deshmukh, Amol; Chiu, Cheng-Chau; Chen, Yun-Wen; Kuo, Jer-Lai

    2016-09-28

    We study the hydrogen adsorption in porous frameworks composed of silsesquioxane cages linked via boron substituted aromatic structures by first-principles modeling. Such polyhedral oligomeric silsesquioxane (POSS) frameworks can be further modified by decorating them with metal atoms binding to the ring structures of the linkers. We have considered Sc- and Ti-doped frameworks which bind H2 via so-called Kubas interaction between hydrogen molecules and transition metal atoms. It will be demonstrated that the maximum H2 gravimetric capacity can be improved to more than 7.5 wt % by using longer linkers with more ring structures. However, the maximum H2 volumetric capacity can be tuned to more than 70 g/L by varying the size of silsesquioxane cages. We are optimistic that by varying the building blocks, POSS frameworks can be modified to meet the targets for the gravimetric and volumetric capacities set by the U.S. Department of Energy.

  18. From pico to nano: biofunctionalization of cube-octameric silsesquioxanes by peptides and miniproteins.

    PubMed

    Fabritz, Sebastian; Hörner, Sebastian; Könning, Doreen; Empting, Martin; Reinwarth, Michael; Dietz, Christian; Glotzbach, Bernhard; Frauendorf, Holm; Kolmar, Harald; Avrutina, Olga

    2012-08-21

    Polyhedral silsesquioxanes are considered valuable conjugation scaffolds. Nevertheless, only a few examples of silsesquioxane-assembled peptide oligomers have been reported to date. We developed a new bioorthogonal cube-octameric silsesquioxane (COSS) scaffold bearing eight aminooxy coupling sites allowing for the conjugation of diverse peptides via oxime ligation. We found that the coupling efficacy depends on the ligand in view of steric hindrance and electrostatic repulsion. For the first time scaffold-based conjugation of cystine-knot miniproteins having a backbone of about thirty amino acids was successfully accomplished without loss of bioactivity. Atomic force microscopy (AFM) provided further knowledge on the size of COSS verifying them as picoscaffolds growing upon bioconjugation to nano-dimension.

  19. Octa, deca, and dodeca(4-nitrophenyl) cage silsesquioxanes via 4-trimethylsilylphenyl derivatives.

    PubMed

    Miyazato, Akio; Pakjamsai, Chitsakon; Kawakami, Yusuke

    2010-04-07

    Pure octa, deca, and dodeca(4-nitrophenyl) cage silsesquioxanes were obtained by regio-selective 4-nitration of octa, deca, and dodeca(4-trimethylsilylphenyl) cage silsesquioxanes via ipso-substitution of trimethylsilyl-phenyl bonds by fuming nitric acid. 3-Nitration of octa(4-methylphenyl)octasilesquioxane was also described. The starting octa(4-methyl-, 4-isopropyl- and 4-trimethylsilylphenyl)octasilsesquioxanes were selectively formed in 9-21% isolated yield in the presence of hydrochloric acid. Mixtures of octa, deca and dodecasilsesquioxanes, with decasilsesquioxane as the main component, were formed in the presence of tetrabutylammmonium fluoride as a catalyst. All the cage compounds could be separated mainly by crystallization.

  20. MEMBRANE TECHNOLOGY: OPPORTUNITIES FOR POLYHEDRAL OLIGOMERIC SILSESQUIOXANES (POSS) IN MEMBRANE-BASED SEPARATIONS

    EPA Science Inventory

    Membrane Technology: Opportunities for Polyhedral Oligomeric Silsesquioxanes (POSS?) in Membrane-Based Separations

    Leland M. Vane, Ph.D.
    U.S. Environmental Protection Agency
    Office of Research & Development
    Cincinnati, OH 45268
    Vane.Leland@epa.gov

    A sign...

  1. MEMBRANE TECHNOLOGY: OPPORTUNITIES FOR POLYHEDRAL OLIGOMERIC SILSESQUIOXANES (POSS) IN MEMBRANE-BASED SEPARATIONS

    EPA Science Inventory

    Membrane Technology: Opportunities for Polyhedral Oligomeric Silsesquioxanes (POSS?) in Membrane-Based Separations

    Leland M. Vane, Ph.D.
    U.S. Environmental Protection Agency
    Office of Research & Development
    Cincinnati, OH 45268
    Vane.Leland@epa.gov

    A sign...

  2. 2-Amino 4-methylpyridinium 3-chlorobenzoate - A phase matchable organic nonlinear optical material for optoelectronics device applications

    NASA Astrophysics Data System (ADS)

    Babu, B.; Chandrasekaran, J.; Thirumurugan, R.; Anitha, K.; Saravanabhavan, M.

    2017-09-01

    2-Amino 4-methylpyridinium 3-chlorobenzoate (2A4M3CB) was synthesized and good quality single crystals of the size of 8 × 2 × 1.2 mm3 were harvested from methanol by the slow evaporation solution growth technique at ambient temperature. Single crystal XRD reveals that 2A4M3CB crystallized in monoclinic system with the noncentrosymmetric space group P21. The crystalline phases and functional groups of 2A4M3CB have been identified and confirmed through powder X-ray diffraction and Fourier transform infrared (FTIR) studies, respectively. 1H and 13C NMR were recorded to interpret the molecular structure. The optical transmittance window and the lower cutoff wavelength of the 2A4M3CB have been identified by UV-Vis-NIR studies. Thermal and mechanical stability of the 2A4M3CB crystals were explained by TG/DTA and Vickers hardness analysis. Charge transport mechanism and photo response properties were analyzed through dielectric and photoconductivity studies. Powder second harmonic generation (SHG) characteristics and phase matching ability were explored by Kurtz and Perry powder SHG technique.

  3. Demonstration of a Directly Photopatternable Spin-On-Glass Based on Hydrogen Silsesquioxane and Photobase Generators.

    PubMed

    Harkness; Takeuchi; Tachikawa

    1998-07-28

    A commercially available spin-on-glass material, hydrogen silsesquioxane, has been rendered photopatternable to micrometer dimensions by the introduction of a photobase generator at concentrations of <5 wt %. The cure process proceeds via hydrolysis of the silyl hydride linkage by residual water in the film, as activated by a photogenerated base catalyst. Subsequent reaction of the generated silanol with neighboring silyl hydride groups yields a thermally stable siloxane cross-link. The photochemical cross-linking of hydrogen silsesquioxane shows high sensitivity (<40 mJ/cm2) and is not inhibited by molecular oxygen. The resultant oxide films can be further cured at elevated temperature either under an inert atmosphere to minimize the dielectric constant or heated in an air atmosphere to complete the conversion to silica glass. The oxidative nature of both the photo and thermal cure processes and the release of only traces of hydrogen as byproduct results in minimal weight loss in the film during processing.

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

    PubMed

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

    2015-11-18

    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 with controlled dense and hollow structures of 100-200 nm. The hybrid composition of silsesquioxanes with 50% organic content homogeneously 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 a photoreaction of the organic fragments within the particles, as confirmed by spectroscopic monitorings. Furthermore, such nanoparticles were applied for the first time for the on-demand delivery of plasmid DNA in HeLa cancer cells via light actuation.

  5. Enzymatically degradable hybrid organic-inorganic bridged silsesquioxane nanoparticles for in vitro imaging

    NASA Astrophysics Data System (ADS)

    Fatieiev, Y.; Croissant, J. G.; Julfakyan, K.; Deng, L.; Anjum, D. H.; Gurinov, A.; Khashab, N. M.

    2015-09-01

    We describe biodegradable bridged silsesquioxane (BS) composite nanomaterials with an unusually high organic content (ca. 50%) based on oxamide components mimicking amino acid biocleavable groups. Unlike most bulk BS materials, the design of sub-200 nm nearly monodisperse nanoparticles (NPs) was achieved. These enzymatically degradable BS NPs were further tested as promising imaging nanoprobes.We describe biodegradable bridged silsesquioxane (BS) composite nanomaterials with an unusually high organic content (ca. 50%) based on oxamide components mimicking amino acid biocleavable groups. Unlike most bulk BS materials, the design of sub-200 nm nearly monodisperse nanoparticles (NPs) was achieved. These enzymatically degradable BS NPs were further tested as promising imaging nanoprobes. Electronic supplementary information (ESI) available: Detailed synthetic procedure, experimental procedure and Fig. S1-15. See DOI: 10.1039/c5nr03065j

  6. The structure and bonding properties of chosen phenyl ladder-like silsesquioxane clusters

    NASA Astrophysics Data System (ADS)

    Koleżyński, Andrzej; Jastrzębski, Witold; Szczypka, Wojciech; Kowalewska, Anna; Nowacka, Maria; Sitarz, Maciej

    2013-07-01

    The poly(phenyl silsesquioxanes) were synthesized at 30-36 °C via direct co-hydrolysis and condensation using sequential one batch, two-step reactions in the presence of potassium carbonate as the base catalyst and in the mixture THF/H2O. The structure and properties of the obtained materials were analyzed using NMR, TGA, SEC, XRD and FTIR methods. For chosen ladder-like phenyl silsesquioxane model clusters the DFT calculations by means of Gaussian09 program using B98 (DFT) method and a set 6-31G (d) of basis functions were carried out and respective infrared spectra were constructed and compared with the experimentally obtained ones. The results of topological analysis of total electron density obtained in SCF calculations (Quantum Theory of Atoms in Molecules approach) and structural analysis based on Bond Valence Method were used in detailed analysis of bonding properties in these clusters.

  7. Nano-sized Mn oxide/agglomerated silsesquioxane composite as a good catalyst for water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Madadkhani, Sepideh

    2016-12-01

    Water splitting to hydrogen and oxygen is an important reaction to store sustainable energies, and water oxidation is identified as the bottleneck for water splitting because it requires the high activation energy to perform. Herein a nano-sized Mn oxide/agglomerated silsesquioxane composite was used to synthesize an efficient catalyst for water oxidation. The composite was synthesized by a straightforward and simple procedure and characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, dynamic light scattering, X-ray diffraction spectrometry, and electrochemical methods. Silsesquioxane causes good dispersion of Mn in the composite. The water-oxidizing activity of this composite was studied in the presence of cerium(IV) ammonium nitrate. The composite at the best calcination temperature (300 °C) shows a turnover frequency 0.3 (mmol O2/mol Mn.s). Regarding the low-cost, environmentally friendly precursors, simple synthesis, and efficiency for water oxidation, the composite is a promising catalyst that can be used in artificial photosynthetic systems for water splitting. We used Agglomerated silsesquioxane as a support for nano-sized Mn oxide to synthesize a good water-oxidizing catalyst.

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

    PubMed

    Barra, Giuseppina; Vertuccio, Luigi; Vietri, Umberto; Naddeo, Carlo; Hadavinia, Homayoun; Guadagno, Liberata

    2017-09-25

    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. Silsesquioxane-based 193 nm bilayer resists: characterization and lithographic evaluation

    NASA Astrophysics Data System (ADS)

    Ito, Hiroshi; Truong, Hoa D.; Burns, Sean D.; Pfeiffer, Dirk; Huang, Wu-Song; Khojasteh, Mahmoud M.; Varanasi, P. Rao; Lercel, Mike

    2005-05-01

    Polysilsesquioxane-based 193 nm positive bilayer resists are described. In this design Si for etch resistance is placed in every repeat unit and acid-labile protected and acidic groups (and polar units) are in the side chain, allowing to incorporate each lithographically critical functionality in sufficient quantity. Fluoroalcohol is employed as an acid group instead of carboxylic acid because of its more attractive dissolution properties. Polymers were carefully analyzed by 19F, 13C, and 29Si NMR to determine composition and to quantify residual acetyl, silanol, and Q/T. Hydrogen-bonding between tertiary ester and fluoroalcohol in the polysilsesquioxanes was investigated by FT-IR and the effect of lactone incorporation on the thermal deprotection temperature elucidated. In order to better understand the dissolution behavior of exposed resist films, the silsesquioxane resist polymers were partially (ca. 30%) and fully deprotected in solution with acid and their dissolution kinetics investigated by using a quartz crystal microbalance (QCM). It has been found that the exposed areas of the silsesquioxane resists can have a very fast dissolution rate (Rmax) of >20,000 A/sec (or even >100,000 A/sec). Heating the fully deprotected model polymers to 150°C did not reduce the dissolution rate much, suggesting thermal condensation of silanol end groups is insignificant. Model deprotected polymers containing triphenylsulfonium nonaflate were exposed to 254 nm radiation, baked, and subjected to QCM measurements in order to determine whether or not acid-catalyzed silanol condensation would reduce the dissolution rate. A combination of high dose and high temperature bake resulted in significant reduction of the dissolution rate in the silsesquioxane polymer containing a small trifluoroalcohol. However, the dissolution behavior of the polymer bearing a bulky norbornene hexafluoroalcohol was unaffected by exposure and bake. Chemical and development contrast curves were generated

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

    PubMed

    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.

  11. Deducing nanopore structure and growth mechanisms in porogen-templated silsesquioxane thin films

    NASA Astrophysics Data System (ADS)

    Peng, Hua-Gen; Vallery, Richard S.; Liu, Ming; Frieze, William E.; Gidley, David W.; Yim, Jin-Heong; Jeong, Hyun-Dam; Kim, Jongmin

    2005-10-01

    Adjusting the functional group of a porogen is found to have a tremendous effect on the pore structre of porous low dielectric constant films with silsesquioxane as the matrix precursor. The pore size and interconnection length measured by positronium annihilation lifetime spectroscopy can be used to deduce the pore shape and its evolution with porosity from templates of isolated porogen molecules through film percolation. Inert, self-linkable, and amphiphilic porogens are demonstrated to randomly aggregate three-dimensionally, linearly polymerize, and form micelles, respectively.

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

    SciTech Connect

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

    2014-05-15

    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.

  13. Morphological Behavior of Thin Polyhedral Oligomeric Silsesquioxane Films at the Molecular Scale

    SciTech Connect

    G Evmenenko; B Stripe; P Dutta

    2011-12-31

    Synchrotron X-ray reflectivity (XRR) was used to study the structure of thin films of polyhedral oligomeric silsesquioxanes (POSS) with side organic chains of different flexibility and containing terminal epoxy groups. POSS films were deposited from volatile solvents on hydroxylated and hydrogen-passivated silicon surfaces. The XRR data show a variety of structural morphologies, including autophobic molecular monolayers and bilayers as well as uniform films. The role of conformational and energetic factors governing the development of different morphologies in a restricted geometry is discussed.

  14. Investigation on the vibrational and structural properties of a self-structured bridged silsesquioxane.

    PubMed

    Creff, Gaëlle; Arrachart, Guilhem; Hermet, Patrick; Wadepohl, Hubert; Almairac, Robert; Maurin, David; Sauvajol, Jean-Louis; Carcel, Carole; Moreau, Joël J E; Dieudonné, Philippe; Man, Michel Wong Chi; Bantignies, Jean-Louis

    2012-04-28

    The crystalline structure of ureidopyrimidinone-based silane (UPY) has been determined. The local and long range order structuring of the bridged silsesquioxane (MUPY) resulting from the sol-gel hydrolysis-condensation of the former precursor has been investigated by MFTIR (Mid Fourier Transform InfraRed) combined with DFT (Density Functional Theory) and XRD (X-ray diffraction) studies. These studies showed that a long range structuring exists within the organic fragments with the transcription of the DDAA (Donor-Donor-Acceptor-Acceptor) H-bonding array from UPY to MUPY whereas a disordered siloxane network was revealed in the hybrid material.

  15. Assembly of DNA curtains using hydrogen silsesquioxane as a barrier to lipid diffusion.

    PubMed

    Fazio, T A; Lee, Ja Yil; Wind, S J; Greene, E C

    2012-09-18

    We have established a single-molecule imaging experimental platform called "DNA curtains" in which DNA molecules tethered to a lipid bilayer are organized into patterns at nanofabricated metallic barriers on the surface of a microfluidic sample chamber. This technology has wide applications for real-time single-molecule imaging of protein-nucleic acid interactions. Here, we demonstrate that DNA curtains can also be made from hydrogen silsesquioxane (HSQ). HSQ offers important advantages over metallic barriers because it can be lithographically patterned directly onto fused silica slides without any requirement for further processing steps, thereby offering the potential for rapid prototype development and/or scale up for manufacturing.

  16. Synthesis of disulfide-based biodegradable bridged silsesquioxane nanoparticles for two-photon imaging and therapy of cancer cells.

    PubMed

    Croissant, Jonas G; Mauriello-Jimenez, Chiara; Maynadier, Marie; Cattoën, Xavier; Wong Chi Man, Michel; Raehm, Laurence; Mongin, Olivier; Blanchard-Desce, Mireille; Garcia, Marcel; Gary-Bobo, Magali; Maillard, Philippe; Durand, Jean-Olivier

    2015-08-07

    Biodegradable bridged silsesquioxane (BS) nanomaterials for two-photon-excited (TPE) imaging and therapy of breast cancer cells were described. A versatile synthesis was developed to design monodisperse tetra-alkoxysilylated diamino-diphenylbutadiene or Zn-porphyrin-based nanospheres of 30 to 50 nm.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    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 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. PMID:26062725

  19. Polymerizable Molecular Silsesquioxane Cage Armored Hybrid Microcapsules with In Situ Shell Functionalization.

    PubMed

    Xing, Yuxiu; Peng, Jun; Xu, Kai; Lin, Weihong; Gao, Shuxi; Ren, Yuanyuan; Gui, Xuefeng; Liang, Shengyuan; Chen, Mingcai

    2016-02-01

    We prepared core-shell polymer-silsesquioxane hybrid microcapsules from cage-like methacryloxypropyl silsesquioxanes (CMSQs) and styrene (St). The presence of CMSQ can moderately reduce the interfacial tension between St and water and help to emulsify the monomer prior to polymerization. Dynamic light scattering (DLS) and TEM analysis demonstrated that uniform core-shell latex particles were achieved. The polymer latex particles were subsequently transformed into well-defined hollow nanospheres by removing the polystyrene (PS) core with 1:1 ethanol/cyclohexane. High-resolution TEM and nitrogen adsorption-desorption analysis showed that the final nanospheres possessed hollow cavities and had porous shells; the pore size was approximately 2-3 nm. The nanospheres exhibited large surface areas (up to 486 m(2)  g(-1) ) and preferential adsorption, and they demonstrated the highest reported methylene blue adsorption capacity (95.1 mg g(-1) ). Moreover, the uniform distribution of the methacryloyl moiety on the hollow nanospheres endowed them with more potential properties. These results could provide a new benchmark for preparing hollow microspheres by a facile one-step template-free method for various applications.

  20. Superplastic behavior of silica nanowires obtained by direct patterning of silsesquioxane-based precursors

    NASA Astrophysics Data System (ADS)

    Yılmaz, Mustafa; Wollschläger, Nicole; Nasr Esfahani, Mohammad; Österle, Werner; Leblebici, Yusuf; Erdem Alaca, B.

    2017-03-01

    Silica nanowires spanning 10 μm-deep trenches are fabricated from different types of silsesquioxane-based precursors by direct e-beam patterning on silicon followed by release through deep reactive ion etching. Nanowire aspect ratios as large as 150 are achieved with a critical dimension of about 50 nm and nearly rectangular cross-sections. In situ bending tests are carried out inside a scanning electron microscope, where the etch depth of 10 μ {{m}} provides sufficient space for deformation. Silica NWs are indeed observed to exhibit superplastic behavior without fracture with deflections reaching the full etch depth, about two orders of magnitude larger than the nanowire thickness. A large-deformation elastic bending model is utilized for predicting the deviation from the elastic behavior. The results of forty different tests indicate a critical stress level of 0.1–0.4 GPa for the onset of plasticity. The study hints at the possibility of fabricating silica nanowires in a monolithic fashion through direct e-beam patterning of silsesquioxane-based resins. The fabrication technology is compatible with semiconductor manufacturing and provides silica nanowires with a very good structural integrity.

  1. Superplastic behavior of silica nanowires obtained by direct patterning of silsesquioxane-based precursors.

    PubMed

    Yılmaz, Mustafa; Wollschläger, Nicole; Esfahani, Mohammad Nasr; Österle, Werner; Leblebici, Yusuf; Alaca, B Erdem

    2017-03-17

    Silica nanowires spanning 10 μm-deep trenches are fabricated from different types of silsesquioxane-based precursors by direct e-beam patterning on silicon followed by release through deep reactive ion etching. Nanowire aspect ratios as large as 150 are achieved with a critical dimension of about 50 nm and nearly rectangular cross-sections. In situ bending tests are carried out inside a scanning electron microscope, where the etch depth of 10 [Formula: see text] provides sufficient space for deformation. Silica NWs are indeed observed to exhibit superplastic behavior without fracture with deflections reaching the full etch depth, about two orders of magnitude larger than the nanowire thickness. A large-deformation elastic bending model is utilized for predicting the deviation from the elastic behavior. The results of forty different tests indicate a critical stress level of 0.1-0.4 GPa for the onset of plasticity. The study hints at the possibility of fabricating silica nanowires in a monolithic fashion through direct e-beam patterning of silsesquioxane-based resins. The fabrication technology is compatible with semiconductor manufacturing and provides silica nanowires with a very good structural integrity.

  2. Synthesis and characterization of magnetic carbon nanotubes/silsesquioxane nanocomposite thin films

    NASA Astrophysics Data System (ADS)

    Osorio, Alice Gonçalves; Machado, Geraldo Beyer; Pereira, Marcelo Barbalho; Benvenutti, Edilson Valmir; Pereira, Luis Gustavo; Bergmann, Carlos Perez; Oliveira, Artur Harres de; Costa, Tania Maria Haas

    2016-05-01

    In the present study, magnetic carbon nanotubes (CNTs)/silsesquioxane nanocomposites were produced by sol-gel method and deposited as thin film by dip-coating process. Blank films and films with CNTs were characterized in order to evaluate their chemical composition and morphology. Profilometry technique showed the formation of films with 305 ± 22 nm of thickness for blank samples (without CNTs) and 173 ± 05 nm thickness for samples with CNTs. Microscopy techniques indicated the presence of CNTs well dispersed in the films and, with the aid of Raman and Fourier Transform Infrared spectroscopy, chemical composition of silsesquioxane matrix was evidenced and the presence of CNTs was confirmed in the films. Finally, the magnetic response of the deposited films was analyzed by Alternating Gradient-Field Magnetometer and results indicated that films reinforced with CNTs showed a hysteresis loop that indicates a coercivity of 103 Oe and the blank film did not show any significant response to the field applied. Hence, the authors suggest that this hybrid organic-inorganic material has potential to be applied as a new material for magnetic storage.

  3. Studies on the growth aspects, structural, thermal, dielectric and third order nonlinear optical properties of solution grown 4-methylpyridinium p-nitrophenolate single crystal

    NASA Astrophysics Data System (ADS)

    Devi, S. Reena; Kalaiyarasi, S.; Zahid, I. MD.; Kumar, R. Mohan

    2016-11-01

    An ionic organic optical crystal of 4-methylpyridinium p-nitrophenolate was grown from methanol by slow evaporation method at ambient temperature. Powder and single crystal X-ray diffraction studies revealed the crystal system and its crystalline perfection. The rocking curve recorded from HRXRD study confirmed the crystal quality. FTIR spectral analysis confirmed the functional groups present in the title compound. UV-visible spectral study revealed the optical window and band gap of grown crystal. The thermal, electrical and surface laser damage threshold properties of harvested crystal were examined by using TGA/DTA, LCR/Impedance Analyzer and Nd:YAG laser system respectively. The third order nonlinear optical property of grown crystal was elucidated by Z-scan technique.

  4. Synthesis, Characterization, Tautomeric Structure and Solvatochromic Behavior of Novel 4-(5-Arylazo-2-Hydroxystyryl)-1-Methylpyridinium Iodide as Potential Molecular Photoprobe

    PubMed Central

    Altalbawy, Farag; Darwish, Elham; Medhat, Mohamed; El-Zaiat, Sayed; Saleh, Hagar

    2016-01-01

    A novel series of the title compound 4-(5-arylazo-2-hydroxystyryl)-1-methylpyridinium iodide 6 has been synthesized via condensation reactions of the arylazosalicylaldehyde derivatives 4a–i with 1-methyl-picolinium iodide 5. The structures of the new arylazo compounds were characterized by 1H NMR, IR, mass spectroscopy, as well as spectral and elemental analyses. The electronic absorption spectra of arylazomerocyanine compounds 6 were measured in different buffer solutions and solvents. The pK′s and pK*′s in both the ground and excited states, respectively, were determined for the series and their correlations with the Hammett equation were examined. The results indicated that the title arylazomerocyanine dyes 6 exist in the azo form 6A in both ground and excited states. The substituent and solvent effects (solvatochromism) of the title compound arylazomerocyanine dyes were determined using the Kamlet-Taft equation and subsequently discussed. PMID:28774142

  5. Computational molecular design of polyhedral oligomeric silsesquioxane based organic-inorganic hybrid semiconductors

    NASA Astrophysics Data System (ADS)

    Qi, Feng

    Cubic silsesquioxanes (T8 SQs), with the formula of [RSiO1.5] 8, enable advanced materials design. In this thesis, a computational materials science framework, including ab initio density functional theory (DFT) calculations, molecular dynamics (MD), and Monte Carlo (MC) simulations, was developed to perform computational molecular design and crystal engineering of silsesquioxane based diacene-SQ and then octa(halogenphenyl)-SQ molecular systems. The goal of this project was to identify novel molecular architectures, a priori, that exhibit targeted self-assembly behaviors and result in materials with improved electronic properties. First, existing force fields, including our in house charge transfer reactive (CTR) force field, and COMPASS, were evaluated for simulating cubic silsesquioxane systems. All force fields reproduced the experimental structure of SQ-based crystals very well. However, only the FLX force field reproduced the experimentally observed vibrational properties and thermodynamic behavior. Next, targeting materials performance, such as high electronic mobility, a series of diacene-SQ molecules were designed and their crystal structures predicted by following the computational molecular design recipe that accounts for transport theory, symmetry relationships, polymorph prediction procedures, and solid state electronic property evaluation methods. Computationally derived diacene-SQ crystals are predicted to exhibit advanced electronic properties, such as very small band gaps and parallel packing of the acene groups in crystal structures, indicating excellent transport properties, as well as improved thermal and mechanical properties. Finally, a series of new small-band gap octa(halogenphenyl)-SQ molecular systems were identified by computationally exploring alternative architectures and functionalization of recently synthesized octa(halogenphenyl)-SQ crystals. These hybrid molecular crystals also feature other unique properties, such as solution

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Cubic Polyhedral Oligomeric Silsesquioxane Based Functional Materials: Synthesis, Assembly, and Applications.

    PubMed

    Ye, Qun; Zhou, Hui; Xu, Jianwei

    2016-05-06

    Organically modified cubic polyhedral oligomeric silsesquioxanes (POSS) have attracted increasing attention in the design of novel functional hybrid materials for applications such as porous materials, liquid crystals, semiconductors, high-temperature lubricants, fuel cells, and lithium batteries. The nanosized POSS moiety can be conveniently modified on the periphery with a variety of functional groups to lead to hybrid materials with desired functions. In addition, suitable mono-functionalized POSS derivatives can be incorporated into polymers as side chains via various synthetic strategies to offer a wide class of functional polymeric materials with tunable physical properties for targeted applications. In this Focus Review, we aim to summarize the recent developments on the chemistry and applications of POSS-based molecules and polymers. Moreover, the properties as well as assembly behavior of the POSS-based functional hybrid materials will be reviewed, and the relationship of the performance of the hybrid materials with the intrinsic nature of the POSS unit will be addressed.

  8. Theoretical studies of bonding properties and vibrational spectra of chosen ladder-like silsesquioxane clusters

    NASA Astrophysics Data System (ADS)

    Szczypka, Wojciech; Jeleń, Piotr; Koleżyński, Andrzej

    2014-10-01

    In this work the DFT calculations were carried out by means of Gaussian 09 program using B3LYP XC functional and 6-311G(d) basis set for chosen ladder-like silsesquioxane model clusters. Vibrational frequencies computations and infrared spectra were obtained subsequently for above mentioned structures. The results of topological analysis of total electron density obtained in SCF calculations (Quantum Theory of Atoms in Molecules approach) and structural analysis based on Bond Valence Method are presented in order to analyze length and ramification of ladder-like structures and various functional group influence. The calculated infrared spectra show that peak derived from vibrations of Si-O “chains” is shifting towards lower frequencies with increasing length of the ladder while at the same time, the overall strains (BVM) are diminishing.

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

    PubMed

    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.

  10. Eu³⁺-based bridged silsesquioxanes for transparent luminescent solar concentrators.

    PubMed

    Freitas, Vânia T; Fu, Lianshe; Cojocariu, Ana M; Cattoën, Xavier; Bartlett, John R; Le Parc, Rozenn; Bantignies, Jean-Louis; Man, Michel Wong Chi; André, Paulo S; Ferreira, Rute A S; Carlos, Luís D

    2015-04-29

    The sol-gel preparation of a bridged silsesquioxane containing europium(III) salts and 2-thenoyltrifluoroacetone has been achieved from a new ethane tetracarboxamide-based organosilane. Free-standing films with thicknesses up to 440 μm and maximum absolute quantum yield (q) of 0.34 ± 0.03 (excitation at 320 nm) were prepared by the drop cast method, while thin films (∼200-400 nm) spin-coated on glass substrates led to highly luminescent coatings with q = 0.60 ± 0.02 (excitation at 345 nm). The thin films were tested as planar luminescent solar concentrators and the optimized device displays an optical conversion efficiency of 12.3% in the absorbing spectral region of the active layer (300-380 nm).

  11. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    DOE PAGES

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; ...

    2015-02-17

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initialmore » monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate.« less

  12. Understanding Controls on Wetting at Fluorinated Polyhedral Oligomeric Silsesquioxane/Polymer Surfaces.

    PubMed

    Ye, Yi; Tian, Ming; Zhang, Chen; Du, Zhongjie; Mi, Jianguo

    2016-01-12

    Fluorinated polyhedral oligomeric silsesquioxane (F-POSS) nanoparticles have been widely used to enhance the hydrophobicity or oleophobicity of polymer films via constructing the specific micro/nanoscale roughness. In this work, we study the oleophobicity of pure and F-POSS-decorated poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) films using a dynamic density functional theory approach. The role of nanoparticle size and coverage and the chemical features of F-POSS and the polymer film in the wetting behavior of diiodomethane droplets has been integrated to the remaining ratio of surface potential to quantitatively characterize the corner effect. It is shown that, on the basis of universal force field parameters, the theoretically predicted contact angles are in general agreement with the available experimental data.

  13. Hydrogen silsesquioxane mold coatings for improved replication of nanopatterns by injection molding

    NASA Astrophysics Data System (ADS)

    Hobæk, Thor Christian; Matschuk, Maria; Kafka, Jan; Pranov, Henrik J.; Larsen, Niels B.

    2015-03-01

    We demonstrate the replication of nanosized pillars in polymer (cyclic olefin copolymer) by injection molding using nanostructured thermally cured hydrogen silsesquioxane (HSQ) ceramic coatings on stainless steel mold inserts with mold nanostructures produced by a simple embossing process. At isothermal mold conditions, the average pillar height increases by up to 100% and a more uniform height distribution is observed compared to a traditional metal mold insert. Thermal heat transfer simulations predict that the HSQ film retards the cooling of the polymer melt during the initial stages of replication, thus allowing more time to fill the nanoscale cavities compared to standard metal molds. A monolayer of a fluorinated silane (heptadecafluorotrichlorosilane) deposited on the mold surface reduces the mold/polymer interfacial energy to support demolding of the polymer replica. The mechanical stability of thermally cured HSQ makes it a promising material for nanopattern replication on an industrial scale without the need for slow and energy intensive variotherm processes.

  14. Light emissions from a silicon nanocrystal thin film prepared by phase separation of hydrogen silsesquioxane

    NASA Astrophysics Data System (ADS)

    Zhang, Chi; Wang, Dong-Chen; Zhou, Zhi-Quan; Hu, Fei; Lu, Ming

    2017-05-01

    We report a facile method to prepare thin film of Si nanocrystals embedded SiO2 (Si-NC:SiO2) by annealing a photoresist of hydrogen silsesquioxane (HSQ) at 1100 °C in nitrogen via a phase separation process. The spatial density, photoluminescence intensity, the photoluminescence efficiency and electroluminescence intensity of Si-NC of the sample made from HSQ, or HSQ sample, were 15.0, 5.5, 1.5 and 7.9 times as large as those of the sample made by a traditional method of annealing SiOx (1

  15. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    PubMed Central

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; Gibaud, A.; Lin, B.; Meron, M.

    2015-01-01

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initial monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate. PMID:25687953

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

    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.

  17. Free carbon phase in SiOC glasses derived from ladder-like silsesquioxanes

    NASA Astrophysics Data System (ADS)

    Jeleń, P.; Bik, M.; Nocuń, M.; Gawęda, M.; Długoń, E.; Sitarz, M.

    2016-12-01

    The main objective of this paper is to attempt to determine the structure of free carbon phase in SiOC glasses derived from ladder-like silsesquioxane precursors. The samples were fired in argon flowing atmosphere, in a wide temperature range (200-800° C). Conducted XRD, Raman, MIR spectroscopy research allowed to determine the structure of obtained materials. Combined XPS and Raman studies enabled to establishing the point of formation of free carbon in silicon oxycarbide matrix. Two most popular concepts were confronted with Raman and XPS results of free carbon phase in studied materials. This allowed to conclude that for temperatures below 800 °C carbon is present in a form of graphite domains inside glassy matrix.

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

    NASA Astrophysics Data System (ADS)

    Wang, Xiqiao; Corn, John; Hagelberg, Frank

    2013-11-01

    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 MH2n@Tm, 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 MH2@T8, it is found in all cases considered that including MH2 into the POSS cage is an endothermic process. For MH2@T10 and M = Ti, Ru, Os, Pt, inclusion of the MH2 guest into the cage turns out to be exothermic, and also leaves the cage intact. For MH4@Tm, this behavior is only observed for one system, OsH4@T10.

  19. Properties of PMR Polyimides Improved by Preparation of Polyhedral Oligomeric Silsesquioxane (POSS) Nanocomposites

    NASA Technical Reports Server (NTRS)

    Campbell, Sandi G.; Lee, Andre

    2005-01-01

    The field of hybrid organic-inorganic materials has grown drastically over the last several years. This interest stems from our ever-increasing ability to custom-build and control molecular structure at several length scales. This ability to control both the composition and structure of hybrid materials is sometimes broadly referred to as nanocomposite systems. One class of hybrid (organic-inorganic) nanostructured material is polyhedral oligomeric silsesquioxane (POSS), shown in the preceding diagram. The hybrid composition gives POSS materials dramatically enhanced properties relative to traditional hydrocarbons and inorganics. An important benefit of this technology is that it makes possible the formulations of nanostructured chemicals with excellent thermal and oxidative stability. This is largely due to the inorganic component.

  20. Mobile charge, soft breakdown, and self-healing in hydrogen silsesquioxane based intermetal dielectric

    NASA Astrophysics Data System (ADS)

    Devine, R. A. B.

    2002-09-01

    The electrical characteristics of hydrogen silsesquioxane based flowable oxide (FOxregistered) films proposed for interconnect isolation applications have been studied. It is demonstrated that negative and positive charges exist in the as-made, cured films with densities of 0.95 x1012 and 1.5 x1012 cm-2, respectively for thicknesses of 114 nm. The negative charges can be removed from the films by application of modest electric fields (positive or negative, approx1.75 MV cm-1). The positive charge can be similarly displaced but not removed from the film; this results in time dependent relaxation and redistribution of the positive charge if the films are left unbiased. Time dependent irreversible evolution of the leakage current under positive and negative bias (approx3 MV cm-1) shows a slow breakdown phenomena. An unusual self-healing effect is evidenced in these films.

  1. Polyhedral Oligomeric Silsesquioxane Enhances the Brightness of Perovskite Nanocrystal-Based Green Light-Emitting Devices.

    PubMed

    Huang, He; Lin, Hong; Kershaw, Stephen V; Susha, Andrei S; Choy, Wallace C H; Rogach, Andrey L

    2016-11-03

    The beneficial role of the insulating material polyhedral oligomeric silsesquioxane (POSS) as a solution additive or an additional hole-blocking layer to enhance the performance of electroluminescent green light-emitting devices (LEDs) based on CsPbBr3 perovskite nanocrystals is demonstrated. POSS improves the surface coverage and the morphological features of the films deposited either from supernatant or suspension of perovskite nanocrystals. The external quantum efficiency and the luminance efficiency of LEDs with an additional POSS layer reach 0.35% and 1.20 cd/A, respectively, constituting a more than 17-fold enhancement to the reference devices without POSS; the LED peak luminance reaches 2983 cd/m(2), and the device stability is improved. The POSS acts as a hole-blocking layer between the perovskite nanocrystals and TPBi, keeping both electrons and holes located within the active layer for an efficient recombination.

  2. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    SciTech Connect

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; Gibaud, A.; Lin, B.; Meron, M.

    2015-02-17

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initial monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate.

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

    SciTech Connect

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

    2015-12-17

    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. Integrated Chemical Systems: The Simultaneous Formation of Hybrid Nanocomposites of Iron Oxide and Organo Silsesquioxanes

    SciTech Connect

    Zhao, L; Clapsaddle, B; Jr., J S; Schaefer, D; Shea, K

    2004-10-15

    A sol-gel approach for the synthesis of hybrid nanocomposites of iron oxide and bridged polysilsesquioxanes has been established. The procedures allow for the simultaneous formation of iron oxide and polysilsesquioxane networks in monolithic xerogels and aerogels. These hybrid nanocomposites are synthesized from FeCl{sub 3} {center_dot} 6H{sub 2}O and functionalized silsesquioxane monomers in a one-pot reaction using epoxides as a gelation agent. The porosity and microstructure of the materials has been determined by nitrogen porosimetry, electron microscopy and ultra small angle X-ray scattering (USAXS). The hybrid nanocomposites exhibit a uniform dispersion of both components with no evidence for phase separation at length scales > 5 nm. At this limit of resolution it is not possible to distinguish between two independent interpenetrating networks integrated at molecular length scales or a random copolymer or mixtures of both.

  5. Encapsulation of titanium (IV) silsesquioxane into the NH{sub 4}USY zeolite: Preparation, characterization and application

    SciTech Connect

    Ribeiro do Carmo, Devaney Dias Filho, Newton Luiz; Ramos Stradiotto, Nelson

    2007-10-02

    This work describes the encapsulation of titanium (IV) silsesquioxane into the supercavities of NH{sub 4}USY ultra stabilized zeolite, after chemical treatment. The modified zeolite was characterized by Fourier transform infrared spectra, Nuclear magnetic resonance, scanning electronic microscopy, X-ray diffraction and thermogravity. This encapsulated titanium (IV) silsesquioxane can adsorb Azure A chloride after treatment with H{sub 3}PO{sub 4}, without modifier leaching problems. In an electrochemical study, the cyclic voltammograms of the graphite paste modified electrode, shows two redox couples with formal potential (E{sup 0}') -0.1 V and 0.21 V to I and II redox couples respectively (v=700mVs{sup -1}; Britton Robinson buffer (B-R) solution, pH 3) versus SCE ascribed to a monomer and dimmer of azure. This paper shows the use of ultra stabilized zeolite in the electrochemical field as host for molecules with nanometric dimensions.

  6. Enhanced two-photon fluorescence imaging and therapy of cancer cells via Gold@bridged silsesquioxane nanoparticles.

    PubMed

    Croissant, Jonas; Maynadier, Marie; Mongin, Olivier; Hugues, Vincent; Blanchard-Desce, Mireille; Chaix, Arnaud; Cattoën, Xavier; Wong Chi Man, Michel; Gallud, Audrey; Gary-Bobo, Magali; Garcia, Marcel; Raehm, Laurence; Durand, Jean-Olivier

    2015-01-21

    A two-photon photosensitizer with four triethoxysilyl groups is synthesized through the click reaction. This photosensitizer allows the design of bridged silsesquioxane (BS) nanoparticles through a sol-gel process; moreover, gold core BS shells or BS nanoparticles decorated with gold nanospheres are synthesized. An enhancement of the two-photon properties is noted with gold and the nanoparticles are efficient for two-photon imaging and two-photon photodynamic therapy of cancer cells.

  7. Growth and characterization of an organic single crystal: 2-[2-(4-diethylamino-phenyl)-vinyl]-1-methyl-pyridinium iodide.

    PubMed

    Senthil, K; Kalainathan, S; Ruban Kumar, A

    2014-05-05

    Optically transparent crystal of the organic salt DEASI (2-[2-(4-Diethylamino-phenyl)-vinyl]-1-methyl-pyridinium iodide) has been synthesized by using knoevenagel condensation reaction method. The synthesized material has been purified by successfully recrystallization process. Single crystals of DEASI have been grown by slow evaporation technique at room temperature. The solubility of the title material has been determined at different temperature in acetonitrile/methanol mixture. The cell parameters and crystallinity of the title crystal were determined by single crystal XRD. The powder diffraction was carried out to study the reflection plane of the grown crystal and diffraction peaks were indexed. The presence of different functional groups in the crystal was confirmed by Fourier transform infrared (FTIR) analysis. (1)H NMR spectrum was recorded to confirm the presence of hydrogen nuclei in the synthesized material. The optical property of the title crystal was studied by UV-Vis-NIR spectroscopic analysis. The melting point and thermal property of DEASI were studied using TGA/DSC technique. The Vicker's hardness (Hv) was carried out to know the category. The dielectric constant and dielectric loss of the compound decreases with an increase in frequencies. Chemical etching studies showed that the DEASI grows in the two dimensional growth mechanisms. The Kurtz-Perry powder second harmonic generation (SHG) test has done for title crystal. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Structure and conformation of 2,3-diethoxycarbonyl-1-methylpyridinium iodide studied by NMR, FTIR, Raman, X-ray diffraction and DFT methods.

    PubMed

    Barczyński, P; Ratajczak-Sitarz, M; Nowaczyk, Ł; Katrusiak, A; Dega-Szafran, Z; Komasa, A; Szafran, M

    2013-11-01

    Computational and spectroscopic properties of 2,3-diethoxycarbonyl-1-methylpyridinium iodide, 1, were studied. The crystal structure of 1 was analyzed by X-ray diffraction. Molecular geometry of title compound has been calculated using the density functional theory (DFT) at B3LYP/6-311G(d,p) level of theory and was compared with the experimental data. Iodide anion interacts electrostatically with the positively charged pyridinium nitrogen atom and via weak CH⋯I(-) hydrogen bonds. In crystals the N-methyl and ethoxycarbonyl groups are disordered in two orientations. The structures of 2 (in vacuum), 3 (in CHCl3) and 4 (in DMSO) optimized by the B3LYP/6-311G(d,p) approach are different than that in crystal 1. The experimental (13)C and (1)H chemical shifts (δexp) of the investigated ester in CDCl3 and DMSO-d6 correlate linearly with GIAO/B3LYP/6-311G(d,p) magnetic isotropic shielding constants calculated according to the screening solvation model (COSMO), δexp=a+b σcalc. The FTIR and Raman spectra of the solid compound are consisted with the X-ray structure.

  9. Growth and characterization of an organic single crystal: 2-[2-(4-Diethylamino-phenyl)-vinyl]-1-methyl-pyridinium iodide

    NASA Astrophysics Data System (ADS)

    Senthil, K.; Kalainathan, S.; Ruban Kumar, A.

    Optically transparent crystal of the organic salt DEASI (2-[2-(4-Diethylamino-phenyl)-vinyl]-1-methyl-pyridinium iodide) has been synthesized by using knoevenagel condensation reaction method. The synthesized material has been purified by successfully recrystallization process. Single crystals of DEASI have been grown by slow evaporation technique at room temperature. The solubility of the title material has been determined at different temperature in acetonitrile/methanol mixture. The cell parameters and crystallinity of the title crystal were determined by single crystal XRD. The powder diffraction was carried out to study the reflection plane of the grown crystal and diffraction peaks were indexed. The presence of different functional groups in the crystal was confirmed by Fourier transform infrared (FTIR) analysis. 1H NMR spectrum was recorded to confirm the presence of hydrogen nuclei in the synthesized material. The optical property of the title crystal was studied by UV-Vis-NIR spectroscopic analysis. The melting point and thermal property of DEASI were studied using TGA/DSC technique. The Vicker’s hardness (Hv) was carried out to know the category. The dielectric constant and dielectric loss of the compound decreases with an increase in frequencies. Chemical etching studies showed that the DEASI grows in the two dimensional growth mechanisms. The Kurtz-Perry powder second harmonic generation (SHG) test has done for title crystal.

  10. Study of different routes to develop asymmetric double decker silsesquioxane (DDSQ)

    NASA Astrophysics Data System (ADS)

    Attanayake, Gayanthi Kumari

    Silsesquioxane cages can be considered as well-defined nanosized molecules (1-3 nm) and have attracted widening interests due to their possible use as components of resourceful inorganic/organic hybrid materials, as well as their applications in optics, catalysis, polymers and electronics. Double-decker silsesquioxane (DDSQ) nanoparticles have attracted much attention recently due to the ease of which these particles can be incorporated into polymeric materials and their unique capability to reinforce polymers.These systems are of high interest to scientists, due to their unique chemical and physical properties (solubility, non-flammability, oxidation resistance, and very good dielectric properties). For example, the United States Air Force and NASA use DDSQ incorporated polymers as thermoset material and flame retardants. This thesis discussed mainly three projects. One project centered on the research to improve and optimize the synthetic routes for a large scale synthesis of DDSQ functionalized oligoimides. These procedures offer the opportunity to combine several synthetic steps into a single reaction vessel, thereby cutting processing time and costs. The second project discussed is on the synthesis of a novel (phenylethynyl)phenyl DDSQ oligomer that can be used for high temperature application. This oligomer was successfully synthesized through a one pot route with 70% yield by avoiding the tedious separation techniques, fractional distillations and Kugelroher distillation. This novel oligomer will be characterized using TGA (Thermal Gravimetric Analysis) and DSC (Differential Scanning Calorimetry) for future studies. Another novel synthetic approach towards the synthesis of (phenylethynyl)phenyl DDSQ oligomers is also discussed. This new approach was based on Pd-catalyzed silylation of aryl halides. Even though Pd-catalyzed silylation of aryl halides was successful for the T7(iBu) cage, this chemistry was not applicable for DDSQ-H cage. The main project was

  11. Surface modification of polyhedral oligomeric silsesquioxane block copolymer films by 157 nm laser light

    NASA Astrophysics Data System (ADS)

    Sarantopoulou, Evangelia; Kollia, Zoe; Cefalas, Alkiviadis Constantinos; Siokou, Ageliki Elina; Argitis, Panagiotis; Bellas, Vassilios; Kobe, Spomenka

    2009-06-01

    Thin films of ethyl polyhedral oligomeric silsesquioxane (ethyl-POSS) containing polymers at different compositions were chemically modified using laser irradiation at 157 nm. The irradiation caused photodissociation of C-O and C-H bonds followed by the formation of new chemical bonds. The content of Si-O and C-O bonds increased, as did the surface hardness. Vacuum ultraviolet (VUV) absorption, mass spectrometry, x-ray photoelectron spectroscopy, and atomic force microscopy imaging and indentation were used to evaluate the effects of the 157 nm irradiation. The chemical modification was restricted to a thin surface layer. The layer depth was determined by the penetration depth of the 157 nm VUV photons inside the thin copolymer layer. With prolonged VUV irradiation, the absorbance of the polymers increased, eventually becoming saturated. The chemical changes were accompanied by surface hardening, as evidenced by the increase in the Young's modulus from 4 to 24 GPa due to glassification of the irradiated parts. The chemically modified layer acts as a shield against photodissociation and degradation of the deeper portion of the POSS polymer by VUV radiation. Applications include the protection of solar cells on low orbit satellites from solar VUV photons.

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

    PubMed

    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.

  13. A Polyhedral Oligomeric Silsesquioxane-Polyoxometalate Hybrid Shape Amphiphile: Facile Synthesis, Characterization and Crystal Structure

    NASA Astrophysics Data System (ADS)

    Liu, Hao; Wang, Jing; Yue, Kan; Jiang, Jing; Zhang, Wen-Bin; Cheng, Stephen

    2013-03-01

    This study contains the synthesis and characterization of a novel shape amphiphile composed of two covalently conjugated inorganic nanoparticles, i.e. an isobutyl substituted polyhedral oligomeric silsesquioxane (BPOSS) cage and a Lindqvist-type hexamolybdate ([Mo6O19]2-) cluster, and its crystal structure. The facile one-step coupling strategy was realized via the highly efficient palladium-catalyzed Sonogashira reaction between an alkyne-bearing POSS derivative (BPOSS-Alkyne) and an iodo-functionalized Lindqvist precursor (Lind-Iodide) in high yield. The precisely defined molecular structure was thoroughly characterized by combination of routine techniques, such as 1H and 13C NMR, FT-IR, and MALDI-TOF mass spectroscopy. The persistent shape and chemical incompatibility of the two building blocks, as well as the rigid p-phenylene ethynylene linker, drive BPOSS-Lind to pack into a monoclinic lattice, which was confirmed by bright field transmission electron microscopy (TEM), selected area electron diffraction (SAED), small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS). This work introduces a new dumbbell-shaped giant hybrid molecule (BPOSS-Lind) and shed light on the packing behavior of this shape amphiphile.

  14. A covalently-linked microporous organic-inorganic hybrid framework containing polyhedral oligomeric silsesquioxane moieties.

    PubMed

    Peng, Ye; Ben, Teng; Xu, Jun; Xue, Ming; Jing, Xiaofei; Deng, Feng; Qiu, Shilun; Zhu, Guangshan

    2011-03-28

    By a Yamamoto-type of Ullmann cross-coupling reaction, a well-defined covalently-linked microporous organic-inorganic hybrid framework polyoctaphenylsilsesquioxane (JUC-Z1) was effectively prepared from the nano building block p-iodio-octaphenylsilsesquioxane (I8OPS) with a yield of ca. 100%. The structure of JUC-Z1 was characterized by (13)C CP/MAS NMR and (29)Si MAS NMR experiments. Fourier transform infrared spectroscopy (FTIR) was performed to confirm the presence of functions in the framework. The results showed that inorganic silsesquioxane cubes were linearly covalently-linked by biphenyls, offering a highly cross-coupling framework. The powder X-ray diffraction (PXRD) pattern and transmission electron microscope (TEM) image show that JUC-Z1 is spherical with uniform micropores. N(2) adsorption results suggest that the hybrid framework has a narrow pore size distribution from 11.8 to 20.0 Å, with a BET surface area of 283 m(2)g(-1) and a pore volume of 0.226 cm(3)g(-1). A thermogravimetric (TG) analysis indicates the thermal stability of JUC-Z1 up to 397 °C in air. Moreover, a liquid sorption experiment reveals the favorable sorption of benzene and water.

  15. Low-voltage-exposure-enabled hydrogen silsesquioxane bilayer-like process for three-dimensional nanofabrication

    NASA Astrophysics Data System (ADS)

    Xiang, Quan; Chen, Yiqin; Wang, Yasi; Zheng, Mengjie; Li, Zhiqin; Peng, Wei; Zhou, Yanming; Feng, Bo; Chen, Yifang; Duan, Huigao

    2016-06-01

    We report a bilayer-like electron-beam lithographic process to obtain three-dimensional (3D) nanostructures by using only a single hydrogen silsesquioxane (HSQ) resist layer. The process utilizes the short penetration depth of low-energy (1.5 keV) electron irradiation to first obtain a partially cross-linked HSQ top layer and then uses a high-voltage electron beam (30 keV) to obtain self-aligned undercut (e.g. mushroom-shaped) and freestanding HSQ nanostructures. Based on the well-defined 3D resist patterns, 3D metallic nanostructures were directly fabricated with high fidelity by just depositing a metallic layer. As an example, Ag-coated mushroom-shaped nanostructures were fabricated, which showed lower plasmon resonance damping compared to their planar counterparts. In addition, the undercut 3D nanostructures also enable more reliable lift-off in comparison with the planar nanostructures, with which high-quality silver nanohole arrays were fabricated which show distinct and extraordinary optical transmission in the visible range.

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

    PubMed

    Wang, Weiguo; Sun, Xiang; Huang, Li; Gao, Yu; Ban, Jinghao; Shen, Lijuan; Chen, Jihua

    2014-01-01

    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.

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

    PubMed Central

    Wang, Weiguo; Sun, Xiang; Huang, Li; Gao, Yu; Ban, Jinghao; Shen, Lijuan; Chen, Jihua

    2014-01-01

    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. PMID:24550674

  18. Investigation of the Hydrogen Silsesquioxane (HSQ) Electron Resist as Insulating Material in Phase Change Memory Devices

    NASA Astrophysics Data System (ADS)

    Zhou, Jiao; Ji, Hongkai; Lan, Tian; Yan, Junbing; Zhou, Wenli; Miao, Xiangshui

    2015-01-01

    Phase change random access memory (PCRAM) affords many advantages over conventional solid-state memories due to its nonvolatility, high speed, and scalability. However, high programming current to amorphize the crystalline phase through the melt-quench process of PCRAM, known as the RESET current, poses a critical challenge and has become the most significant obstacle for its widespread commercialization. In this work, an excellent negative tone resist for high resolution electron beam lithography, hydrogen silsesquioxane (HSQ), has been investigated as the insulating material which locally blocks the contact between the bottom electrode and the phase change material in PCRAM devices. Fabrications of the highly scaled HSQ nanopore arrays (as small as 16 nm) are presented. The insulating properties of the HSQ material are studied, especially under e-beam exposure plus thermal curing. Some other critical issues about the thickness adjustment of HSQ films and the influence of the PCRAM electrode on electron scattering in e-beam lithography are discussed. In addition, the HSQ material was successfully integrated into the PCRAM devices, achieving ultra-low RESET current (sub-100 μA), outstanding on/off ratios (~50), and improved endurance at tens of nanometers.

  19. Investigation of the Hydrogen Silsesquioxane (HSQ) Electron Resist as Insulating Material in Phase Change Memory Devices

    NASA Astrophysics Data System (ADS)

    Zhou, Jiao; Ji, Hongkai; Lan, Tian; Yan, Junbing; Zhou, Wenli; Miao, Xiangshui

    2014-09-01

    Phase change random access memory (PCRAM) affords many advantages over conventional solid-state memories due to its nonvolatility, high speed, and scalability. However, high programming current to amorphize the crystalline phase through the melt-quench process of PCRAM, known as the RESET current, poses a critical challenge and has become the most significant obstacle for its widespread commercialization. In this work, an excellent negative tone resist for high resolution electron beam lithography, hydrogen silsesquioxane (HSQ), has been investigated as the insulating material which locally blocks the contact between the bottom electrode and the phase change material in PCRAM devices. Fabrications of the highly scaled HSQ nanopore arrays (as small as 16 nm) are presented. The insulating properties of the HSQ material are studied, especially under e-beam exposure plus thermal curing. Some other critical issues about the thickness adjustment of HSQ films and the influence of the PCRAM electrode on electron scattering in e-beam lithography are discussed. In addition, the HSQ material was successfully integrated into the PCRAM devices, achieving ultra-low RESET current (sub-100 μA), outstanding on/off ratios (~50), and improved endurance at tens of nanometers.

  20. Synthesis and Self-Assembly Behaviors of Polyhedral Oligomeric Silsesquioxane Based Giant Molecular Shape Amphiphiles

    NASA Astrophysics Data System (ADS)

    Yue, Kan; Yu, Xinfei; Liu, Chang; Zhang, Wen-Bin; Cheng, Stephen

    2013-03-01

    Recently, our group has focus on the synthesis and characterization of novel giant molecular shape amphiphiles (GMSAs) based on functionalized molecular nanoparticles (MNPs), such as polyhedral oligomeric silsesquioxane (POSS), tethered with polymeric tails. A general synthetic method via the combination of sequential ?click? reactions has been developed and several model GMSAs with various tail lengths and distinct molecular topologies, which can be referred as the ?giant surfactants?, ?giant lipids?, ?giant gemini surfactants?, and ?giant bolaform surfactants? etc., have been demonstrated. Studies on their self-assembly behaviors in the bulk have revealed the formation of different ordered mesophase structures with feature sizes around 10 nanometers, which have been investigated in detail by small angle X-ray scattering (SAXS) technique and transmission electron microscopy (TEM). These findings have general implications on understanding the underlying principles of self-assembly behaviors of GMSAs, and might have potential applications in nano-patterning technology. This work is supported by NSF (DMR-0906898) and the Joint-Hope Foundation.

  1. Assessment of antifouling efficacy of polyhedral oligomeric silsesquioxane based poly (urea-urethane-imide) hybrid membranes.

    PubMed

    Ajit Walter, P; Muthukumar, T; Reddy, B S R

    2015-09-01

    A series of polyhedral oligomeric silsesquioxane (POSS) based poly(urea-urethane-imide) (PUUI-POSS) membranes were synthesized by varying the proportions of imide using 2,4-toluene diisocyanate (TDI) and bis(aminopropyl) terminated polydimethylsiloxane (PDMS). The molecular structures of poly(urea-urethane-imide)s were characterized by Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic technique. Incorporation of imide domain and its influence on surface roughness was investigated by atomic force microscopy (AFM). Hydrophobicity of polymeric membrane surfaces was determined by contact angle measurement. The thermal properties of the polymers were studied by thermogravimetric analysis. The antimicrobial activities and inhibition of bacterial attachment of these polymeric membranes were studied on Gram-positive (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli) by the disc-diffusion method. The antifouling performance has been evaluated for the polymeric membranes against two bacteria (Staphylococcus aureus (ATCC 6538)) (Escherichia coli (ATCC 8739)). The polymeric membranes were incorporated with imide moiety to improve thermal stability of the polymeric materials. The synthesized polymeric membranes have shown good morphological properties for better antifouling activities. This study found that these membranes are capable of preventing micro-organisms besides offering excellent bio-fouling resistance. © 2015 The Society for Applied Microbiology.

  2. Cardiovascular application of polyhedral oligomeric silsesquioxane nanomaterials: a glimpse into prospective horizons

    PubMed Central

    Ghanbari, Hossein; de Mel, Achala; Seifalian, Alexander M

    2011-01-01

    Revolutionary advances in nanotechnology propose novel materials with superior properties for biomedical application. One of the most promising nanomaterials for biomedical application is polyhedral oligomeric silsesquioxane (POSS), an amazing nanocage consisting of an inner inorganic framework of silicon and oxygen atoms and an outer shell of organic groups. The unique properties of this nanoparticle has led to the development of a wide range of nanostructured copolymers with significantly enhanced properties including improved mechanical, chemical, and physical characteristics. Since POSS nanomaterials are highly biocompatible, biomedical application of POSS nanostructures has been intensely explored. One of the most promising areas of application of POSS nanomaterials is the development of cardiovascular implants. The incorporation of POSS into biocompatible polymers has resulted in advanced nanocomposite materials with improved hemocompatibility, antithrombogenicity, enhanced mechanical and surface properties, calcification resistance, and reduced inflammatory response, which make these materials the material of choice for cardiovascular implants. These highly versatile POSS derivatives have opened new horizons to the field of cardiovascular implant. Currently, application of POSS containing polymers in the development of new generation cardiovascular implants including heart valve prostheses, bypass grafts, and coronary stents is under intensive investigation, with encouraging outcomes. PMID:21589645

  3. Nanometer-scale fabrication of hydrogen silsesquioxane (HSQ) films with post exposure baking.

    PubMed

    Kim, Dong-Hyun; Kang, Se-Koo; Yeom, Geun-Young; Jang, Jae-Hyung

    2013-03-01

    A nanometer-scale grating structure with a 60-nm-wide gap and 200-nm-wide ridge has been successfully demonstrated on a silicon-on-insulator substrate by using a 220-nm-thick hydrogen silsesquioxane (HSQ) negative tone electron beam resist. A post exposure baking (PEB) process and hot development process with low concentration (3.5 wt%) of tetramethylammonium hydroxide (TMAH) solution were introduced to realize the grating pattern. To study the effects of post exposure baking on the HSQ resist, Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analyses were carried out. From the FT-IR and XPS analyses, it was verified that a thin SiO2 with high cross-linked network structure was formed on the HSQ surface during the PEB step. This SiO2 layer prevents the formation of unwanted bonds on the HSQ surface, which results in clearly defined grating structures with a 60-nm-gap and 200-nm-wide-ridge on the 220-nm-thick HSQ resist. The nanometer-scale grating pattern was successfully transfered to the 280-nm-thick silicon layer of a silicon-on-insulator (SOI) substrate by using inductively-coupled-plasma-reactive-ion-etching (ICP-RIE).

  4. Solute-solvent and solvent-solvent interactions in the preferential solvation of 4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide in 24 binary solvent mixtures.

    PubMed

    Bevilaqua, Tharly; Gonçalves, Thaini F; Venturini, Cristina de G; Machado, Vanderlei G

    2006-11-01

    The molar transition energy (E(T)) polarity values for the dye 4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide were collected in binary mixtures comprising a hydrogen-bond accepting (HBA) solvent (acetone, acetonitrile, dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF)) and a hydrogen-bond donating (HBD) solvent (water, methanol, ethanol, propan-2-ol, and butan-1-ol). Data referring to mixtures of water with alcohols were also analyzed. These data were used in the study of the preferential solvation of the probe, in terms of both solute-solvent and solvent-solvent interactions. These latter interactions are of importance in explaining the synergistic behavior observed for many mixed solvent systems. All data were successfully fitted to a model based on solvent-exchange equilibria. The E(T) values of the dye dissolved in the solvents show that the position of the solvatochromic absorption band of the dye is dependent on the medium polarity. The solvation of the dye in HBA solvents occurs with a very important contribution from ion-dipole interactions. In HBD solvents, the hydrogen bonding between the dimethylamino group in the dye and the OH group in the solvent plays an important role in the solvation of the dye. The interaction of the hydroxylic solvent with the other component in the mixture can lead to the formation of hydrogen-bonded complexes, which solvate the dye using a lower polar moiety, i.e. alkyl groups in the solvents. The dye has a hydrophobic nature and a dimethylamino group with a minor capability for hydrogen bonding with the medium in comparison with the phenolate group present in Reichardt's pyridiniophenolate. Thus, the probe is able to detect solvent-solvent interactions, which are implicit to the observed synergistic behavior.

  5. Solute-solvent and solvent-solvent interactions in the preferential solvation of 4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide in 24 binary solvent mixtures

    NASA Astrophysics Data System (ADS)

    Bevilaqua, Tharly; Gonçalves, Thaini F.; Venturini, Cristina de G.; Machado, Vanderlei G.

    2006-11-01

    The molar transition energy ( ET) polarity values for the dye 4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide were collected in binary mixtures comprising a hydrogen-bond accepting (HBA) solvent (acetone, acetonitrile, dimethyl sulfoxide (DMSO), and N, N-dimethylformamide (DMF)) and a hydrogen-bond donating (HBD) solvent (water, methanol, ethanol, propan-2-ol, and butan-1-ol). Data referring to mixtures of water with alcohols were also analyzed. These data were used in the study of the preferential solvation of the probe, in terms of both solute-solvent and solvent-solvent interactions. These latter interactions are of importance in explaining the synergistic behavior observed for many mixed solvent systems. All data were successfully fitted to a model based on solvent-exchange equilibria. The ET values of the dye dissolved in the solvents show that the position of the solvatochromic absorption band of the dye is dependent on the medium polarity. The solvation of the dye in HBA solvents occurs with a very important contribution from ion-dipole interactions. In HBD solvents, the hydrogen bonding between the dimethylamino group in the dye and the OH group in the solvent plays an important role in the solvation of the dye. The interaction of the hydroxylic solvent with the other component in the mixture can lead to the formation of hydrogen-bonded complexes, which solvate the dye using a lower polar moiety, i.e. alkyl groups in the solvents. The dye has a hydrophobic nature and a dimethylamino group with a minor capability for hydrogen bonding with the medium in comparison with the phenolate group present in Reichardt's pyridiniophenolate. Thus, the probe is able to detect solvent-solvent interactions, which are implicit to the observed synergistic behavior.

  6. New nanoplatforms based on UCNPs linking with polyhedral oligomeric silsesquioxane (POSS) for multimodal bioimaging

    NASA Astrophysics Data System (ADS)

    Ge, Xiaoqian; Dong, Liang; Sun, Lining; Song, Zhengmei; Wei, Ruoyan; Shi, Liyi; Chen, Haige

    2015-04-01

    A new and facile method was used to transfer upconversion luminescent nanoparticles from hydrophobic to hydrophilic using polyhedral oligomeric silsesquioxane (POSS) linking on the surface of upconversion nanoparticles. In comparison with the unmodified upconversion nanoparticles, the POSS modified upconversion nanoplatforms [POSS-UCNPs(Er), POSS-UCNPs(Tm)] displayed good monodispersion in water and exhibited good water-solubility, while their particle size did not change substantially. Due to the low cytotoxicity and good biocompatibility as determined by methyl thiazolyl tetrazolium (MTT) assay and histology and hematology analysis, the POSS modified upconversion nanoplatforms were successfully applied to upconversion luminescence imaging of living cells in vitro and nude mouse in vivo (upon excitation at 980 nm). In addition, the doped Gd3+ ion endows the POSS-UCNPs with effective T1 signal enhancement and the POSS-UCNPs were successfully applied to in vivo magnetic resonance imaging (MRI) for a Kunming mouse, which makes them potential MRI positive-contrast agents. More importantly, the corner organic groups of POSS can be easily modified, resulting in kinds of POSS-UCNPs with many potential applications. Therefore, the method and results may provide more exciting opportunities for multimodal bioimaging and multifunctional applications.A new and facile method was used to transfer upconversion luminescent nanoparticles from hydrophobic to hydrophilic using polyhedral oligomeric silsesquioxane (POSS) linking on the surface of upconversion nanoparticles. In comparison with the unmodified upconversion nanoparticles, the POSS modified upconversion nanoplatforms [POSS-UCNPs(Er), POSS-UCNPs(Tm)] displayed good monodispersion in water and exhibited good water-solubility, while their particle size did not change substantially. Due to the low cytotoxicity and good biocompatibility as determined by methyl thiazolyl tetrazolium (MTT) assay and histology and hematology

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

    PubMed

    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.

  8. Marginal integrity of restorations produced with a model composite based on polyhedral oligomeric silsesquioxane (POSS)

    PubMed Central

    CORREA, Luciano Ribeiro; BORGES, Alexandre Luiz Souto; GUIMARÃES, Heloisa Bailly; ALMEIDA, Elis Regina Nunes; POSKUS, Laiza Tatiana; SILVA, Eduardo Moreira

    2015-01-01

    Marginal integrity is one of the most crucial aspects involved in the clinical longevity of resin composite restorations. Objective To analyze the marginal integrity of restorations produced with a model composite based on polyhedral oligomeric silsesquioxane (POSS). Material and Methods A base composite (B) was produced with an organic matrix with UDMA/TEGDMA and 70 wt.% of barium borosilicate glass particles. To produce the model composite, 25 wt.% of UDMA were replaced by POSS (P25). The composites P90 and TPH3 (TP3) were used as positive and negative controls, respectively. Marginal integrity (%MI) was analyzed in bonded class I cavities. The volumetric polymerization shrinkage (%VS) and the polymerization shrinkage stress (Pss - MPa) were also evaluated. Results The values for %MI were as follows: P90 (100%) = TP3 (98.3%) = B (96.9%) > P25 (93.2%), (p<0.05). The %VS ranged from 1.4% (P90) to 4.9% (P25), while Pss ranged from 2.3 MPa (P90) to 3.9 MPa (B). For both properties, the composite P25 presented the worst results (4.9% and 3.6 MPa). Linear regression analysis showed a strong positive correlation between %VS and Pss (r=0.97), whereas the correlation between Pss and %MI was found to be moderate (r=0.76). Conclusions The addition of 25 wt.% of POSS in methacrylate organic matrix did not improve the marginal integrity of class I restorations. Filtek P90 showed lower polymerization shrinkage and shrinkage stress when compared to the experimental and commercial methacrylate composite. PMID:26537714

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    Génois, Isabelle

    2017-01-01

    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. PMID:28786939

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

    PubMed

    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.

  12. Organic-inorganic hybrid compounds containing polyhedral oligomeric silsesquioxane for conservation of stone heritage.

    PubMed

    Son, Seunghwan; Won, Jongok; Kim, Jeong-Jin; Jang, Yun Deuk; Kang, Yong Soo; Kim, Sa Dug

    2009-02-01

    Alkoxysilane solutions based on tetraethoxysilane (TEOS) have been widely used for the consolidation of decaying heritage stone surfaces. TEOS-based products polymerize within the porous structure of the decaying stone, significantly increasing the cohesion of the grains of stone components. However, they suffer from practical drawbacks, such as crack formation of the gel during the drying phase due to the developing capillary force and dense gel fractures left inside of the stone. In this study, a TEOS-based stone consolidant containing functional (3-glycidoxypropyl)trimethoxysilane (GPTMS) and polyhedral oligomeric silsesquioxane (POSS) has been prepared in order to reduce gel crack formation during the drying phase. The addition of nanometer-sized POSS and/or GPTMS having a flexible segment reduces the capillary force developed during solvent evaporation. The properties of the TEOS/GPTMS/POSS composite solutions were compared with those of commercial products (Wacker OH and Unil sandsteinfestiger OH 1:1). The gelation time was similar to that of commercial consolidants, and the TEOS/GPTMS/POSS solution was stable over a period of up to 6 months. The addition of POSS and GPTMS provided a crack-free gel, while the gel from the commercial consolidants exhibited cracks after drying. The surface hydrophobicity of the treated decayed granite increased with the addition of POSS and GPTMS, and it was higher than that of the commercial product, implying the possibility of POSS and GPTMS as barriers to the penetration of water. This result implies that the TEOS/GPTMS/POSS solution showed a high suitability for the consolidation of granite heritage.

  13. Photocurable silsesquioxane-based formulations as versatile resins for nanoimprint lithography.

    PubMed

    Lee, Bong Kuk; Cha, Nam-Goo; Hong, Lan-Young; Kim, Dong-Pyo; Tanaka, Hidekazu; Lee, Hea Yeon; Kawai, Tomoji

    2010-09-21

    Methacrylate octafunctionalized silsesquioxane (SSQMA) was shown to be an ideal material with high performance for ultraviolet (UV)-based nanoimprint lithography (NIL). The total viscosity of SSQMA-based formulations was adjusted to between 0.8 and 50 cP by incorporating low-viscosity acrylic additives, making the formulations suitable for UV-based NIL. The cured SSQMA-based formulations showed numerous desirable characteristics, including low volumetric shrinkage (4%), high Young's modulus (2.445-4.272 GPa), high resistance to oxygen plasma, high transparency to UV light, and high resistance to organic/aqueous media, as a functional imprint material for UV-based NIL and step-and-flash imprint lithography (SFIL). Using both techniques, the SSQMA-based formulations were easily transferred to relief structures with excellent imprint fidelity and minimal residual thickness. Formulations containing 50% SSQMA (wt %) were able to reproduce high-aspect-ratio nanostructures with aspect ratios as high as 4.5 using bilayer SFIL. Transparent rigiflex molds and hard replica molds with sub-50-nm size features were reproducibly duplicated by using UV-NIL with the SSQMA-based resin. Nanostructures with feature sizes down to 50 nm were successfully reproduced using these molds in both UV- and thermal-NIL processes. After repeating 20 imprinting cycles at relatively high temperature and pressure, no detectable collapse or contamination on the replica surface was observed. These properties of the SSQMA-based resins make them suitable as inexpensive and convenient components in all NIL processes that are based on physical contact.

  14. Effect of polyhedral silsesquioxane (POSS) on the flexural strength and color of interim materials.

    PubMed

    Hamza, Tamer A; Johnston, William M; Schricker, Scott R

    2014-08-01

    Polyhedral silsesquioxane (POSS) nanofillers can reinforce interim materials. However, the interaction between the POSS and the brand and its effect on color are unknown. The purpose of this study was to determine the effect on the flexural strength, color, and color stability of 4 commercially available interim materials modified with 1 wt% POSS. Four commercial interim resin materials were used in this study: Jet, Trim, Temphase, and Protemp. The flexural strength of the interim materials was measured with and without 1 wt% POSS with an Instron universal testing machine. The color of the interim material and the material with 1 wt% POSS were evaluated, followed by the evaluation of the color change after coffee staining. The data were analyzed with a 2-way analysis of variance (ANOVA) followed by the Tukey standardized range test (HSD) to determine statistical significance (α=.05). POSS enhanced the flexural strength of Protemp and Trim but had no effect on Temphase and Jet. POSS had a significant affect on the color (L*, a*, b*), but only 2 pairwise differences (in L* Trim versus Trim POSS and in a* Temphase versus Temphase POSS) were detected. The effect of POSS on color change after coffee staining was minimal. POSS only had a significant effect on ΔL, and only 1 pairwise difference was detected (Temphase versus Temphase POSS). The collapsed means revealed significant differences in color change among brands after coffee staining. The reinforcement effect of POSS on flexural strength depended on the brand, suggesting that the chemistry of the resin affects the ability of POSS to modify mechanical properties. POSS affected the initial color of the interim materials but had little effect on the color change after coffee staining. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  15. Marginal integrity of restorations produced with a model composite based on polyhedral oligomeric silsesquioxane (POSS).

    PubMed

    Correa Netto, Luciano Ribeiro; Borges, Alexandre Luiz Souto; Guimarães, Heloisa Bailly; Almeida, Elis Regina Nunes de; Poskus, Laiza Tatiana; Silva, Eduardo Moreira da

    2015-10-01

    Marginal integrity is one of the most crucial aspects involved in the clinical longevity of resin composite restorations. To analyze the marginal integrity of restorations produced with a model composite based on polyhedral oligomeric silsesquioxane (POSS). A base composite (B) was produced with an organic matrix with UDMA/TEGDMA and 70 wt.% of barium borosilicate glass particles. To produce the model composite, 25 wt.% of UDMA were replaced by POSS (P25). The composites P90 and TPH3 (TP3) were used as positive and negative controls, respectively. Marginal integrity (%MI) was analyzed in bonded class I cavities. The volumetric polymerization shrinkage (%VS) and the polymerization shrinkage stress (Pss - MPa) were also evaluated. The values for %MI were as follows: P90 (100%) = TP3 (98.3%) = B (96.9%) > P25 (93.2%), (p<0.05). The %VS ranged from 1.4% (P90) to 4.9% (P25), while Pss ranged from 2.3 MPa (P90) to 3.9 MPa (B). For both properties, the composite P25 presented the worst results (4.9% and 3.6 MPa). Linear regression analysis showed a strong positive correlation between %VS and Pss (r=0.97), whereas the correlation between Pss and %MI was found to be moderate (r=0.76). The addition of 25 wt.% of POSS in methacrylate organic matrix did not improve the marginal integrity of class I restorations. Filtek P90 showed lower polymerization shrinkage and shrinkage stress when compared to the experimental and commercial methacrylate composite.

  16. Syntheses of silsesquioxane (POSS)-based inorganic/organic hybrid and the application in reinforcement for an epoxy resin.

    PubMed

    Ni, Caihua; Ni, Guifeng; Zhang, Liping; Mi, Jiaquan; Yao, Bolong; Zhu, Changping

    2011-10-01

    A new inorganic/organic hybrid material containing silsesquioxane was prepared by the reaction of caged octa (aminopropyl silsesquioxane) (POSS-NH(2)) with n-butyl glycidyl ether (nBGE) and 1,4-butanediol diglycidyl ether (BDGE). The copolymers of POSS, nBGE, and BDGE could be obtained with varied feed ratio of POSS-NH(2), nBGE, and BDGE in the preparation. The hybrid material was added into an epoxy resin (E51) for enhancing the toughening and thermal properties of the epoxy resin. The results showed that the toughening and the thermal properties of the cured epoxy resin were greatly improved by the addition of the hybrid. The enhancement was ascribed to nano-scale effect of the POSS structure and the formation of anchor structure in the cured network. The investigation of kinetics for the curing process of the hybrid-modified epoxy resin revealed that two kinds of curing reactions occurred in different temperature ranges. They were attributed to the reactions between amino groups of the curing agent with epoxy groups of E51 and with residue epoxy groups in the hybrid. The reacting activation energies were calculated based on Kissinger's and Flynn-Wall-Ozawa's methods, respectively.

  17. A hybrid material as a sorbent phase for the disposable pipette extraction technique enhances efficiency in the determination of phenolic endocrine-disrupting compounds.

    PubMed

    Corazza, Gabriela; Merib, Josias; Magosso, Hérica A; Bittencourt, Otávio R; Carasek, Eduardo

    2017-09-01

    In this study, the hybrid material 3-n-propyl(3-methylpyridinium) silsesquioxane chloride (Si3Py(+)Cl(-)) was synthesized and investigated as a novel sorbent phase for the disposable pipette extraction (DPX) technique coupled to high-performance liquid chromatography-florescence detection. This sorbent phase was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Aqueous samples containing the phenolic endocrine-disrupting compounds bisphenol A (BPA), 17α-ethynylestradiol (EE2), 4-tert-octylphenol (4-t-OP), 4-octylphenol (4-OP) and 4-nonylphenol (4-NP) were subjected to DPX procedures and a series of optimizations was performed to determine the ideal extraction conditions using this approach. The proposed sorbent phase exhibited higher extraction efficiency than DPX-RP (reversed phase tips containing styrene-divinylbenzene), commonly used for the determination of the phenolic endocrine- disrupting-compounds under study. Satisfactory analytical performance was achieved with linear ranges from 2 to 100μgL(-1) for 4-t-OP and 1-100μgL(-1) for the other analytes. Limits of detection of 0.60μgL(-1) for 4-t-OP and 0.30μgL(-1) for other analytes, RSDs ranging from 1 to 20% and relative recoveries of 83-116% were obtained. Based on these satisfactory results, this sorbent phase represents a valuable alternative for the extraction of compounds with polar moieties in their structure. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Z-form DNA specific binding geometry of Zn(II) meso-tetrakis(N-methylpyridinium-4-yl)porphyrin probed by linear dichroism spectroscopy.

    PubMed

    Gong, Lindan; Jang, Yoon Jung; Kim, Jinheung; Kim, Seog K

    2012-08-16

    Zn(II) meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (ZnTMPyP) produced a unique linear dichroism (LD) spectrum when forming a complex with Z-form poly[d(G-C)(2)]. The spectrum was characterized by a large positive wavelength-dependent LD signal in the Soret absorption region. The magnitudes of LD in both the DNA and Soret band increased as the [porphyrin]/[DNA base] ratio increased and were larger by 20-40 times compared to the negative LD of the ZnTMPyP bound to B-form poly[d(G-C)(2)] and poly[d(A-T)(2)]. The angles calculated from LD were respectively 49° and 42° for B(x) and B(y) transitions of the porphyrin with respect to the local helix axis of Z-form poly[d(G-C)(2)]. The appearance of the unique LD spectrum for the Z-form poly[d(G-C)(2)] complex was accompanied by a bisignate circular dichroism spectrum in the Soret region, whose magnitude was proportional to the square of the porphyrin concentration, suggesting a stacking interaction between Z-form poly[d(G-C)(2)]-bound ZnTMPyP with other bound ZnTMPyP. From these observations, a conceivable binding mode of ZnTMPyP to Z-form poly[d(G-C)(2)] complex was proposed, in which ZnTMPyP binds at the major groove or across the groove. In contrast with Z-form poly[d(G-C)(2)], ZnTMPyP binds to poly[d(A-T)(2)] in a monomeric manner with the angles of 57° and 59° for the two porphyrin's transition moments with respect to the local polynucleotide helix axis. The polarized spectral properties of ZnTMPyP bound to B-form poly[d(G-C)(2)] coincide with the intercalated nonmetallic TMPyP, namely, a negative CD signal in the Soret band and a negative wavelength-dependent reduced LD signal, with a magnitude larger than that in the DNA absorption region in spite of its axial ligands.

  19. Dispersion states and surface characteristics of physically blended polyhedral oligomeric silsesquioxane/polymer hybrid nanocomposites

    NASA Astrophysics Data System (ADS)

    Misra, Rahul

    Control of dispersion and segregation states of nanostructured additives is one of the biggest challenges in realizing the optimum potential of high performance hybrid polymer nanocomposites. Polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals, with their hybrid organic-inorganic nature and flexible functionalization with a variety of organic substituents, yield possibilities to control dispersion and tune compatibility in a wide range of polymer systems. The overall goal of this research is to investigate the fundamental parameters that influence the dispersion and segregation states of POSS nanostructured chemicals, and to understand chain dynamics and conformations in physically blended POSS hybrid polymer nanocomposites (HPNC's). Multiple structural and mechanical factors influencing macro to nano scale surface and bulk properties were successfully investigated and correlated. A strategy based on thermodynamic principles for selective control of POSS dispersion states in a given polymer matrix is developed and discussed. This dissertation consists of eight chapters. Chapter 1 provides a detailed introduction about the development and current research interest in POSS/polymer nanocomposites. This chapter also discusses limitations of current advanced nanoprobe techniques. Chapter 2 establishes the overall goal of this research and specific research ii objectives. Chapter 3 establishes the preferential surface migration behavior of physically dispersed, non-reactive, closed cage octaisobutyl POSS (Oib-POSS) in a non-polar polypropylene matrix. Furthermore, influence of POSS surface segregation on the surface properties, especially nano-tribomechanical behavior is also discussed. Chapter 4 expands the studies by melt blending two different types of POSS molecules, a non-reactive, closed cage Oib-POSS and an open cage trisilanolphenyl POSS (Tsp-POSS), in a nylon 6 matrix. This chapter discusses the morphology, nano-dispersion and macro- to

  20. Thermal Stability and Ablation Behavior of Modified Polydimethylsiloxane-Based Polyurethane Composites Reinforced with Polyhedral Oligomeric Silsesquioxane.

    PubMed

    Han, Zhongyou; Xi, Yukun; Kwon, Younghwan

    2016-02-01

    Series of polydimethylsiloxane (PDMS)-based polyurethane (PU)/polyhedral oligomeric silsesquioxane (POSS) composites are prepared using ether or polyether modified diol/polyol PDMS prepolymers, isophorone diisocyanate (IPDI) and either non-reactive or reactive POSS. The effect of POSS incorporated chemically or physically, number of ethylene oxide units and crosslinking on PDMS based PU is investigated in terms of thermal stability and ablation properties. The ablation property is measured using an oxyacetylene torch test, and the ablation rate is evaluated. The results show that POSS molecules make a considerable influence on the ablative resistance, because they act as protective silica forming precursors under oxyacetylene condition. POSS molecules, especially methyl POSS, in PU matrix leads to the formation of densely accumulated spherical silica layers on the top of the ablated surface, resulting in improved ablation resistance.

  1. Phosphoric acid doped polybenzimidazole/imidazolium-modified silsesquioxane hybrid proton conducting membranes for anhydrous proton exchange membrane application

    NASA Astrophysics Data System (ADS)

    Lin, Bencai; Chu, Fuqiang; Yuan, Ningyi; Shang, Hui; Ren, Yurong; Gu, Zongzong; Ding, Jianning; Wei, Yingqiang; Yu, Xiaomin

    2014-04-01

    Phosphoric acid doped polybenzimidazole (PBI)/imidazolium-modified silsesquioxane (Im-SiO3/2) hybrid membranes with high proton conductivity at high temperature under anhydrous conditions are synthesized and characterized. The presence of Im-SiO3/2 is confirmed by FT-IR and energy-dispersive X-ray spectroscopy (EDS) mapping of silicon element. The phosphoric acid uptake and proton conductivity of the hybrid membranes increase with the Im-SiO3/2 content, and the conductivity of PBI/Im-SiO3/2-20 reaching 6.3 × 10-2 S cm-1 at 180 °C. Compared with pure PBI membranes, the introduction of Im-SiO3/2 is effective in preventing the release of the phosphoric acid component from the hybrid membranes. The properties of the prepared hybrid membranes indicate their promising prospects in anhydrous proton exchange membrane applications.

  2. Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides.

    PubMed

    Bilyachenko, Alexey N; Yalymov, Alexey I; Shul'pina, Lidia S; Mandelli, Dalmo; Korlyukov, Alexander A; Vologzhanina, Anna V; Es'kova, Marina A; Shubina, Elena S; Levitsky, Mikhail M; Shul'pin, Georgiy B

    2016-05-19

    New hexanuclear nickel(II) silsesquioxane [(PhSiO1.5)12(NiO)₆(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,5)12(NiO)₆(NaCl)(C₄H₈O₂)13(PhCN)₂(H₂O)₂ and studied by X-ray and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers.

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

    NASA Astrophysics Data System (ADS)

    Przybylak, Marcin; Maciejewski, Hieronim; Dutkiewicz, Agnieszka

    2016-11-01

    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.

  4. Patterning the mechanical properties of hydrogen silsesquioxane films using electron beam irradiation for application in mechano cell guidance

    PubMed Central

    Lanniel, Mathieu; Lu, Bingrui; Chen, Yifang; Allen, Stephanie; Buttery, Lee; Williams, Phil; Huq, Ejaz; Alexander, Morgan

    2011-01-01

    Hydrogen silsesquioxane (HSQ) is a material with the potential for studying the effect of surface stiffness on stem cell differentiation. Here, the effects of electron beam dose on the topography and the mechanical properties of HSQ obtained with or without trimethylamine (TMA) development are characterised by atomic force microscopy imaging and indentation. A correlation between the surface stiffness (uniform across the sample) and electron beam exposure is observed. Surface roughness of HSQ samples developed in TMA decreases exponentially with increasing electron beam exposure. Surface coating with plasma polymerised allylamine (ppAAm) leads to an overall decrease in stiffness values. However, the increase in surface stiffness with increasing electron beam exposure is still evident. The ppAAm coating is shown to facilitate human mesenchymal stem cell adhesion. PMID:21494321

  5. Conformation Transformation Determined by Different Self-Assembled Phases in a DNA Complex with Cationic Polyhedral Oligomeric Silsesquioxane Lipid

    SciTech Connect

    Cui,L.; Chen, D.; Zhu, L.

    2008-01-01

    In this work, a novel cube-shaped cationic lipid based on the imidazolium salt of polyhedral oligomeric silsesquioxane (POSS) was complexed with double-stranded DNA. Because of the negative spontaneous curvature of the cationic POSS imidazolium lipid, an inverted hexagonal phase resulted above the melting point of POSS crystals. Depending on the competition between the crystallization of POSS molecules and the negative spontaneous curvature of cationic POSS imidazolium lipids, different self-assembled phase morphologies were obtained. A lamellar phase was obtained when the POSS crystallization was relatively slow. When the POSS crystallization was fast, an inverted hexagonal phase was obtained with POSS lamellar crystals grown in the interstitials of DNA cylinders. On the basis of a circular dichroism study, double-stranded DNA adopted the B-form helical conformation in the inverted hexagonal phase, whereas the helical conformation was largely destroyed in the lamellar phase.

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

    NASA Astrophysics Data System (ADS)

    Somasekharan, Lakshmipriya; Thomas, Sabu; Comoy, Corinne; Sivasankarapillai, Anilkumar; Kalarikkal, Nandakumar; Lamouroux, Emmanuel

    2016-11-01

    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%.

  7. V2O5/SiO2 surface inspired, silsesquioxane-derived oxovanadium complexes and their properties.

    PubMed

    Ohde, Christian; Brandt, Marcus; Limberg, Christian; Döbler, Jens; Ziemer, Burckhard; Sauer, Joachim

    2008-01-21

    Inspired by surface species proposed to occur on heterogeneous catalysts novel oxovanadium(v) silsesquioxanes were synthesised. Reaction of a T8-silsequioxane containing two geminal OH groups with O=V(O(i)Pr)3 led to a dinuclear compound where the geminal disiloxide functions of two silsesquioxanes are bridging two O=V(O(i)Pr) moieties (2). Formation of 2 shows that--in contrast to proposals made for silica surfaces--in molecular chemistry a bidentate coordination of geminal siloxides to one vanadium centre is not favourable. With the background that species being doubly anchored to a support have been suggested to play active roles on V2O5/SiO2 catalysts an anionic complex has been prepared where a divalent dioxovanadium unit replaces one Si corner of a (RSiO1.5)8, cube (a Si-OH function remains pending) (3). 3 has been intensely investigated by vibrational spectroscopy, and to support assignments not only of the v(V=O) bands but also of the v(V-O-Si) bands, whose positions are of interest in the area of heterogeneous catalysis, isotopic enrichment studies and DFT calculations have been performed. The corresponding investigations were aided by the synthesis and analysis of a silylated derivative of 3, 4. Moreover, with regard to their potential as structural and spectroscopic models all complexes were characterised by single crystal X-ray diffraction. Finally, 2 and 3 were tested as potential catalysts for the photooxidation of cyclohexane and benzene with O2. While 2 shows a slightly higher activity than vanadylacetylacetonate, 3 leads to significantly increased turnover numbers for the conversion of benzene to phenol.

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

    PubMed

    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.

  9. SOD-like activity of Mn(II) beta-octabromo-meso-tetrakis(N-methylpyridinium-3-yl)porphyrin equals that of the enzyme itself.

    PubMed

    DeFreitas-Silva, Gilson; Rebouças, Júlio S; Spasojević, Ivan; Benov, Ludmil; Idemori, Ynara M; Batinić-Haberle, Ines

    2008-09-01

    Mn porphyrins are among the most efficient SOD mimics with potency approaching that of SOD enzymes. The most potent ones, Mn(III) N-alkylpyridylporphyrins bear positive charges in a close proximity to the metal site, affording thermodynamic and kinetic facilitation for the reaction with negatively charged superoxide. The addition of electron-withdrawing bromines onto beta-pyrrolic positions dramatically improves thermodynamic facilitation for the O2*- dismutation. We have previously characterized the para isomer, Mn(II)Br(8)TM-4-PyP(4+) [Mn(II) beta-octabromo-meso-tetrakis(N-methylpyridinium-4-yl)porphyrin]. Herein we fully characterized its meta analogue, Mn(II)Br(8)TM-3-PyP(4+) with respect to UV/vis spectroscopy, electron spray mass spectrometry, electrochemistry, O2*- dismutation, metal-ligand stability, and the ability to protect SOD-deficient Escherichia coli in comparison with its para analogue. The increased electron-deficiency of the metal center stabilizes Mn in its +2 oxidation state. The metal-centered Mn(III)/Mn(II) reduction potential, E((1/2))=+468 mV vs NHE, is increased by 416 mV with respect to non-brominated analogue, Mn(III)TM-3-PyP(5+) and is only 12 mV less positive than for para isomer. Yet, the complex is significantly more stable towards the loss of metal than its para analogue. As expected, based on the structure-activity relationships, an increase in E((1/2)) results in a higher catalytic rate constant for the O2*- dismutation, log k(cat)> or =8.85; 1.5-fold increase with respect to the para isomer. The IC(50) was calculated to be < or =3.7 nM. Manipulation of the electron-deficiency of a cationic porphyrin resulted, therefore, in the highest k(cat) ever reported for a metalloporphyrin, being essentially identical to the k(cat) of superoxide dismutases (log k(cat)=8.84-9.30). The positive kinetic salt effect points to the unexpected, unique and first time recorded behavior of Mn beta-octabrominated porphyrins when compared to other Mn

  10. Synthesis, spectroscopic characterization and X-ray crystal structure of 2-(4-methylpyridinium)-5-(4-pyridinium)-1,3-dithiolane-2,4-dicarboxylic acid dithiocyanate monohydrate

    NASA Astrophysics Data System (ADS)

    Castiñeiras, A.; Gil, M. J.; Sevillano, P.

    2000-04-01

    2-(4-Methylpyridinium)-5-(4-pyridinium)-1,3-dithiolane-2,4-dicarboxylic acid dithiocyanate monohydrate ( 2) was obtained by a spontaneous double electrophilic addition reaction between two molecules of 3-(4-pyridine)-2-mercaptopropenoic acid ( 1), and characterized by spectroscopic methods. The structure of 2, isolated as crystals, was determined by X-ray diffraction method: monoclinic, P2 1/ c, a=8.5174(7) Å, b=7.4996(5) Å, c=34.014(3) Å, β=93.303(7)°, V=2169.1(3) Å3, Z=4. In the lattice of 2 the stability is mainly due to intra and intermolecular stack formation between the aromatic ring system of pyridine and the carboxylic groups.

  11. Synthesis, characterisation and in vitro investigation of photodynamic activity of 5-(4-octadecanamidophenyl)-10,15,20-tris(N-methylpyridinium-3-yl)porphyrin trichloride on HeLa cells using low light fluence rate.

    PubMed

    Malatesti, Nela; Harej, Anja; Kraljević Pavelić, Sandra; Lončarić, Martin; Zorc, Hrvoje; Wittine, Karlo; Andjelkovic, Uros; Josic, Djuro

    2016-09-01

    Photodynamic therapy (PDT) is a treatment that aims to kill cancer cells by reactive oxygen species, mainly singlet oxygen, produced through light activation of a photosensitiser (PS). Amongst photosensitisers that attracted the most attention in the last decade are cationic and amphiphilic molecules based on porphyrin, chlorin and phthalocyanine structures. Our aim was to join this search for more optimal balance of the lipophilic and hydrophilic moieties in a PS. A new amphiphilic porphyrin, 5-(4-octadecanamidophenyl)-10,15,20-tris(N-methylpyridinium-3-yl)porphyrin trichloride (5) was synthesised and characterised by (1)H NMR, UV-vis and fluorescence spectroscopy, and by MALDI-TOF/TOF spectrometry. In vitro photodynamic activity of 5 was evaluated on HeLa cell lines and compared to the activity of the hydrophilic 5-(4-acetamidophenyl)-10,15,20-tris(N-methylpyridinium-3-yl)porphyrin trichloride (7). Low fluence rate (2mWcm(-2)) of red light (643nm) was used for the activation, and both porphyrins showed a drug dose-response as well as a light dose-response relationship, but the amphiphilic porphyrin was presented with significantly lower IC50 values. The obtained IC50 values for 5 were 1.4μM at 15min irradiation time and 0.7μM when the time of irradiation was 30min, while for 7 these values were 37 and 6 times higher, respectively. These results confirm the importance of the lipophilic component in a PS and show a potential for 5 to be used as a PS in PDT applications.

  12. Highly stable nanofluid based on polyhedral oligomeric silsesquioxane-decorated graphene oxide nanosheets and its enhanced electro-responsive behavior.

    PubMed

    Li, Yizhuo; Guan, Yanqing; Liu, Yang; Yin, Jianbo; Zhao, Xiaopeng

    2016-05-13

    Graphene oxide (GO) shows potential as an anisotropic nanofiller or a dispersed phase of electro-responsive electrorheological (ER) nanofluid due to its small size and high aspect ratio. But it is difficult to disperse GO in non-polar oil due to the hydrophilic nature of GO and thus the resulting fluid is often subject to dispersion instability and low ER effect. These disadvantages largely limit the real application of GO-based ER nanofluid. In this paper, we develop the polyhedral oligomeric silsesquioxane (POSS)-decorated GO (POSS-GO) nanosheets and demonstrate that decorating with POSS overcomes the dispersion instability of GO in silicone oil and enhances the ER effect. The morphology and structure of samples are characterized by atomic force microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and x-ray photoelectronic spectroscopy. The results show that the POSS-GO nanosheets are ultrathin with ∼3 nm thickness and have good compatibility with silicone oil and, as a result, the nanofluid of POSS-GO nanosheets in silicone oil shows high dispersion stability. After standing for one year at room temperature, no sedimentation occurs. Under an external electric field, the ER efficiency of the POSS-GO nanofluid is ten times as high as that of the pure GO fluid. This enhanced electro-responsive behavior is related to the fact that decorating with POSS partly reduces the GO and compresses the dielectrophoretic effect of the negatively charged pure GO fluid.

  13. Mass-fractal growth in niobia/silsesquioxane mixtures: a small-angle X-ray scattering study

    PubMed Central

    Besselink, Rogier; ten Elshof, Johan E.

    2014-01-01

    The nucleation and growth of niobium pentaethoxide (NPE)-derived clusters in ethanol, through acid-catalyzed hydrolysis/condensation in the presence and absence of the silsesquioxane 1,2-bis(triethoxysilyl)ethane (BTESE), was monitored at 298–333 K by small-angle X-ray scattering. The data were analyzed with a newly derived model for polydisperse mass-fractal-like structures. At 298–313 K in the absence of BTESE the data indicated the development of relatively monodisperse NPE-derived structures with self-preserving polydispersity during growth. The growth exponent was consistent with irreversible diffusion-limited cluster agglomeration. At 333 K the growth exponent was characteristic for fast-gelling reaction-limited cluster agglomeration. The reaction yielded substantially higher degrees of polydispersity. In the presence of BTESE the growth exponents were substantially smaller. The smaller growth exponent in this case is not consistent with irreversible Smoluchowski-type agglomeration. Instead, reversible Lifshitz–Slyozov-type agglomeration seems to be more consistent with the experimental data. PMID:25294980

  14. Erosion effects of atomic oxygen on polyhedral oligomeric silsesquioxane-polyimide hybrid films in low earth orbit space environment.

    PubMed

    Duo, Shuwang; Song, Mimi; Liu, Tingzhi; Hu, Changyuan; Li, Meishuan

    2013-02-01

    A novel polyimide (PI) hybrid nanocomposite containing polyhedral oligomeric silsesquioxane (POSS) had been prepared by copolymerization of trisilanolphenyl-POSS, 4,4'-oxydianiline (ODA), and pyromellitic dianhydride (PMDA). The AO resistance of these PI/POSS hybrid films was tested in the ground-based AO simulation facility. Exposed and unexposed surfaces were characterized by SEM and X-ray photoelectron spectroscopy. SEM images showed that the surface of the 20 wt% PI/POSS became much less rough than that of the pristine polyimide. Mass measurements of the samples showed that the erosion yield of the PI/POSS (20 wt.%) hybrid film was 1.2 x 10(-25) cm3/atom, and reduced to 4% of the polyimide film. The XPS data indicated that the carbon content of the near-surface region was decreased from 60.1 to 13.2 at% after AO exposure. The oxygen and silicon concentrations in the near-surface region increased to 1.96 after AO exposure. The nanometer-sized structure of POSS, with its large surface area, had led AO-irradiated samples to form a SiO2 passivation layer, which protected the underlying polymer from further AO attack. The incorporation of POSS into the polyimide could dramatically improve the AO resistance of polyimide films in low earth orbit environment.

  15. Mesoporous silica nanoparticles with organo-bridged silsesquioxane framework as innovative platforms for bioimaging and therapeutic agent delivery.

    PubMed

    Du, Xin; Li, Xiaoyu; Xiong, Lin; Zhang, Xueji; Kleitz, Freddy; Qiao, Shi Zhang

    2016-06-01

    Mesoporous silica material with organo-bridged silsesquioxane frameworks is a kind of synergistic combination of inorganic silica, mesopores and organics, resulting in some novel or enhanced physicochemical and biocompatible properties compared with conventional mesoporous silica materials with pure Si-O composition. With the rapid development of nanotechnology, monodispersed nanoscale periodic mesoporous organosilica nanoparticles (PMO NPs) and organo-bridged mesoporous silica nanoparticles (MSNs) with various organic groups and structures have recently been synthesized from 100%, or less, bridged organosilica precursors, respectively. Since then, these materials have been employed as carrier platforms to construct bioimaging and/or therapeutic agent delivery nanosystems for nano-biomedical application, and they demonstrate some unique and/or enhanced properties and performances. This review article provides a comprehensive overview of the controlled synthesis of PMO NPs and organo-bridged MSNs, physicochemical and biocompatible properties, and their nano-biomedical application as bioimaging agent and/or therapeutic agent delivery system. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    PubMed

    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).

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

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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 SF6 and O2 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.

  19. Fabrication of Large-Area Hierarchical Structure Array Using Siliconized-Silsesquioxane as a Nanoscale Etching Barrier.

    PubMed

    Lee, Bong Kuk; Baek, In-Bok; Kim, Yarkyeon; Jang, Won Ick; Yoon, Yong Sun; Yu, Han Young

    2015-06-24

    A material approach to fabricate a large-area hierarchical structure array is presented. The replica molding and oxygen (O2) plasma etching processes were combined to fabricate a large-area hierarchical structure array. Liquid blends consisting of siliconized silsesquioxane acrylate (Si-SSQA), ethylene glycol dimethacrylate (EGDMA), and photoinitiator are developed as a roughness amplifying material during O2 plasma etching. Microstructures composed of the Si-SSQA/EGDMA mixtures are fabricated by replica molding. Nanoscale roughness on molded microstructures is realized by O2 etching. The nanoscale roughness on microstructures is efficiently controlled by varying the etching time and the weight ratio of Si-SSQA to EGDMA. The hierarchical structures fabricated by combining replica molding and O2 plasma etching showed superhydrophilicity with long-term stability, resulting in the formation of hydroxyl-terminated silicon oxide layer with the reorientation limit. On the other hand, the hierarchical structures modified with a perfluorinated monolayer showed superhydrophobicity. The increment of water contact angles is consistent with increment of the nano/microroughness of hierarchical structures and decrement of the top contact area of water/hierarchical structures.

  20. Synthesis and optical characteristics of organic light-emitting dot based on well-defined octa-functionalized silsesquioxane

    NASA Astrophysics Data System (ADS)

    Xiao, Yang; Lu, Xuehong; Zhang, Xinhai; He, Chaobin

    2010-10-01

    This article reports the synthesis and characterization of a quantum-confined luminescent dot with size 2-3 nm using well-defined m-octa(bromophenyl) silsesquioxane ( m-OBPS) as core. The highly regioselective bromination of octaphenylsilsesquioxane (OPS), which is an electron-deficient nanometer-sized molecule, has been synthesized using combined catalyst of iodine and zinc chloride at room temperature in dichloromethane solvent. Based on m-OBPS, a hybrid luminescent dot with well-defined structure was synthesized. UV absorption and PL spectra of this light-emitting dot remain same in dilute solution, condensed state, and solid solution. Furthermore, time-resolved PL study indicates that the exciton decay time of the light-emitting dot remains similar regardless in dilute solution, condensed state, or blended with other polymers, suggesting that the charge carriers are well confined within the individual light-emitting dot due to the unique star-like structure and shielding alkyl chain layer. The light-emitting nano-particles can be considered as isolated chromophores as both inter- and intra- molecular aggregation are prohibited.

  1. Highly stable nanofluid based on polyhedral oligomeric silsesquioxane-decorated graphene oxide nanosheets and its enhanced electro-responsive behavior

    NASA Astrophysics Data System (ADS)

    Li, Yizhuo; Guan, Yanqing; Liu, Yang; Yin, Jianbo; Zhao, Xiaopeng

    2016-05-01

    Graphene oxide (GO) shows potential as an anisotropic nanofiller or a dispersed phase of electro-responsive electrorheological (ER) nanofluid due to its small size and high aspect ratio. But it is difficult to disperse GO in non-polar oil due to the hydrophilic nature of GO and thus the resulting fluid is often subject to dispersion instability and low ER effect. These disadvantages largely limit the real application of GO-based ER nanofluid. In this paper, we develop the polyhedral oligomeric silsesquioxane (POSS)-decorated GO (POSS-GO) nanosheets and demonstrate that decorating with POSS overcomes the dispersion instability of GO in silicone oil and enhances the ER effect. The morphology and structure of samples are characterized by atomic force microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and x-ray photoelectronic spectroscopy. The results show that the POSS-GO nanosheets are ultrathin with ∼3 nm thickness and have good compatibility with silicone oil and, as a result, the nanofluid of POSS-GO nanosheets in silicone oil shows high dispersion stability. After standing for one year at room temperature, no sedimentation occurs. Under an external electric field, the ER efficiency of the POSS-GO nanofluid is ten times as high as that of the pure GO fluid. This enhanced electro-responsive behavior is related to the fact that decorating with POSS partly reduces the GO and compresses the dielectrophoretic effect of the negatively charged pure GO fluid.

  2. Evaporation-Induced Self-Assembly of Hybrid Bridged Silsesquioxane Film and Particulate Mesophases with Integral Organic Functionality

    SciTech Connect

    LU,YUNFENG; FAN,HONGYOU; DOKE,NILESH; LOY,DOUGLAS A.; ASSINK,ROGER A.; LAVAN,DAVID A.; BRINKER,C. JEFFREY

    2000-06-12

    Since the discovery of surfactant-templated silica mesophases, the development of organic modification schemes to impart functionality to the pore surfaces has received much attention. Most recently, using the general class of compounds referred to as bridged silsesquioxanes (RO){sub 3}Si-R{prime}-Si(OR){sub 3} (Scheme 1), three research groups have reported the formation of a new class of poly(bridgedsilsesquioxane) mesophases BSQMs with integral organic functionality. In contrast to previous hybrid mesophases where organic ligands or molecules are situated on pore surfaces, this class of materials necessarily incorporates the organic constituents into the framework as molecularly dispersed bridging ligands. Although it is anticipated that this new mesostructural organization should result in synergistic properties derived from the molecular scale mixing of the inorganic and organic components, few properties of BSQMs have been measured. In addition samples prepared to date have been in the form of granular precipitates, precluding their use in applications like membranes, fluidics, and low k dielectric films needed for all foreseeable future generations of microelectronics.

  3. Durable and Hydrophobic Organic-Inorganic Hybrid Coatings via Fluoride Rearrangement of Phenyl T12 Silsesquioxane and Siloxanes.

    PubMed

    Krug, David J; Laine, Richard M

    2017-03-08

    There have been many successful efforts to enhance the water shedding properties of hydrophobic and superhydrophobic coatings, but durability is often a secondary concern. Here, we describe durable and hydrophobic coatings prepared via fluoride catalyzed rearrangement reaction of dodecaphenylsilsesquioxane [PhSiO1.5]12 (DDPS) with octamethylcyclotetrasiloxane (D4). Hydrophobic properties and wear resistance are maximized by incorporating both low surface energy moieties and cross-linkable moieties into the siloxane network. Water contact angles as high as 150 ± 4° were achieved even after 150 wear cycles with SiC sandpaper (2000 grit, 2 kPa). These hybrid organic-inorganic copolymers also have high thermal stabilities after curing at 250 °C (Td5% ≥ 340 °C in air) due to the siloxane network with a maximum Td5% of >460 °C measured for the system with the highest silsesquioxane content. The coating systems presented here offer a unique combination of hydrophobicity and mechanical/thermal stability and could greatly expand the utility of water repellent coatings.

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

    PubMed

    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.

  5. 2-Methylpyridinium/pyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olates as potent anticonvulsant agents—synthesis and crystal structure

    NASA Astrophysics Data System (ADS)

    Mangaiyarkarasi, G.; Kalaivani, D.

    2013-12-01

    The molecular salt, 2-methylpyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropy-rimidin-4-olate) ( I), is prepared from the ethanolic solution of 1-chloro-2,4-dinitrobenzene, pyrimidine-2,4,6-(1H,3H,5H)-trione (barbituric acid) and 2-methylpyridine at room temperature, and the molecular salt, pyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate ( II), is prepared from the same reactants, by dissolving them in hot DMSO and ethanol mixture at 70°C. The structures of I and II are characterized by visible, IR, 1H-NMR, 13C-NMR and elemental analysis and confirmed by single crystal X-ray analysis. Both the salts crystallize in triclinic crystal system with sp. gr. . They possess noticeable anticonvulsant activity even at low concentration (25 mg/kg). Acute toxicity studies of these complexes indicate that LD50 values are greater than 1500 mg/kg and the tested animals do not show any behavioural changes.

  6. COSMO-RS analysis on mixing properties obtained for the systems 1-butyl-X-methylpyridinium tetrafluoroborate [X = 2,3,4] and 1,ω-dibromoalkanes [ω = 1-6].

    PubMed

    Navas, Ana; Ortega, Juan; Palomar, José; Díaz, Carlos; Vreekamp, Remko

    2011-05-07

    A theoretical-experimental study for a set of 18 binary systems comprised of [bXmpy][BF(4)] (X=2-4) + 1,ω-Br(CH(2))(v)Br (v =ω=1-6) at a temperature of 298.15 K is presented. The solubility curves are determined for each binary system, establishing the intervals of measurement for the excess properties, H(E)(m) and V(E)(m). These properties are then determined for those systems that present a miscibility zone. Binary systems containing 1,ω-dibromoalkanes with ω=5,6 present reduced solubility intervals at the temperature of 298.15 K. However, the mixtures with 1,1-dibromomethane were totally miscible with the three isomers of 1-butyl-X-methylpyridinium tetrafluoroborate. Mixtures with dibromomethane present H(E)(m) <0, whereas H(E)(m) >0 for the other binary systems. Sigmoidal curves were observed for the V(E)(m) describing expansion and contraction processes for all the systems, except for the mixtures of [b2mpy][BF(4)] with the smaller dibromoalkanes, which present contraction effects. The COSMO-RS methodology was used to estimate the solubilities and the intermolecular interaction energies, giving an acceptable explanation of the behavioral structure of pure compounds and solutions. This journal is © the Owner Societies 2011

  7. 2-Methylpyridinium/pyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olates as potent anticonvulsant agents—synthesis and crystal structure

    SciTech Connect

    Mangaiyarkarasi, G.; Kalaivani, D.

    2013-12-15

    The molecular salt, 2-methylpyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropy-rimidin-4-olate) (I), is prepared from the ethanolic solution of 1-chloro-2,4-dinitrobenzene, pyrimidine-2,4,6-(1H,3H,5H)-trione (barbituric acid) and 2-methylpyridine at room temperature, and the molecular salt, pyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate (II), is prepared from the same reactants, by dissolving them in hot DMSO and ethanol mixture at 70°C. The structures of I and II are characterized by visible, IR, {sup 1}H-NMR, {sup 13}C-NMR and elemental analysis and confirmed by single crystal X-ray analysis. Both the salts crystallize in triclinic crystal system with sp. gr. P-bar1. They possess noticeable anticonvulsant activity even at low concentration (25 mg/kg). Acute toxicity studies of these complexes indicate that LD{sub 50} values are greater than 1500 mg/kg and the tested animals do not show any behavioural changes.

  8. A comparative study of the interaction of 5,10,15,20-tetrakis (N-methylpyridinium-4-yl)porphyrin and its zinc complex with DNA using fluorescence spectroscopy and topoisomerisation.

    PubMed Central

    Kelly, J M; Murphy, M J; McConnell, D J; OhUigin, C

    1985-01-01

    Binding of 5,10,15,20-tetrakis (N-methylpyridinium-4-yl)porphyrin (H2TMPyP4+) and its zinc complex (ZnTMPyP4+) to DNA is demonstrated by their coelectrophoresis and by absorption and fluorescence spectroscopic methods. Topoisomerisation of pBR322 DNA shows that H2TMPyP4+ unwinds DNA as efficiently as ethidium bromide showing that it intercalates at many sites. ZnTMPyP4+ may cause limited unwinding. Marked changes in the fluorescence spectra of the porphyrins are found in the presence of DNA. The fluorescence intensity of either H2TMPyP4+ or ZnTMPyP4+ is enhanced in the presence of poly (d(A-T)), whereas in the presence of poly (d(G-C] the fluorescence intensity of ZnTMPyP4+ is only slightly affected and that of H2TMPyP4+ markedly reduced. Both the porphyrins photosensitize the cleavage of DNA in aerated solution upon visible light irradiation. Images PMID:2987789

  9. A one-step method for the synthesis of a vinyl-containing silsesquioxane and other organolithic macromolecular precursors

    SciTech Connect

    Yuchs, S.E.; Carrado, K.A.

    1996-01-03

    Octasilsesquioxanes are well-known molecules that are presently being used as molecular building blocks in the synthesis of ceramic materials. These materials are synthesized by a variety of means, including mixing several different solution species, photochlorination of [Si{sub 8}O{sub 12}]H{sub 8} followed by treatment with neat methyl cyanide, use of acetic acid and trimethoxy-silane saturated with anhydrous HCl, and employment of excess reactants and long time scales (1-3 years). These methods were inconvenient because they were multistep procedures that used high quantities of starting materials and long reaction times, and delivered low yields of the desired products. Recently, Moran et al. reported a simple method for the synthesis of octakis(dimethylsiloxyl)octasilsesquioxane, [Si{sub 8}O{sub 12}](OSi(CH{sub 3}){sub 2}H){sub 8}. Their method involves the treatment of tetramethylammonium silicate with chlorodimethylsesquioxane in a mixed organic solvent. A one-step synthesis for the introduction of a vinyl functional group onto an octasilsesquioxane molecule has now been developed using the method of Moran. The target molecule, Octakis(vinyldimethylsiloxyl)octasilsesquioxane, [Si{sub 8}O{sub 12}](OSi-(CH{sub 3}){sub 2}(CHCH{sub 2})){sub 8}, is synthesized in high yields using tetramethylammonium silicate and chlorodimethylvinylsilane. The target molecule and several new derivatives have been synthesized and characterized by high-resolution {sup 1}H, {sup 13}C, and {sup 29}Si NMR and by IR. This method is more practical than previous synthesis schemes for the preparation of the vinyl derivative. This new synthesis route allows for the rapid formation of an air-stable silsesquioxane molecule that is easily derivatized to form new organolithic macromolecular materials (OMM`s).

  10. Functionalized bridged silsesquioxane-based nanostructured microspheres: performance as novel drug-delivery devices in bone tissue-related applications.

    PubMed

    Romeo, Hernán Esteban; Fanovich, María Alejandra

    2012-05-01

    Two kinds of functionalized nanostructured hybrid microspheres, based on the bridged silsesquioxane family, were synthesized by employing the sol-gel method via self-assembly of two different organic-inorganic bridged monomers. The architecture reached at molecular level allowed the incorporation of acetylsalicylic acid (ASA) as an anti-inflammatory model drug. The ASA-functionalized microspheres were characterized as delivery devices in simulated body fluid (SBF). The release behaviors of the synthesized microspheres (Fickian or anomalous diffusion mechanisms) were shown to be dependent on the chemical nature of the bridged monomers employed to synthesize the hybrid materials. The functionalized microspheres were proposed as delivery systems into calcium phosphate cements (CPCs), in order to slow down the characteristic drug-delivery kinetics of this kind of bone tissue-related materials. The incorporation of the new functionalized microparticles into the CPCs represented a viable methodology to modify the ASA-release kinetics in comparison to a conventional CPC containing the drug dispersed into the solid phase. The ASA-delivery profiles obtained from the microsphere-loaded CPCs showed that 40-60% of drug can be released after 2 weeks of testing in SBF. The inclusion of the microspheres into the CPC matrices allowed modification of the release profiles through a mechanism that involved two stages: (1) the diffusion of the drug through the organic-inorganic matrix of the microspheres (according to a Fickian or anomalous diffusion, depending on the nanostructuring) and (2) the subsequent diffusion of the drug through the ceramic matrix of the hardened cements. The release behavior of the composite cements was shown to be dependent on the nanostructuring of the hybrid microspheres, which can be selectively tailored by choosing the desired chemical structure of the bridged precursors employed in the sol-gel synthesis. The obtained results demonstrated the ability of

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

    NASA Astrophysics Data System (ADS)

    Iordanov, Liubomir

    The effect of low-viscosity reactive diluents on the UV-curing kinetics of the photoinitiated cationic polymerization of a polyhedral oligomeric silsesquioxane molecule having 8 glycidyl substituents (glycidyl POSS) was examined. This compound has many beneficial properties such hardness, scratch resistance, and high thermal stability, which make it suitable for UV coating applications. However, these properties are outweighed by a high viscosity that causes diffusion limitations, thus lowering the rate of polymerization. 3,3'-(oxybis(methylene))bis(3-ethyloxetane) (DOX), Limonene Dioxide (LDO), and alpha-Pinene Oxide (alphaPO) were all used as reactive diluents. Glycidyl POSS was copolymerized with each and the effect of weight percent (wt% ) composition and viscosity on the overall polymer reactivity was evaluated. The progress of the reaction was measured using optical pyrometry, and viscosity was measured using a cone-and-plate viscometer. Shear rheological studies were used to monitor the thermal curing behavior of glycidyl POSS with and without photoinitiator. The induction time (tind) and time at peak reaction temperature (tpeak) were both used to observe the progress of the reaction. At any given composition of diluent, DOX performed better than either LDO or alphaPO; DOX needed only 20 wt% dilution to show a definite induction time, whereas LDO needed almost 50 wt% dilution to produce the same effect. Similarly, LDO showed reaction times that were at least twice as long as those of DOX when compared at the same viscosity. These results successfully demonstrate that through simple copolymerization with reactive diluents, the viscosity and reactivity of glycidyl POSS can be tailored to enhance its practical use in UV coating applications.

  12. Novel heart valve prosthesis with self-endothelialization potential made of modified polyhedral oligomeric silsesquioxane-nanocomposite material.

    PubMed

    Ghanbari, Hossein; Radenkovic, Dina; Marashi, Sayed Mahdi; Parsno, Shirin; Roohpour, Nima; Burriesci, Gaetano; Seifalian, Alexander M

    2016-06-13

    In the cardiovascular system, the endothelial layer provides a natural antithrombogenic surface on the inner portion of the heart and associated vessels. For a synthetic material therefore, the ability to attract and retain endothelial or endothelial progenitor cells (EPCs), ultimately creating a single endothelial layer on its surface, is of prime importance. The authors have developed a nanocomposite polymer, based on a combination of polyhedral oligomeric silsesquioxane nanoparticles and polycarbonate urea urethane (POSS-PCU), which is biocompatible and has been used in human for the world's first synthetic trachea, tear duct, and bypass graft. In this study, the authors modified the surface of this casted nanocomposite by grafting fibronectin derived bioactive peptides [glycine-arginine-glycine-aspartic acid-glycine (GRGDG) and lauric acid conjugated GRGDG (GRGDG-LA)] to enhance the endothelialization for using heart valves leaflets from circulating EPCs. Human peripheral blood mononuclear cells were separated using Ficoll-Paque centrifugation, with harvested EPCs purified using CD34 microbead labeling and magnetic-activated cell sorting. Cells were seeded onto 96 well plates coated with POSS-PCU, GRGDG/GRGDG-LA modified POSS-PCU and PCU polymers, for a period of 21 days. Cells were studied under light, confocal, and scanning electron microscope (SEM). Fluorescence-activated cell sorting was used to analyze cell surface markers. Cell attachment and proliferation was observed in all POSS-PCU samples, significantly higher than the activity seen within the control PCU polymers (p < 0.05). Microscopic examination revealed clonal expansion and morphological changes in cells seeded on POSS-PCU. The cells expressed increasing levels of mature endothelial cell markers over time with a concurrent reduction in hematopoietic stem cell marker expression. SEM showed a mixed population of morphologically differentiated endothelial cells and EPCs. These results support

  13. Tunable porosity of crosslinked-polyhedral oligomeric silsesquioxane (POSS) supports for palladium-catalyzed aerobic alcohol oxidation in water.

    PubMed

    Sangtrirutnugul, Preeyanuch; Chaiprasert, Thanawat; Hunsiri, Warodom; Jitjaroendee, Thanudkit; Songkhum, Patsaya; Laohhasurayotin, Kritapas; Osotchan, Tanakorn; Ervithayasuporn, Vuthichai

    2017-03-24

    Polyhedral oligomeric silsesquioxane (POSS)-based materials, poly-POSS-Tn [n = 8 (1), 10 (2), 12 (3), and mix (4)], were prepared in high yields via free radical polymerization of corresponding pure forms of methacrylate-functionalized POSS monomers, MMA-POSS-Tn (n = 8, 10, 12), and the mixture form, MMA-POSS-Tmix. Powder X-ray diffraction (XRD) spectra and BET analysis indicate that 1-4 are amorphous materials with high surface areas (683-839 m2•g-1). The surface areas and total pore volumes follow the trend: poly-POSS-T12 > poly-POSS-T10 > poly-POSS-Tmix > poly-POSS-T8. In addition, based on Barrett-Joyner-Halenda (BJH) analysis, poly-POSS-T12 contains the highest amount of mesopores. The Pd nanoparticles immobilized on poly-POSS-Tn [n = 8 (5), 10 (6), 12 (7), and mix (8)] are well dispersed with 4-6 wt% Pd content and similar average particle size of 6.2-6.5 nm, according to transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDX) and microwave plasma-atomic emission spectroscopy (MP-AES). At 90 oC, the stabilized Pd nanoparticles in 5-8 catalyzed aerobic oxidation of benzyl alcohol to benzaldehyde in 72-100% yields at 6 h using a mixture of a H2O/Pluronic (P123) solution. The PdNp@poly-POSS-T8 catalyst (5) exhibited the lowest catalytic activity, as a result of its lowest surface areas, total pore volumes, and amounts of mesopores. With the catalyst 8, various benzyl alcohol derivatives were converted to the corresponding aldehydes in good to excellent yields. However, with alcoholic substrates featuring electron-withdrawing substituents, high conversions were achieved with one equivalent of K2CO3 additive and longer reaction times.

  14. Biocompatibility of Synthetic Poly(ester urethane)/Polyhedral Oligomeric Silsesquioxane Matrices with Embryonic Stem Cell Proliferation and Differentiation

    PubMed Central

    Guo, Yan-Lin; Wang, Wenshou; Otaigbe, Joshua U.

    2010-01-01

    Incorporation of polyhedral oligomeric silsesquioxanes (POSS) into poly (ester urethane)s (PEU) as a building block results in a PEU/POSS hybrid polymer with increased mechanical strength and thermostability. An attractive feature of the new polymer is that it forms a porous matrix when cast in the form of a thin film, making it potentially useful in tissue engineering. In this study, we present detailed microscopic analysis of the PEU/POSS matrix and demonstrate its biocompatibility with cell culture. The PEU/POSS polymer forms a continuous porous matrix with open pores and interconnected grooves. From SEM image analysis, it is calculated that there are about 950 pores per mm2 of the matrix area with pore size ranging from 1 to 15 μm in diameter. The area occupied by the pores represents approximately 7.6 % of matrix area. Using mouse embryonic stem cells (ESCs), we demonstrate that the PEU/POSS matrix provides excellent support for cell proliferation and differentiation. Under the cell culture condition optimized to maintain self-renewal, ESCs grown on a PEU/POSS matrix exhibit undifferentiated morphology, express pluripotency markers, and have similar growth rate to cells grown on gelatin. When induced for differentiation, ESCs underwent dramatic morphological change, characterized by the loss of clonogenecity and increased cell size with well-expanded cytoskeleton networks. Differentiated cells are able to form a continuous monolayer that is closely embedded on the matrix. The excellent compatibility between the PEU/POSS matrix and ESC proliferation/differentiation demonstrates the potential of using PEU/POSS polymers in future ESC-based tissue engineering. PMID:20213627

  15. From surface-inspired oxovanadium silsesquioxane models to active catalysts for the oxidation of alcohols with O(2)-the cinnamic acid/metavanadate system.

    PubMed

    Ohde, Christian; Limberg, Christian

    2010-06-18

    Silsesquioxane dioxovanadate(V) complexes were investigated with respect to their potential as a catalyst for the oxidative dehydrogenation of alcohols with O(2) as an oxidant. The turnover frequencies determined were comparatively low, but during the oxidation of cinnamic alcohol an increase in activity was observed in the course of the process, which was inspected more closely. It turned out that during the oxidation of cinnamic alcohol, not only was the aldehyde formed but also cinnamic acid, which in turn reacts with the silsesquioxane complex employed to give NBu(4)[O(2)V(O(2)CC(2)H(2)Ph)(2)], which can also be obtained from NBu(4)VO(3) and cinnamic acid and represents a far more active catalyst, not only for cinnamic alcohol but also for other activated alcohols and hydrocarbons. The rate-determining step of the conversion corresponds to an hydrogen-atom abstraction from the C-H units, as shown by the determination of the kinetic isotope effect in case of 9-hydroxyfluorene, and the reoxidation of the reduced catalyst proceeds via a peroxo intermediate, which is also capable of oxidizing one alcohol equivalent. Furthermore the influence of the organic residues at the carboxylate ligands on the catalyst performance was investigated, which showed that the activity increases with decreasing pK(s) value. Moreover, it was found that during the oxidation the catalyst slowly decomposes, but can be regenerated by addition of excessive carboxylic acid.

  16. Fluorinated and Thermo-Cross-Linked Polyhedral Oligomeric Silsesquioxanes: New Organic-Inorganic Hybrid Materials for High-Performance Dielectric Application.

    PubMed

    Wang, Jiajia; Sun, Jing; Zhou, Junfeng; Jin, Kaikai; Fang, Qiang

    2017-04-12

    A fluorinated and thermo-cross-linked polyhedral oligomeric silsesquioxane (POSS) has been successfully synthesized by thermal polymerization of a fluorinated POSS monomer having an inorganic silsesquioxane core and organic side chains bearing thermo-cross-linkable trifluorovinyl ether groups. This new inorganic-organic hybrid polymer shows high thermostability with a 5 wt % loss temperature of 436 °C, as well as good transparency (a sheet with an average thickness of 1.5 mm shows high transmittance of 92% varying from 400 to 1100 nm). Moreover, the polymer exhibits both low dielectric constant (<2.56) and low dissipation factor (<3.1 × 10(-3)) in a wide range of frequencies from 40 Hz to 30 MHz even at a high frequency of 5 GHz. The polymer also shows low water uptake (<0.04%) and low Dk (near 2.63) after immersing it in water at room temperature for 3 days. These data imply that this polymer is very suitable to be utilized as a high-performance dielectric material for fabrication of high-frequency printed circuit boards or encapsulation resins for integrated circuit dies in the microelectronic industry. Furthermore, this work also provides a route for the preparation of fluorinated POSS-based polymers.

  17. Ferrocene adsorbed into the porous octakis(hydridodimethylsiloxy)silsesquioxane after thermolysis in tetrahydrofuran media: An applied surface for ascorbic acid determination

    SciTech Connect

    Ribeiro do Carmo, Devaney; Lataro Paim, Leonardo; Ramos Stradiotto, Nelson

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Octakis(hydridodimethylsiloxi)silsesquioxane was synthesized and Ferrocene was adsorbed. Black-Right-Pointing-Pointer Polymeric net through electrostatic interactions was observed. Black-Right-Pointing-Pointer The novel materials presents electroacatalytic activity for Ascorbic acid. -- Abstract: Octakis(hydridodimethylsiloxi)silsesquioxane (Q{sub 8}M{sub 8}{sup H}) was synthesized and Ferrocene was adsorbed in a polymeric net through electrostatic interactions, with anion forming after the cleavage of any siloxy groups (ESFc). The nanostructured materials (Q{sub 8}M{sub 8}{sup H} and EsFc) were characterized by Fourier transform infrared spectra (FT-IR), nuclear magnetic resonance (NMR), X-ray diffraction (XRD), Thermogravimetric analyses and Voltammetric technique The cyclic voltammograms of the graphite paste electrode modified with ESFc showed one redox couple with E{sup 0} Prime = 0.320 V (1.0 mol L{sup -1} NaCl, v = 50 mV s{sup -1}), with a diffusion-controlled process and the redox process shows electrocatalytic activity for the oxidation of ascorbic acid.

  18. Small calibre polyhedral oligomeric silsesquioxane nanocomposite cardiovascular grafts: influence of porosity on the structure, haemocompatibility and mechanical properties.

    PubMed

    Ahmed, Maqsood; Ghanbari, Hossein; Cousins, Brian G; Hamilton, George; Seifalian, Alexander M

    2011-11-01

    There is a significant worldwide demand for a small calibre vascular graft for use as a bypass or replacement conduit. An important feature in determining the success of a graft is the wall structure, which includes porosity, pore size and pore interconnectivity, as these play a crucial role in determining the long-term patency of a bypass graft. In this study we fabricate a small diameter (<5mm) vascular graft from polyhedral oligomeric silsesquioxane-poly(carbonate urea)urethane (POSS-PCU) via an extrusion, phase inversion method using an automated, custom built machine. Through the dispersion of a porogen, sodium bicarbonate (NaHCO(3)), in controlled concentrations (0-55%) we were able to produce grafts with well-defined pore morphologies. The impact of NaHCO(3) concentration on the structure of the graft wall and its influence on the mechanical and haemocompatibility properties are evaluated here. Scanning electron microscopy and mercury porosimetry were used to characterise graft structure. Atomic force microscopy elucidated any changes in surface morphology. The addition of NaHCO(3) improved the pore interconnectivity and increasing the concentration of NaHCO(3) led to grafts with rougher surfaces and larger pore sizes. The ultimate tensile strength and suture retention decreased with increasing concentrations of NaHCO(3), while graft compliance increased. To evaluate haemocompatibility platelets and peripheral blood mononuclear cells (PBMC) were incubated on a range of different graft samples. Platelet adhesion, PBMC surface receptor expression (CD14, CD86, CD69 and HLA-DR) and cytokine release (PF4, IL-1β, IL-6, IL-10, TNFα) were all measured. Increasing numbers of platelets adhered to grafts produced with no NaHCO(3), which exhibited a smooth surface morphology, and PBMC adherent on these grafts expressed higher levels of CD14 and CD86. Whilst the different graft samples induced varying levels of cytokine secretion in vitro, no distinct pattern

  19. The insertion of gas molecules into polyhedral oligomeric silsesquioxane (POSS) cages: understanding the energy of insertion using quantum chemical calculations.

    PubMed

    Skelton, A A; Fried, J R

    2013-03-28

    Density functional theory (DFT) calculations using the B3LYP and ωB97XD functionals and Møller-Plesset (MP2) calculations have been used to determine the energy of insertion of seven molecules (CO2, N2, O2, CO, CH4, He and H2O) into two sizes of polyhedral oligomeric silsesquioxane (POSS) cages, T10 and T12. Geometry optimization results of each molecule inserted into the center of the POSS cage and transition-energy searches of the molecules in the largest face of both T10 and T12 (identified as the Si5 face) are discussed. The main factors that affect the energy of a molecule in a particular POSS cage are the size (number of atoms) and shape of the POSS cage and the strength of dispersion and electrostatic interactions. The largest of the molecules, CO2 and CH4, have the largest interaction energies within the center and the face of the T10 and T12 cages. Interaction energies for the diatomic molecules increase in the order H2 < O2 < N2 ∼ CO and differences between interaction energies can be attributed, in part, to differences in electron transfer between the cage and molecule. Electrostatic interactions also play a significant role in determining the interaction energy. For example, H2 and He are only slightly charged when inside the POSS cages, providing little repulsive or attractive interactions, while polar CO provides significant repulsive interaction. In the case of water, the interaction energies are low because of hydrogen bonding between the water hydrogen atoms and the POSS oxygen atoms. The interaction energies of the absorbates at the center of T12 are typically smaller than for T10 due to the larger cavity size of T12. The Si5 face has the same basic structure for both T10 and T12 cages and, consequently, the interaction energies of the absorbate molecules at the face are similar. Interaction energies obtained using MP2 calculations are lower than those obtained from DFT calculations depending on the choice of the functional. For example, use

  20. Nanofabrication of super-high-aspect-ratio structures in hydrogen silsesquioxane from direct-write e-beam lithography and hot development.

    SciTech Connect

    Ocola, L. E.; Tirumala, V. R.; Center for Nanoscale Materials; NIST

    2008-11-01

    Super-high-aspect-ratio structures (>10) in hydrogen silsesquioxane resist using direct write electron beam lithography at 100 kV and hot development and rinse are reported. Posts of 100 nm in width and 1.2 {micro}m tall have been successfully fabricated without the need of supercritical drying. Hot rinse solution with isopropyl alcohol has been used to reduce surface tension effects during drying. Dose absorption effects have been observed and modeled using known Monte Carlo models. These results indicate that for e-beam exposures of thick negative resists (>1 {micro}m), the bottom of the structures will have less cross-link density and therefore will be less stiff than the top. These results will have impact in the design of high-aspect-ratio structures that can be used in microelectromechanical system devices and high-aspect-ratio Fresnel zone plates.

  1. Using time-of-flight secondary ion mass spectrometry and multivariate statistical analysis to detect and image octabenzyl-polyhedral oligomeric silsesquioxane in polycarbonate

    NASA Astrophysics Data System (ADS)

    Smentkowski, V. S.; Duong, H. M.; Tamaki, R.; Keenan, M. R.; Ohlhausen, J. A. Tony; Kotula, P. G.

    2006-11-01

    Silsesquioxane, with an empirical formula of RSiO 3/2, has the potential to combine the mechanical properties of plastics with the oxidative stability of ceramics in one material [D.W. Scott, J. Am. Chem. Soc. 68 (1946) 356; K.J. Shea, D.A. Loy, Acc. Chem. Res. 34 (2001) 707; K.-M. Kim, D.-K. Keum, Y. Chujo, Macromolecules 36 (2003) 867; M.J. Abad, L. Barral, D.P. Fasce, R.J.J. William, Macromolecules 36 (2003) 3128]. The high sensitivity, surface specificity, and ability to detect and image high mass additives make time-of-flight secondary ion mass spectrometry (ToF-SIMS) a powerful surface analytical instrument for the characterization of polymer composite surfaces in an analytical laboratory [J.C. Vickerman, D. Briggs (Eds.), ToF-SIMS Surface Analysis by Mass Spectrometry, Surface Spectra/IMPublications, UK, 2001; X. Vanden Eynde, P. Bertand, Surf. Interface Anal. 27 (1999) 157; P.M. Thompson, Anal. Chem. 63 (1991) 2447; S.J. Simko, S.R. Bryan, D.P. Griffis, R.W. Murray, R.W. Linton, Anal. Chem. 57 (1985) 1198; S. Affrossman, S.A. O'Neill, M. Stamm, Macromolecules 31 (1998) 6280]. In this paper, we compare ToF-SIMS spectra of control samples with spectra generated from polymer nano-composites based on octabenzyl-polyhedral oligomeric silsesquioxane (BnPOSS) as well as spectra (and images) generated from multivariate statistical analysis (MVSA) of the entire spectral image. We will demonstrate that ToF-SIMS is able to detect and image low concentrations of BnPOSS in polycarbonate. We emphasize the use of MVSA tools for converting the massive amount of data contained in a ToF-SIMS spectral image into a smaller number of useful chemical components (spectra and images) that fully describe the ToF-SIMS measurement.

  2. Systematic investigation on the central metal ion dependent binding geometry of M-meso-tetrakis(N-methylpyridinium-4-yl)porphyrin to DNA and their efficiency as an acceptor in DNA-mediated energy transfer.

    PubMed

    Kim, Young Rhan; Gong, Lindan; Park, Jongjin; Jang, Yoon Jung; Kim, Jinheung; Kim, Seog K

    2012-02-23

    Binding geometry to DNA and the efficiency as a donor for energy transfer of various metallo- and nonmetallo-porphyrins were investigated mainly by polarized light spectrscopy and fluorescence measurements. Planar porphyrins including nonmetallo meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP), CuTMPyP, and NiTMPyP produced large red-shift and hypochromism in absorption spectrum and a negative circular dichroism (CD) in the Soret band suggesting that these porphyrins intercalate between DNA base-pairs as expected. In the intercalation pocket, the molecular plane of these porphyrins tilts to a large extent. From a linear dichroism (LD) study, the angle between the two electric transition moments in the Soret band were 16°, 12°, and 11° for TMPyP, NiTMPyP, and CuTMPyP, respectively. On the other hand, porphyrins with axial ligands namely, VOTMPyP, TiOTMPyP, and CoTMPyP, produced a positive CD signal in the Soret band. Hyperchromism and less red-shift were apparent in the absorption spectrum. These observations indicated that the porphyrins with an axial ligand bind outside of the DNA. The angles of both the B(x) and B(y) transition with respect to the local DNA helix were 39°~46° for all porphyrins. From these results, the conceivable binding site of porphyrins with axial ligands is suggested to be the minor groove. All porphyrins were able to quench the fluorescence of intercalated ethidium. Strong overlap between emission spectrum of ethidium and the absorption spectrum of porphyrins when they simultaneously bound to DNA was found suggesting the mechanism behind energy transfer is, at least in part, the Förster type resonance energy transfer (FRET). The minimum distance in base pairs between ethidium and porphyrin required to permit the excited ethidium to emit a photon was the longest for CoTMPyP being 17.6 base pairs and was the shortest for CuTMPyP and NiTMPyP at 8.0 base pairs. The variation in the distance was almost proportional to the extent of

  3. Solvent-controlled synthesis of tetranuclear cage-like copper(II) silsesquioxanes. Remarkable features of the cage structures and their high catalytic activity in oxidation with peroxides.

    PubMed

    Dronova, Marina S; Bilyachenko, Alexey N; Yalymov, Alexey I; Kozlov, Yuriy N; Shul'pina, Lidia S; Korlyukov, Alexander A; Arkhipov, Dmitry E; Levitsky, Mikhail M; Shubina, Elena S; Shul'pin, Georgiy B

    2014-01-14

    Two principally different in their molecular architecture isomeric tetranuclear copper(ii) silsesquioxanes, "Globule"-like compound [(PhSiO1.5)12(CuO)4(NaO0.5)4] (1) and "Sandwich"-like derivative [(PhSiO1.5)6(CuO)4(NaO0.5)4(PhSiO1.5)6] (2), were synthesized by the partial cleavage of polymeric copper(ii) silsesquioxane [(PhSiO1.5)2(CuO)]n by tetraphenylcyclotetrasiloxanolate. The route leading to the formation of either 1 or 2 entirely depends on the nature and composition of the solvent used for this reaction. Thus, the process in an ethanol-1-butanol solution gives compound 1. When a 1,4-dioxane-methanol mixture was used, compound 2 was prepared. The structures and unusual crystal packing of the cages were confirmed by the X-ray studies. It has been found that the reaction of benzene with H2O2 in acetonitrile solution at 50 °C catalyzed by 1 requires addition of trifluoroacetic acid (TFA) in low concentration and gives phenol with a turnover number (TON) of 250 after 3 h. The initial reaction rate W0 linearly depends on the concentration of catalyst 2. The oxidation of 1-phenylethanol to acetophenone with hydrogen peroxide catalyzed by complex 1 in the presence of TFA is not efficient. In contrast, 1 exhibited excellent activity in the oxidation with tert-butyl hydroperoxide (TBHP) in the absence of any acid (the yield of acetophenone was close to the quantitative, TON attained 475 after 2 h). A kinetic study of this reaction led to the conclusion that the process occurs with the participation of radicals tert-BuO˙ produced in the Cu-promoted decomposition of TBHP. The mode of dependence of W0 on the initial concentration of TBHP indicates the formation of an intermediate adduct between the catalyst 1 and TBHP (characterized by the equilibrium constant K1≈ 2 M(-1) for the conditions of conducted experiments) followed by subsequent decomposition of the adduct (k2≈ 0.2 s(-1)) to generate an intermediate species tert-BuO˙ which induces the alcohol oxidation.

  4. Creating Quasi Two-Dimensional Cluster-Assembled Materials through Self-Assembly of a Janus Polyoxometalate-Silsesquioxane Co-Cluster.

    PubMed

    Wu, Han; Zhang, Yu-Qi; Hu, Min-Biao; Ren, Li-Jun; Lin, Yue; Wang, Wei

    2017-05-30

    Clusters are an important class of nanoscale molecules or superatoms that exhibit an amazing diversity in structure, chemical composition, shape, and functionality. Assembling two types of clusters is creating emerging cluster-assembled materials (CAMs). In this paper, we report an effective approach to produce quasi two-dimensional (2D) CAMs of two types of spherelike clusters, polyhedral oligomeric silsesquioxanes (POSS), and polyoxometalates (POM). To avoid macrophase separation between the two clusters, they are covalently linked to form a POM-POSS cocluster with Janus characteristics and a dumbbell shape. This Janus characteristics enables the cocluster to self-assemble into diverse nanoaggregates, as conventional amphiphilic molecules and macromolecules do, in selective solvents. In our study, we obtained micelles, vesicles, nanosheets, and nanoribbons by tuning the n-hexane content in mixed solvents of acetone and n-hexane. Ordered packing of clusters in the nanosheets and nanoribbons were directly visualized using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) technique. We infer that the increase of packing order results in the vesicle-to-sheet transition and the change in packing mode causes the sheet-to-ribbon transitions. Our findings have verified the effectivity of creating quasi 2D cluster-assembled materials though the cocluster self-assembly as a new approach to produce novel CAMs.

  5. Organic-inorganic random copolymers from methacrylate-terminated poly(ethylene oxide) with 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane: synthesis via RAFT polymerization and self-assembly behavior.

    PubMed

    Wei, Kun; Li, Lei; Zheng, Sixun; Wang, Ge; Liang, Qi

    2014-01-14

    In this contribution, we report the synthesis of organic-inorganic random polymers from methacrylate-terminated poly(ethylene oxide) (MAPEO) (Mn = 950) and 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane (MAPOSS) macromers via reversible addition-fragmentation chain transfer (RAFT) polymerization with 4-cyano-4-(thiobenzoylthio) valeric acid (CTBTVA) as the chain transfer agent. The organic-inorganic random copolymers were characterized by means of (1)H NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The results of GPC indicate that the polymerizations were carried out in a controlled fashion. Transmission electron microscopy (TEM) showed that the organic-inorganic random copolymers in bulk were microphase-separated and the POSS microdomains were formed via POSS-POSS interactions. In aqueous solutions the organic-inorganic random copolymers were capable of self-assembling into spherical nanoobjects as evidenced by transmission electron microscopy (TEM) and dynamic laser scattering (DLS). The self-assembly behavior of the organic-inorganic random copolymers was also found to occur in the mixtures with the precursors of epoxy. The nanostructures were further fixed via subsequent curing reaction and thus the organic-inorganic nanocomposites were obtained. The formation of nanophases in epoxy thermosets was confirmed by transmission electron microscopy (TEM) and dynamic mechanical thermal analysis (DMTA). The organic-inorganic nanocomposites displayed the enhanced surface hydrophobicity as evidenced by surface contact angle measurements.

  6. Operating mechanisms of highly-reproducible write-once-read-many-times memory devices based on graphene quantum dot:poly(methyl silsesquioxane) nanocomposites

    NASA Astrophysics Data System (ADS)

    Bok, Chang Han; Wu, Chaoxing; Kim, Tae Whan

    2017-01-01

    Resistive switching memory devices were fabricated utilizing graphene quantum dot (GQD):poly(methyl silsesquioxane) (PMSSQ) hybrid nanocomposites. Current-voltage curves for the Al/GQD:PMSSQ/indium-tin-oxide devices at room temperature showed write-once-read-many-times memory (WORM) characteristics with an ON/OFF ratio of as large as 106 due to the homogeneous dispersion of the GQDs in the PMSSQ matrix. The WORM devices maintained retention times larger than 2 × 104 s under ambient conditions. The devices showed high device-to-device reproducibility with threshold-voltage distributions between 3 and 5 V. The ON state currents remained between 10-6 and 10-3 A, and the OFF state currents maintained between 10-12 and 10-9 A. The operating mechanisms concerning the interaction between the GQDs and the PMSSQ matrix for the resistive-switch phenomenon were analyzed on the basis of the I-V results and with the aid of the energy band diagram.

  7. Hydrophobic interface controlled electrochemical sensing of nitrite based on one step synthesis of polyhedral oligomeric silsesquioxane/reduced graphene oxide nanocomposite.

    PubMed

    Bai, Wushuang; Sheng, Qinglin; Zheng, Jianbin

    2016-04-01

    In this paper, we report a novel hydrophobic interface controlled electrochemical sensing of nitrite based on polyhedral oligomeric silsesquioxane/ reduced graphene oxide nanocomposite (POSS/rGO). The POSS/rGO is prepared by one step hydrothermal synthesis method, and characterized by transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FT-IR), Zeta-potential measurement analyzer, electrochemical impedance spectroscopy (EIS) and zero current potential method respectively. Then the POSS/rGO composite is used to fabricate electrochemical sensor for nitrite detection. According to experimental results, it is found that under control of hydrophobic force, the current peak will be shifted to lower potential (0.72 V) and the possible reason has been analyzed in manuscript. In addition, the POSS/rGO based sensor also has wide linear range (0.5 μM to 120 mM), low detection limit (0.08 μM) and good selectivity. In a word, the hydrophobic force controlled detection in this paper will provide a new platform for electrochemical sensing.

  8. Ethoxy and silsesquioxane derivatives of antimony as dopant precursors: unravelling the structure and thermal stability of surface species on SiO2.

    PubMed

    Alphazan, T; Florian, P; Thieuleux, C

    2017-03-14

    We report here the controlled preparation of SiO2 supported Sb-(mono)layers and their thorough characterization by in situ IR, solid-state NMR and elemental analyses. This study allows for the molecular understanding of the surface Sb species derived from the grafting of ethoxy and polyhedral oligomeric silsesquioxane antimony derivatives as mono- or bi-podal Sb(iii) surface species depending on the number of surface SiOH groups. This result is different from what was observed with the phosphorus analogue (POSS-P) that yielded P(v) species. A monolayer coverage of Sb species onto silica was also obtained using both POSS-Sb and the [Sb(OEt)3]2 derivative with surface densities ranging from ∼0.3 Sb nm(-2) to 1.8 Sb nm(-2), respectively. It is noteworthy that under optimized conditions, a layer of antimony species or suboxides on silica was produced using POSS-Sb without significant Sb loss, highlighting the protective properties of the POSS cage. These results open new perspectives for the controlled and non-destructive Sb-doping (Molecular Layer Doping) of semiconductors dedicated to nano-device applications.

  9. Chromatographic efficiency comparison of polyhedral oligomeric silsesquioxanes-containing hybrid monoliths via photo- and thermally-initiated free-radical polymerization in capillary liquid chromatography for small molecules.

    PubMed

    Wang, Hongwei; Ou, Junjie; Liu, Zhongshan; Lin, Hui; Peng, Xiaojun; Zou, Hanfa

    2015-09-04

    Monolithic poly(methacrylate epoxy cyclosiloxane-co-polyhedral oligomeric silsesquioxanes) (epoxy-MA-POSS) capillary columns have been prepared via either photo- or thermally-initiated polymerization of the corresponding monomers using a 1-propanol/PEG 400 mixture as porogens. Photochemical polymerization was accomplished by irradiation of the UV-transparent capillary for 10min at room temperature, while thermal polymerization was performed at 55°C, 60°C or 65°C for 18h. The evaluation of chromatographic property for two hybrid epoxy-MA-POSS monoliths was carried out. The results indicate that hybrid monoliths fabricated by photochemical initiation exhibit higher column efficiency (97,000-98,400plates/m) than those synthesized by thermal polymerization (41,100-48,000plates/m) in cLC. The higher efficiency of photo-initiated hybrid monoliths is closely related to lower eddy dispersion (A-term) and mass transfer resistance (C-term).

  10. 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

    PubMed Central

    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

    2013-01-01

    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. PMID:24706135

  11. Transformable nanostructures of platinum-containing organosilane hybrids: non-covalent self-assembly of polyhedral oligomeric silsesquioxanes assisted by Pt···Pt and π-π stacking interactions of alkynylplatinum(II) terpyridine moieties.

    PubMed

    Au-Yeung, Ho-Leung; Leung, Sammual Yu-Lut; Tam, Anthony Yiu-Yan; Yam, Vivian Wing-Wah

    2014-12-31

    An alkynylplatinum(II) terpyridine complex functionalized with polyhedral oligomeric silsesquioxanes (POSS) moieties has been demonstrated to exhibit self-association behavior to give various distinguishable nanostructures with interesting morphological transformation from rings to rods in response to solvent conditions through the stabilization of Pt···Pt and π-π stacking interactions as well as hydrophobic-hydrophobic interactions. These changes can be systemically controlled by varying the solvent composition and have been studied by (1)H NMR, electron microscopy, UV-vis absorption, and emission spectroscopies.

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

    PubMed

    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-T10) 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.

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

    PubMed

    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.

  14. Cyclization Phenomena in the Sol-Gel Polymerization of a,w-Bis(triethoxysilyl)alkanes and Incorporation of the Cyclic Structures into Network Silsesquioxane Polymers

    SciTech Connect

    Alam, T.M.; Carpenter, J.P.; Dorhout, P.K.; Greaves, J.; Loy, D.A.; Shaltout, R.; Shea, K.J.; Small, J.H.

    1999-01-04

    Intramolecular cyclizations during acid-catalyzed, sol-gel polymerizations of ct,co- bis(tietioxysilyl)aWmes substintidly lengtien gelties formonomers witietiylene- (l), propylene- (2), and butylene-(3)-bridging groups. These cyclizations reactions were found, using mass spectrometry and %i NMR spectroscopy, to lead preferentially to monomeric and dimeric products based on six and seven membered disilsesquioxane rings. 1,2- Bis(triethoxysilyl)ethane (1) reacts under acidic conditions to give a bicyclic drier (5) that is composed of two annelated seven membered rings. Under the same conditions, 1,3- bis(triethoxysilyl)propane (2), 1,4-bis(triethoxysilyl)butane (3), and z-1,4- bis(triethoxysilyl)but-2-ene (10) undergo an intramolecular condensation reaction to give the six membemd and seven membered cyclic disilsesquioxanes 6, 7, and 11. Subsequently, these cyclic monomers slowly react to form the tricyclic dirners 8,9 and 12. With NaOH as polymerization catalyst these cyclic silsesquioxanes readily ~aeted to afford gels that were shown by CP MAS z%i NMR and infr=d spectroscopes to retain some cyclic structures. Comparison of the porosity and microstructwe of xerogels prepared from the cyclic monomers 6 and 7 with gels prepared directly from their acyclic precursors 2 and 3, indicate that the final pore structure of the xerogels is markedly dependent on the nature of the precursor. In addition, despite the fact that the monomeric cyclic disilsesquioxane species can not be isolated from 1-3 under basic conditions due to their rapid rate of gelation, spectroscopic techniques also detected the presence of the cyclic structures in the resulting polymeric gels.

  15. Preparation and Characterization of Polyhedral Oligomeric Silsesquioxane-Containing, Titania-Thiol-Ene Composite Photocatalytic Coatings, Emphasizing the Hydrophobic-Hydrophilic Transition.

    PubMed

    Jefferson, LaCrissia U; Netchaev, Anton D; Jefcoat, Jennifer A; Windham, Amber D; McFarland, Frederick M; Guo, Song; Buchanan, Randy K; Buchanan, J Paige

    2015-06-17

    Coatings prepared from titania-thiol-ene compositions were found to be both self-cleaning, as measured by changes in water contact angle, and photocatalytic toward the degradation of an organic dye. Stable titania-thiol-ene dispersions at approximately 2 wt % solids were prepared using a combination of high-shear mixing and sonication in acetone solvent from photocatalytic titania, trisilanol isobutyl polyhedral oligomeric silsesquioxane (POSS) dispersant, and select thiol-ene monomers, i.e., trimethylolpropane tris(3-mercaptopropionate) (TMPMP), pentaerythritol allyl ether (APE), and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT). The dispersed particle compositions were characterized by DLS and TEM. The synthetic methods employed yield a strongly bound particle/POSS complex, supported by IR, 29Si NMR, and TGA. The factors of spray techniques, carrier solvent volatility, and particle size and size distributions, in combination, likely all contribute to the highly textured but uniform surfaces observed via SEM and AFM. Polymer composites possessed thermal transitions (e.g., Tg) consistent with composition. In general, the presence of polymer matrix provided mechanical integrity, without significantly compromising or prohibiting other critical performance characteristics, such as film processing, photocatalytic degradation of adsorbed contaminants, and the hydrophobic-hydrophilic transition. In all cases, coatings containing photocatalytic titania were converted from superhydrophobic to superhydrophilic, as defined by changes in the water contact angle. The superhydrophilic state of samples was considered persistent, since long time durations in complete darkness were required to observe any significant hydrophobic return. In a preliminary demonstration, the photocatalytic activity of prepared coatings was confirmed through the degradation of crystal violet dye. This work demonstrates that a scalable process can be found to prepare titania

  16. Photoactive perylenediimide-bridged silsesquioxane functionalized periodic mesoporous organosilica thin films (PMO-SBA15): synthesis, self-assembly, and photoluminescent and enhanced mechanical properties.

    PubMed

    Wahab, M Abdul; Hussain, H; He, Chaobin

    2009-04-21

    Well-organized periodic mesoporous organosilica thin films (designated as PMO-SBA15), having covalently bonded perylene-bridged silesquioxane (PTCDBS) inside their pore channels, are successfully synthesized via sol-gel self-assembly of 1,2-bis(triethoxysilyl)ethane and perylene-bridged silsesquioxane, using micelles of pluronic surfactant (P123) as a template for the first time. The surfactant is successfully removed from the pore channels of PMO-SBA15 by an acidic solvent extraction procedure. The final PMO-SBA15 thin films are characterized by high resolution X-ray diffraction (HRXRD), transmission electron microcopy (TEM), solid-state 29Si and 13C NMR CP/MAS NMR spectroscopy, nitrogen adsorption-desorption measurements, photoluminescence (PL) spectroscopy, and nanoindentation. HRXRD data reveal the formation of well-organized hexagonal channels in the pure PMO-SBA15 films. The intensity of the diffracted X-ray, however, systematically attenuates after incorporation of the perylene functionality inside the hexagonal channels. This is attributed to the low X-ray scattering contrast between the mesostructured organosilica walls and organic moieties (perylene) inside the channels, suggesting the successful incorporation of the photoactive perylene molecules inside the nanochannels. This was further confirmed by photoluminescence spectroscopy and nitrogen adsorption-desorption measurements. Additionally, the mechanical hardness of the functionalized PMO-SBA15 thin films, measured by nanoindentation, is significantly enhanced as compared with that of the pure PMO film. Thermogravimetric analysis (TGA) and elemental analysis suggested the functionalized PMO-SBA15 materials with PTCDBS.

  17. Preparation of polyhedral oligomeric silsesquioxane-based hybrid monolith by ring-opening polymerization and post-functionalization via thiol-ene click reaction.

    PubMed

    Liu, Zhongshan; Ou, Junjie; Lin, Hui; Wang, Hongwei; Dong, Jing; Zou, Hanfa

    2014-05-16

    A polyhedral oligomeric silsesquioxane (POSS) hybrid monolith was simply prepared by using octaglycidyldimethylsilyl POSS (POSS-epoxy) and cystamine dihydrochloride as monomers via ring-opening polymerization. The effects of composition of prepolymerization solution and polycondensation temperature on the morphology and permeability of monolithic column were investigated in detail. The obtained POSS hybrid monolithic column showed 3D skeleton morphology and exhibited high column efficiency of ∼71,000 plates per meter in reversed-phase mechanism. Owing to this POSS hybrid monolith essentially possessing a great number of disulfide bonds, the monolith surface would expose thiol groups after reduction with dithiothreitol (DTT), which supplied active sites to functionalize with various alkene monomers via thiol-ene click reaction. The results indicated that the reduction with DTT could not destroy the 3D skeleton of hybrid monolith. Both stearyl methylacrylate (SMA) and benzyl methacrylate (BMA) were selected to functionalize the hybrid monolithic columns for reversed-phase liquid chromatography (RPLC), while [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)-ammonium hydroxide (MSA) was used to modify the hybrid monolithic column in hydrophilic interaction chromatography (HILIC). These modified hybrid monolithic columns could be successfully applied for separation of small molecules with high efficiency. It is demonstrated that thiol-ene click reaction supplies a facile way to introduce various functional groups to the hybrid monolith possessing thiol groups. Furthermore, due to good permeability of the resulting hybrid monoliths, we also prepared long hybrid monolithic columns in narrow-bore capillaries. The highest column efficiency reached to ∼70,000 plates using a 1-m-long column of 75μm i.d. with a peak capacity of 147 for isocratic chromatography, indicating potential application in separation and analysis of complex biosamples. Copyright © 2014

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

    PubMed

    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 (p<0.05). Hydrophobicity was significantly reduced in both the POSS-PCU and PU samples (p<0.0001). However, the POSS-PCU nanocomposite remained more hydrophobic than the PU sample (p<0.0001). Less platelet adhered to the POSS-PCU compared to the PU (p<0.0001). These results indicate that the use of this nanocomposite 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. Modeling of novel hybrid photonic crystal structures involving cured hydrogen silsesquioxane pillars for improving the light extraction in light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Kadiyala, Anand; Dawson, Jeremy M.

    2016-03-01

    The Solid-State Lighting (SSL) industry utilizes semiconductor based light-emitting diodes (LEDs) as core elements of light sources. LED lighting has several advantages over conventional incandescent bulbs; however, device-level issues such as material quality, low quantum efficiencies, and low light extraction efficiencies still exist. Many techniques have been explored to provide improvement in the area of LED light extraction. Improvement in light extraction efficiency, through the use of integrated optical components such as photonic crystals, is critical for the improvement in the overall efficiency of the device. Fabrication and integration of PhCs into LEDs with little or no degradation in device's electrical characteristics is an important accomplishment to be considered. Use of electron beam lithography and novel electron beam resists like hydrogen silsesquioxane will allow advancements toward achieving this goal. The unique chemical properties of HSQ allows transformation of the patterned resist into silicon dioxide. This leads to hybrid PhC structures that contain the cured form of HSQ and other materials of interest in an LED. In this work, novel hybrid PhC structures in square and triangular lattice configurations will be modeled to improve light extraction in blue InGaN/GaN based LEDs (λ=465 nm) and attain an optimal structure. Feature sizes from 100 nm to 465 nm will be modeled and the effect of the patterned structure (band gap and/or diffraction) on the light extraction will be studied and analyzed. Simulation data from frequency domain and time domain engines in MPB and OptiFDTD respectively will be analyzed and presented.

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

    PubMed

    Mahfuz, Hassan; Powell, Felicia; Granata, Richard; Hosur, Mahesh; Khan, Mujib

    2011-09-21

    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.

  1. A new biodegradable nanocomposite based on polyhedral oligomeric silsesquioxane nanocages: cytocompatibility and investigation into electrohydrodynamic jet fabrication techniques for tissue-engineered scaffolds.

    PubMed

    Raghunath, Joanne; Zhang, Hongbo; Edirisinghe, Mohan J; Darbyshire, Arnold; Butler, Peter E; Seifalian, Alexander M

    2009-01-01

    Our group has developed a non-biodegradable nanocomposite based on POSS (polyhedral oligomeric silsesquioxane) nanocages with PCU [poly(carbonate urethane)] and previous studies have shown good cell-compatibility and antithrombogenic properties. The latest biodegradable formulation is a POSS-modified poly(hexanolactone/carbonate)urethane/urea containing 80% hexanolactone (caprolactone) with the tradename UCL-NanoBio. The direct effect of the polymer on cells was investigated by seeding stem cells on to circular discs of the polymer in 24-well plates; these discs were prepared mainly by electrohydrodynamic jetting. To assess the indirect effect of the polymer, various concentrations of the polymer powder were added to CCM (cell culture medium) and left on a shaker for 10 days. The precipitate was then removed and the CCM was used for culturing the cells seeded on to 24-well plates. Cell viability and growth at 48 and 96 h were assessed using Alamar Blue and lactate dehydrogenase, and morphology was studied by scanning electron microscopy. Cells were shown to adhere well to the polymer, with cell metabolism being comparable with that found on TCP (tissue-culture plastic). Indirect assessment demonstrated some decrease in cell viability with high concentrations of polymer, but showed no difference in cell death between polymer concentrations. The viability of cells seeded on to the polymer was comparable with that of those seeded on to TCP. Cell viability was comparable on both electrosprayed and electrospun scaffolds, but infiltration into the scaffold was much more evident on the electrospun scaffolds. It can be concluded that this new nanocomposite can support the growth and viability of stem cells and that scaffolds of this polymer nanocomposite fabricated by electrohydrodynamic jetting routes have potential use for tissue engineering in the future.

  2. Platinum nanoparticles incorporated in silsesquioxane for use in LbL films for the simultaneous detection of dopamine and ascorbic acid

    NASA Astrophysics Data System (ADS)

    dos Santos, Vagner; de Jesus, Cliciane Guadalupe; dos Santos, Monalisa; Canestraro, Carla Daniele; Zucolotto, Valtencir; Fujiwara, Sérgio Toshio; Garcia, Jarem Raul; Pessoa, Christiana Andrade; Wohnrath, Karen

    2012-09-01

    We describe the preparation of platinum nanoparticles (PtNPs) using the 3- n-propylpyridinium silsesquioxane chloride (SiPy+Cl-) as a nanoreactor and stabilizer. The formation of PtNPs was monitored by UV-Vis spectroscopy by measuring the decrease in the intensity of the band at 375 nm, which is attributed to the electronic absorption of PtCl6 2- ions. TEM images of Pt-SiPy+Cl- nanohybrid indicated an average size of 3-40 nm for PtNPs. The Pt-SiPy+Cl- was used as a polycation in the preparation of layer-by-layer films (LbL) on a glass substrate coated with fluorine-doped tin oxide (FTO) alternating with the polyanion poly(vinyl sulfonic acid) (PVS). The films were electrochemically tested in sulfuric acid to confirm the deposition of Pt-SiPy+Cl- onto the LbL films, observing the adsorption and desorption of hydrogen ( E pa = 0.1 V) and by the redox process of formation for PtO with E pa = 1.3 V and E pc = 0.65 V. FTIR and Raman spectra confirmed the presence of the PVS and Pt-SiPy+Cl- in the LbL films. A linear increase in the absorbance in the UV-Vis spectra of the Pt-SiPy+Cl- at 258 nm (π → π* transition of the pyridine groups) with a number of Pt-SiPy+Cl-/PVS or PVS/SiPy+Cl- bilayers ( R = 0.992) was observed. These LbL films were tested for the determination of dopamine (DA) in the presence of ascorbic acid (AA) with a detection limit (DL) on the order of 2.6 × 10-6 mol L-1 and a quantification limit (QL) of 8.6 × 10-6 mol L-1. The films exhibited a good repeatability and reproducibility, providing a potential difference of 550 mV for the oxidation of DA with AA interferent.

  3. Electronic Properties and Charge Transport of Polyhedral Oligomeric Silsesquioxanes (POSS) Derivatives and Materials Design for Highly Efficient Organic Light Emitting Diodes

    NASA Astrophysics Data System (ADS)

    Zhen, Changgua

    2011-12-01

    Polyhedral oligomeric silsesquioxane (POSS) and its derivatives are used as examples to illustrate the tunability of electronic properties of organic semiconductors by density functional theory (DFT) and time-dependent density functional theory (TDDFT) studies. The results indicate that the POSS cage is quite rigid upon functionalization and thus provides a means for controlling the orientation of organic fragments attached to it. Moreover, the electronic properties such as frontier orbitals distribution and energy level, HOMO-LUMO gap, reorganization energy, and exciton binding energy can be tuned through the choice of functional groups and their positioning. By functionalizing the POSS cage with two pentacene molecules along the diagonal direction, we construct Dipentacene POSS with very high charge mobility predicted by multiscale modeling. Unlike the herringbone pattern in the pentacene single crystal, the Dipentacene POSS molecules adopt a parallel configuration in its single crystal that was predicted with molecular dynamics. This parallel configuration enhances the wavefunction overlap between pentacene segments, resulting in faster charge hopping between the molecules. The insight gained in the tuning of electronic properties and charge transport was used to design materials for organic light emitting diodes (OLEDs). We optimized the molecular structures of emitting materials based on first-principles calculations, resulting in a remarkable improvement in the maximum external quantum efficiency (EQE) of the undoped device from 2.0% to 4.99%. By doping the emitters in suitable host material, 4,4'-bis(carbazol-9-yl)biphenyl (CBP), at the optimal doping concentration, deep blue emission with extremely high maximum EQE of 10.7% and CIE coordinates of (0.151, 0.088) were achieved. The high EQE far exceeds the traditional upper limit of 5% if the singlet generation fraction in fluorescent OLEDs is 25%. A survey of the literature published in the last two decades

  4. Synthesis and Characterization of Ru(II) Tris(1,1O-phenanthroline)-Electron Acceptor Dyads Incorporating the 4-benzoyl-N-methylpyridinium Cation or N-Benzyl-N'-methyl-viologen. Improving the Dynamic Range, Sensitivity and Response Time of Sol-Gel Based Optical Oxygen Sensors

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas; Rawashdeh, Abdel-Monen M.; Elder, Ian A.; Yang, Jinhua; Dass, Amala; Sotiriou-Leventis, Chariklia

    2004-01-01

    The title compounds (1 and 2, above) were synthesized by Sonogashira coupling reactions of appropriate Ru(1I) complexes with the electron a cceptors. Characterization was conducted in solution and in frozen ma trices. Finally, the title compounds were evaluated as dopants of sol-gel materials. It was found that the intramolecular quenching efficie ncy of 4-benzoyl-Nmethylpyridinium cation in solution depends on the solvent: photoluminescence is quenched completely in CH,CN, but not i n methanol or ethanol. On the other hand, intramolecular emission que nching by 4-benzyl-N-methyl viologen is complete in all solvents. The difference between the two quenchers is traced electrochemically to t he solvation of the 4-benzoyl-Nmethylpyridiniums by alcohol. In froze n matrices or adsorbed on the surfaces of silica aerogel, both Ru(I1) complex/electron acceptor dyads of this study are photoluminescent, and the absence of quenching has been traced to the environmental rigi dity. When doped aerogels are cooled at 77 K, the emission intensity increases by approximately 4x, and the spectra shift to the blue, analogous to what is observed with Ru(I1) complexes in solutions undergoi ng fluid-to-rigid transition. However, in contrast to frozen solution s, the luminescent moieties in the bulk of aerogels kept at low tempe ratures are still accessible to gas-phase quenchers diffusing through the mesopores, leading to more sensitive platforms for sensors than o ther room-temperature configurations. Thus the photoluminescence of o ur Ru(I1) complex dyads adsorbed on aerogel is quenchable by O2 both at room temperature and at 77 K. Furthermore, it was also found that O 2 modulates the photoluminescence of aerogels doped with 4-benzoyl -N -methylpyridinium-based dyads over a wider dynamic range compared wi th aerogels doped with either our vislogen-based dyads or with Ru(I1) tris(1,lO-phenanthroline) itself.

  5. Synthesis and Characterization of Ru(II) Tris(1,1O-phenanthroline)-Electron Acceptor Dyads Incorporating the 4-benzoyl-N-methylpyridinium Cation or N-Benzyl-N'-methyl-viologen. Improving the Dynamic Range, Sensitivity and Response Time of Sol-Gel Based Optical Oxygen Sensors

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas; Rawashdeh, Abdel-Monen M.; Elder, Ian A.; Yang, Jinhua; Dass, Amala; Sotiriou-Leventis, Chariklia

    2004-01-01

    The title compounds (1 and 2, above) were synthesized by Sonogashira coupling reactions of appropriate Ru(1I) complexes with the electron a cceptors. Characterization was conducted in solution and in frozen ma trices. Finally, the title compounds were evaluated as dopants of sol-gel materials. It was found that the intramolecular quenching efficie ncy of 4-benzoyl-Nmethylpyridinium cation in solution depends on the solvent: photoluminescence is quenched completely in CH,CN, but not i n methanol or ethanol. On the other hand, intramolecular emission que nching by 4-benzyl-N-methyl viologen is complete in all solvents. The difference between the two quenchers is traced electrochemically to t he solvation of the 4-benzoyl-Nmethylpyridiniums by alcohol. In froze n matrices or adsorbed on the surfaces of silica aerogel, both Ru(I1) complex/electron acceptor dyads of this study are photoluminescent, and the absence of quenching has been traced to the environmental rigi dity. When doped aerogels are cooled at 77 K, the emission intensity increases by approximately 4x, and the spectra shift to the blue, analogous to what is observed with Ru(I1) complexes in solutions undergoi ng fluid-to-rigid transition. However, in contrast to frozen solution s, the luminescent moieties in the bulk of aerogels kept at low tempe ratures are still accessible to gas-phase quenchers diffusing through the mesopores, leading to more sensitive platforms for sensors than o ther room-temperature configurations. Thus the photoluminescence of o ur Ru(I1) complex dyads adsorbed on aerogel is quenchable by O2 both at room temperature and at 77 K. Furthermore, it was also found that O 2 modulates the photoluminescence of aerogels doped with 4-benzoyl -N -methylpyridinium-based dyads over a wider dynamic range compared wi th aerogels doped with either our vislogen-based dyads or with Ru(I1) tris(1,lO-phenanthroline) itself.

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

    NASA Astrophysics Data System (ADS)

    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

  7. 4-[2-(4-cyanophenyl)ethenyl]-N-methylpyridinium tetraphenylborate.

    PubMed

    Jin, Dan; Zhang, De Chun

    2005-11-01

    In the title compound, C(15)H(13)N(2)(+).C(24)H(20)B(-), the pyridyl ring of the cation makes a dihedral angle of 1.6 degrees with the benzene ring. Each is rotated in the same direction with respect to the central -C-CH=CH-C- linkage, by 3.8 and 5.3 degrees, respectively. The anions have a slightly distorted tetrahedral geometry. Molecular packing analysis was carried out using the packing energy portioning scheme in the program OPEC. Around each anion in the crystal structure there are eight anions, which interact with the central anion through C-H...pi interactions. The cations are hydrogen bonded in a head-to-tail fashion, forming chains along [101].

  8. 2-Amino-5-methyl-pyridinium 2-amino-benzoate.

    PubMed

    Thanigaimani, Kaliyaperumal; Farhadikoutenaei, Abbas; Khalib, Nuridayanti Che; Arshad, Suhana; Razak, Ibrahim Abdul

    2012-11-01

    In the 2-amino-benzoate anion of the title salt, C(6)H(9)N(2) (+)·C(7)H(6)NO(2) (-), an intra-molecular N-H⋯O hydrogen bond is observed. The dihedral angle between the ring and the CO(2) group is 8.41 (13)°. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms via a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The ion pairs are further connected via N-H⋯O hydrogen bonds, resulting in a donor-donor-acceptor-acceptor (DDAA) array of quadruple hydrogen bonds. The crystal structure also features a weak N-H⋯O hydrogen bond and a C-H⋯π inter-action, resulting in a three-dimensional network.

  9. Hansen Solubility Parameters for Octahedral Oligomeric Silsesquioxanes

    DTIC Science & Technology

    2012-08-28

    Sci. 2005, 97, 939-945. 40. Cataldo, F. On the Solubility Parameter of C60 and Higher Fullerenes. Fuller. Nanotub . Carbon Nanostruct. 2009, 17, 79-84...First, the cohesive energy for the naphthyl group is calculated by scaling the values for phenyl groups 17 by the number of carbons (10 for...mass of the peripheral carbon atom nearest to each silicon atom actually falls within the cube, so each corner of the cube contains a region that is

  10. Fluorinated Polyhedral Oligomeric Silsesquioxanes (FluoroPOSS)

    DTIC Science & Technology

    2004-04-01

    Fluorodecyl(8T8), Contact Angle of Water on Fluorodecyl POSS Surface, Contact Angle of Mercury on Fluorodecyl POSS Surface, AFM Image of Spin-Cast...Fluorodecyl(8T8) Surface, Surface Energy of Fluorosiloxanes, Contact Angle and Chain Length, POSS Polymer Incorporation, Importance of R groups: Affect...compatibility with polymer matrix, PVDF/Fluoroocytl(8T8) POSS,PVDF/Fluoroocytl(nTn) POSS, Fluorinated Ethylene/Propylene, Poly(chlorotrifluoroethylene), Amorphous FEP, Water Contact Angle .

  11. Hydrophobic Silsesquioxane Nanoparticles and Nanocomposite Surfaces

    DTIC Science & Technology

    2008-09-23

    POSS materials are monodisperse and crystalline. The melting point of the POSS is lower than the processing conditions of the fluoropolymers , so one...obtained from Daikin. Composite Preparation Fluoropolymer composites have been prepared by melt blending five, ten, or fifteen weight percent...compounds also appear to act as a processing aid during fluoropolymer processing , significantly reducing both the torque and load measurements in the

  12. Molecular Structure Analysis of Aminophenyl Silsesquioxane (Preprint)

    DTIC Science & Technology

    2006-10-31

    5 ˚C/min and held at 200˚C for 2 hours, and then heated to 240˚C at a...generated at 45 kV and 200 mA. The diffraction angle ranged from 5 ˚ to 30˚, with step size and scan rate of 0.05˚ and 2 ˚ per minute, respectively...7 9 . 4 9 6 - 7 9 . 4 0 2 - 7 9 . 2 3 1 - 7 9 . 1 8 2 - 7 9 . 1 2 5 - 7 9 . 0 4 5 - 7 8 . 9 0 0 - 7 8 . 8 5 1 - 7 9 . 3 7

  13. Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS)

    DTIC Science & Technology

    2008-01-01

    Both FH and FD are triclinic (P1) showing the presence of one and two crystallographically independent “half” molecules in the asymmetric unit...conformations. The molecular structure of F-POSS contains rigid, rod-like fluoroalkyl chains, which are attached to the silicon atoms of the POSS cage...may also contribute to surface properties, including hydrophobicity. The crystal structures of FH and FD showed a near-parallel arrangement of the

  14. Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS)

    DTIC Science & Technology

    2010-02-01

    Cyrstallographic Data Center ( CCDC ). Assigned CCDC numbers for FH and FD are 608207 and 608209, respectively. Copies of the crystallography data...can be obtained, free of charge, from CCDC , 12 Union Road, Cambridge CB2 1EZ, UK (e-mail: deposit@ccdc.cam.ac.uk). 2.4 F-POSS Coating and Composite

  15. Thermosetting Poly(imide silsesquioxane)s Featuring Reduced Moisture Affinity and Improved Processability (Post Print)

    DTIC Science & Technology

    2013-09-11

    constituents as it provides versatile stereochemistry . 2. EXPERIMENTAL DETAILS Materials. The oligomer framework utilized in this study is derived from...moduli for the three sets of oligomers: (a) cis/trans-, (b) cis-, and (c) trans- in Figure 6. The crossover frequency (indicated by ωco), defined as

  16. Bis-(2-amino-5-methyl-pyridinium) fumarate-fumaric acid (1/1).

    PubMed

    Hemamalini, Madhukar; Fun, Hoong-Kun

    2010-07-24

    In the crystal structure of the title compound, C(6)H(9)N(2) (+)·0.5C(4)H(2)O(4) (2-)·0.5C(4)H(6)O(4), the fumarate dianion and fumaric acid mol-ecule are located on inversion centres. The 2-amino-5-methyl-pyrimidinium cation inter-acts with the carboxyl-ate group of the fumarate anion through a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. These motifs are centrosymmetrically paired via N-H⋯O hydrogen bonds, forming a complementary DDAA array. The carboxyl groups of the fumaric acid mol-ecules and the carboxyl-ate groups of the fumarate anions are hydrogen bonded through O-H⋯O hydrogen bonds, leading to a supra-molecular chain along [101]. The crystal structure is further stabilized by weak C-H⋯O hydrogen bonds.

  17. Magnetite-platinum nanoparticles-modified glassy carbon electrode as electrochemical detector for nitrophenol isomers.

    PubMed

    Gerent, Giles G; Spinelli, Almir

    2017-05-15

    A glassy carbon electrode was modified with magnetite and platinum nanoparticles stabilized with 3-n-propyl-4-picoline silsesquioxane chloride. This chemically-modified electrode is proposed for the first time for the individual or simultaneous electrochemical detection of nitrophenol isomers. Nanoparticles act as catalysts and also increase the surface area. The polymer stabilizes the particles and provides the electrochemical separation of isomers. Under optimized conditions, the reduction peak currents, obtained by differential-pulse voltammetry, of 2-, 3-, and 4-nitrophenol increased linearly with increases in their concentration in the range of 0.1-1.5μmolL(-1). In individual analysis, the detection limits were 33.7nmolL(-1), 45.3nmolL(-1) and 48.2nmolL(-1), respectively. Also, simultaneous analysis was possible for 2-, and 4-nitrophenol. In this case, the separation of the peak potentials was 0.138V and the detection limits were 69.6nmolL(-1) and 58.0nmolL(-1), respectively. These analytical figures of merit evidence the outstanding performance of the modified electrode, which was also successfully applied to the individual determination of isomers in environmental and biological samples. The magnetite and platinum nanoparticles modified glassy carbon electrode was able to detect nitrophenol isomers at the ppm level in rain water and human urine samples.

  18. Polymerization of Fluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS) Macromers

    DTIC Science & Technology

    2012-12-01

    mm Methanol Octane Methylene Iodide Water Superhydrophobic /oleophilic dip-coated fabric Tuteja et al, Science, 2007, 318, 1618 Superamphiphobic...allow for functionalization of F-POSS – Open door for use a building block material for low surface energy materials • Applications – Mechanical...robust superhydrophobic /oleophobic/omniphobic surfaces • Via covalently attached F-POSS to substrate (surface, nanoparticle, polymer matrix) – Effects

  19. Facile Synthesis of Hydrophobic Fluoroalkyl Functionalized Silsesquioxane Nanostructures (Postprint)

    DTIC Science & Technology

    2007-01-01

    any foreign debris.11 In addition, insect species such as the Water Strider possess oriented, spindled microsetae that induce a non-wetting effect...10 Coined the ‘‘lotus effect,’’ the intrinsic non- wetting mechanism induces water beading, and water is naturally repelled from the surface, removing...allowing this class of spider to walk on the surface of water .12 There are many reported approaches that successfully produce artificial, biologi

  20. Fluorinated Silsesquioxanes: Structure, Solubility, and Wetting (Briefing charts)

    DTIC Science & Technology

    2015-08-01

    Designing Omniphobic Surfaces • Constructing super-repellent surfaces – Three key ingredients Roughness (r) Surface Chemistry (e) Surface Geometry...blended in polymers • Potential non‐ionic surfactants 21DISTRIBUTION A. Approved for public release; distribution unlimited. F-POSS Copolymers Polym...336-713-7266, Email: mavandyk@wfubmc.edu Dr. Michael A. Bt·ook, Department of Chemistry , McMaster University, Hamilton, ON L8S 4M1, Canada Tel: 905

  1. Polyhedral Oligomeric Silsesquioxane (POSS) Polyimides as Space-Survivable Materials

    DTIC Science & Technology

    2006-01-01

    Survivable Materials 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER Sandra J. Tomczak (AFRL/PRSM); Vandana Vij...measurements on each sample Multiple samples of Kapton H®, 8.75 % Si8O11 MC-POSS PI, and silica-coated Kapton HN® (provided by Astral Technology Unlimited...Figure 3. SEM images of results from a self-passivation experiment. (a.) Kapton H®, (b.) SiO2 coated Kapton HN® (Provided by Astral

  2. Ultrahydrophobic Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS) (Preprint)

    DTIC Science & Technology

    2007-01-25

    This compound is surprisingly stable to hydrolysis and oxidation. Crystal structures of this compound have also been obtained. Fluorinated carbon...on same surface with contact angle of 154°. Crystals of F-POSS samples have been grown by solvent evaporation and single crystal X-ray structures ...have been obtained. FH and FD are shown at the top of Figure 3. From these structures , it can be observed that the electropositive silicon atoms

  3. Phenylethynyl Silsesquioxanes: Monomer Synthesis, Characterization,Thermolysis and Thermal Properties

    DTIC Science & Technology

    2016-12-14

    Tailorability WEAKNESSES Processability Moisture Uptake Imide USES Electrical Insulation Spacecraft Protection Polymer Matrix Composites Aircraft...Polyimides Image of PiMC laminate post-exposed to RH and subsequent rapid heating Courtesy of NAWCWD Moisture uptake by the resin matrix in PiMCs...R.; Yee, A.F. Composites Science and Technology 2002, 62, 2099–2110 8Distribution A: Approved for Public Release; Distribution Unlimited. PA

  4. Functionalized Fluorinated Polyhedral Oligomeric Silsesquioxane (F-POSS)

    DTIC Science & Technology

    2012-01-01

    AIBN, 60oC n m oo oo Si Si O O Si Si Si SiO O O Si O Si O O O O O Rf Rf RfRf Rf Rf Rf RfO O Si Initial Copolymerizations MMA-F-POSS (MW = 4179 g/mol...O Si O O O O O Rf Rf RfRf Rf Rf Rf RfO O Si Initial Copolymerizations MMA-F-POSS (MW = 4179 g/mol) MMA (MW = 100 g/mol) Weight Mol Ratio

  5. (E)-2-[4-(Diethyl-amino)-styr-yl]-1-methyl-pyridinium 4-meth-oxy-benzene-sulfonate monohydrate.

    PubMed

    Chantrapromma, Suchada; Kaewmanee, Narissara; Boonnak, Nawong; Anantapong, Teerasak; Fun, Hoong-Kun

    2012-09-01

    In the cation of the title compound, C(18)H(23)N(2) (+)·C(7)H(7)O(4)S(-)·H(2)O, one ethyl group of the diethyl-amino unit is disordered over two sets of sites in a 0.665 (6):0.335 (6) ratio. The styrylpyridinium unit is nearly planar, with a dihedral angle between the pyridinium and benzene rings of 4.27 (8)°. In the crystal, the anion ring is almost perpendicular to the aromatic rings of the cation; the sulfonate-substituted benzene ring forms dihedral angles of 89.60 (8) and 89.37 (8)°, respectively, with the pyridinium and benzene rings of the cation. In the crystal, the three components are linked into a three-dimensional network by O-H⋯O and C-H⋯O hydrogen bonds. π-π inter-actions with centroid-centroid distances of 3.6999 (9) and 3.7106 (9) Å are also present.

  6. Photobehaviour of methyl-pyridinium and quinolinium iodide derivatives, free and complexed with DNA. A case of bisintercalation.

    PubMed

    Mazzoli, Alessandra; Carlotti, Benedetta; Consiglio, Giuseppe; Fortuna, Cosimo G; Miolo, Giorgia; Spalletti, Anna

    2014-06-01

    Excited state dynamics of four azinium salts were studied in buffered water and in the presence of salmon testes DNA. Complexation with DNA changes the photobehaviour of the free ligands lowering the photoreactivity and emission in favor of internal conversion. The interaction of these four dyes with DNA was studied with different techniques with the aim to establish the affinity and the type of binding between the ligands and DNA. The results from spectrophotometric and fluorimetric titrations provided evidence of a strong interaction between the azinium salts and the polynucleotide, with a binding constant of about 10(6) M(-1), making them interesting for therapeutical applications. Dichroic measurements allowed us to determine the possible modes of binding for each complex. Short living excited states of the free dyes were detected and characterized by ultrafast absorption spectroscopy. A further decrease of transient lifetimes was observed upon interaction with DNA. The bicationic pyridinium iodide was found to act as a bisintercalative agent, potentially increasing the cytotoxicity with low dose and less collateral effects.

  7. Synthesis of polyhedral oligomeric silsesquioxane (POSS) functionalized carbon nanotubes for improved dispersion in polyurethane films

    NASA Astrophysics Data System (ADS)

    Kou, Xiaonan

    Carbon nanotube (CNT) polymer nanocomposites are promising advanced materials. These materials exhibit the advantages of traditional polymeric materials, such as being light weight and easy to process, combined with the potential to exhibit enhanced mechanical, thermal and electrical properties compared to pure polymers. To achieve substantial improvement of composite properties at low CNT loading, uniform dispersion of CNTs in the polymer matrix and strong CNT-polymer interfacial interaction are needed. However, it is difficult to achieve adequate dispersion and interfacial interactions due to the inert nature of CNTs. In this project, polyhedral oligomeric silsequioxane (POSS) will be used as a dispersing agent for multi-walled carbon nanotubes (MWNTs) in polyurethane (PU) matrices. This dissertation consists of six chapters. Chapter I provides a detailed introduction of the fundamental knowledge of CNTs, PU, and POSS. At the end of this chapter, the motivation and rationale of this research are given. Chapter II establishes the overall goal and specific objectives of this research. Chapter III describes the synthesis and characterization of three POSS modified CNTs and one organosilane modified CNT. Grafting efficiency of the different grafted molecules are calculated and compared. Chapter IV discusses the dispersion behavior of four covalently modified CNTs in both solvents and PU matrices. Differences in dispersion behaviors of the modified CNTs are correlated to the solubility parameters of the grafting molecules and the surface structures of modified CNTs. Chapter V provides further discussion of the dispersion of POSS and silane modified CNTs by reviewing the assessment of the physical properties of PU composites containing the modified CNTs. Morphological, thermal, mechanical and electrical properties are used to estimate the interactions of the modified CNTs with the PU matrix. Chapter VI explores the function of the trisilanolphenyl POSS lithium salt (TSPLi) as a dispersant for CNTs in thermoplastic polyurethane (TPU) during melt extrusion. The dispersion of CNTs and TSPLi modified CNTs are estimated by mechanical and electrical property measurement of the PU/CNT and PU/CNT-POSS composites.

  8. Synthesis of Polyimides Produced from Novel High Temperature Polyhedral Oligomeric Silsesquioxane Dianilines

    DTIC Science & Technology

    2009-03-26

    periphery tar~crinp appltcatiuns with challenging tcmpxaturc and uniclation quircnlc.nis ha< b a n reprted . Copolymcrimtion of he diamine monomer with...Propulsion Uirectonte for Financial supwrl of this research. References [ I I k ~ h i l ~ t . \\ l . HII\\\\<. J.. N.~li+:i. H,\\:I Si11sl1 ?,,L

  9. Fluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS) Based Monomers and Polymers

    DTIC Science & Technology

    2011-07-19

    for use a building block material for low surface energy materials • Applications – Mechanical robust superhydrophobic /oleophobic/omniphobic surfaces...modifiers, and many other applications Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Chem. Rev. 2010, 110, 2081. Phillips, S. H.; Haddad, T. S.; Tomczak...surface energies leading to the creation of superhydrophobic and oleophobic surfaces. (a) Mabry, J. M.; Vij, A.; Iacono, S. T.; Viers, b. D., Angew

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

    DTIC Science & Technology

    2012-08-01

    developed and observed to be an excellent nano-filler for low surface energy applications (1–4). These compounds possess an inorganic silicon-oxygen core... superhydrophobic and superoleophobic surfaces (7–10). Dramatic improvements in water and oil repellency were observed when F-POSS was blended with...monomers are currently being investigated in a variety of copolymers and are expected to deliver new robust, abrasion resistant, superhydrophobic , and

  11. Functional Perfluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS): Building Blocks for Low Surface Energy Materials

    DTIC Science & Technology

    2010-10-21

    low-surface energy material for superhydrophobic and oleophobic surfaces. These F-POSS compounds consist of a silicon-oxide core with a periphery of...for the development of new superhydrophobic and oleophobic materials. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF...F·I’OSS. These no\\e1 structures can he used as the initial building blocks for the development of Ilew superhydrophobic and o!cophobic materials

  12. Incompletely-Condensed Fluoroalkyl Silsesquioxanes and Derivatives: Precursors for Low Surface Energy Materials (Preprint)

    DTIC Science & Technology

    2011-09-13

    superhydrophobic and oleophobic materials. Utilizing triflic acid, open-cage compounds were created and then reacted with a variety of dichlorosilanes...fluorinated nanobuilding blocks with a controlled level of reactive functionality for the development of new superhydrophobic and oleophobic...F-POSS), which are useful as low surface energy materials for superhydrophobic and oleophobic materials. Utilizing triflic acid, open-cage

  13. Water Breakthrough Pressure of Cotton Fabrics Treated with Fluorinated Silsesquioxane / Fluoroelastomer Coatings (Preprint)

    DTIC Science & Technology

    2012-10-01

    significant for practical applications . Unfortunately, there has to date been scant experimental work[24] focused on this aspect of superhydrophobicity in...filaments. Keywords: Breakthrough pressure, F-POSS, Superhydrophobic , Dip-coating 2 The treatment of cotton fabrics to obtain... superhydrophobicity and even superoleophobicity[1-4] has received increasing attention in recent years. Various surface treatments involving siloxanes[5-7

  14. Synthesis and Characterization of Long-Chain Fluorinated Polyhedral Oligomeric Silsesquioxane (F-POSS)

    DTIC Science & Technology

    2010-10-21

    are resistant to welling by both water and oils is of considerable inl~rcst. Non-wctting materials find application as sea)" fingerp ri nt...rcsistant touch screens, and anti-icing materials. I Superhydrophobicity and supcrokophobicity, ddioed as haviog a contact angles of greater than 1500 and...fluorinated hydrocarbons for superhydrophobic propertics. Fluorodecyl POSS (FD), wllich is surrounded by eight 10-carbon alkyl groups with dght carbon

  15. Fluorpolymer Property Enhancement via Incorporation of Fluorinated Polyhedral Oligomeric Silsesquioxanes (FluoroPOSS)

    DTIC Science & Technology

    2007-11-02

    These POSS fluoropolymers may be useful as low friction surfaces or hydrophobic coatings. Contact angle measurements of the POSS fluoropolymers show an...weights and highest densities of any POSS compounds yet produced. They also have remarkable surface properties, which have been observed in water contact ... angle measurements. A number of FluoroPOSS compounds have been produced from their respective trifunctional monomers. These FluoroPOSS compounds have

  16. Thermal Transitions and Reaction Kinetics of Polyhederal Silsesquioxane Containing Phenylethynylphthalimides (Preprint)

    DTIC Science & Technology

    2010-03-18

    hexane, diethylether and dimethylacetimide (DMAc) were obtained from Aldrich and purified prior to use. Magnesium turnings, (N- trimethylsilyl) 2 - 4 ...method.31 Synthetic methods Synthesis of ((N-trimethylsilyl) 2 -aniline- 4 -(dichloromethylsilane) In a drybox under a nitrogen atmosphere, a THF solution...25 mL) of (N-trimethylsilyl) 2 - 4 -bromoaniline (9.483 g, 30.0 mmol) was added in a drop-wise manner to a 250 mL flask containing well-stirred

  17. Thermomechanical Properties of Poly(methyl methacrylates) Containing Tethered and Untethered Polyhedral Oligomeric Silsesquioxanes (POSS)

    DTIC Science & Technology

    2006-05-31

    temperature were performed in a Siemens 2D Small Angle Diffractometer configured in Wide Angle mode using a 12kW rotating anode; these samples (powders...Cp) Si O Si Si SiO O O Si O Si Si SiO O O O O O O R R R R R R R R CH3 R OO CH3 O CH3 O Si O Si Si Si O O O Si O Si Si Si O O O O O O O R R R R R R nx

  18. Preparation of Composite Fluoropolymers with Enhanced Dewetting Using Fluorinated Silsesquioxanes as Drop-In Modifiers (Preprint)

    DTIC Science & Technology

    2010-02-17

    blend formulations have potential use as hydro- and oleophobic materials for seals, fibers, and coatings. 15. SUBJECT TERMS 16. SECURITY...This work demonstred that optimized F-POSS PFCB aryl ether polymer blend formulations have potential use as hydro- and oleophobic materials for seals... oleophobic 20 properties. There are numerous examples of materials that mimic naturally evolved biological systems, albeit they are mostly limited to

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

    DTIC Science & Technology

    2005-10-11

    Fluorodecyl8T8 and fluorooctyl8T8 increased the oleophobicity of PVDF – Unfilled PVDF samples yielded contact angles around 25° – Addition of...the oleophobicity of PVDF PVDF PVDF 5wt% Fluorooctyl8T8 19 DRAFT: Distribution A: Approved for public release; distribution unlimited Results and...fluoropolymers increased the water and organic contact angles – Addition of methyl8T8 to PVDF decreased the oleophobicity , but increased the hydrophobicity

  20. Effects of Peripheral Architecture on the Properties of Aryl Polyhedral Oligomeric Silsesquioxanes

    DTIC Science & Technology

    2012-07-26

    analysis, mass spectrometry, and Fourier transform infrared spectroscopy. The peripheral aryl architecture, although similar in most cases, was found to...techniques, as well as differential scanning calorimetry, thermogravimetric analysis, mass spectrometry, and Fourier transform infrared spectroscopy...component, or in-phase component, of the heat flow. Fourier transform infrared spectroscopy (FTIR) was performed using a Thermo Electron Corporation

  1. Interaction of polyhedral oligomeric silsesquioxane containing epoxycyclohexyl groups with cholesterol at the air/water interface.

    PubMed

    Dopierała, Katarzyna; Maciejewski, Hieronim; Prochaska, Krystyna

    2016-04-01

    Binary mixtures of cholesterol and fully-condensed octakis[{2-(3,4-epoxycyclohexyl) etyl}dimethyl-silyloxy]octasilsesquioxane (OE-POSS) were characterized using Langmuir trough for obtaining surface pressure-area isotherms. The most characteristic feature of the mixed films is the presence of two collapse points on the isotherms. The first one is attributed to the collapse of less stable OE-POSS and it occurs at similar surface pressures for all compositions, while the second one corresponds to cholesterol collapse. Brewster angle microscopy observations confirmed the collapse behavior of the mixed film. Strong condensing effect was observed for the mean molecular areas dependence on cholesterol content in the film. Moreover, formation of microdomains of each component in the matrix of the other one was confirmed by BAM images. For the reasons of molecular structures and interactions a true mixed and homogenous film did not form in the systems considered. Phase separation was observed for all the compositions experimented. The lack of the interactions of OE-POSS with biomembrane components represented by cholesterol is beneficial for applications of OE-POSS in biomedical devices. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Asymmetric Aryl Polyhedral Oligomeric SilSesquioxanes (ArPOSS) with Enhanced Solubility (Preprint)

    DTIC Science & Technology

    2011-03-23

    where Aryl = 1-naphthyl , 2-naphthyl, 9- phenanthren yl, and 1-pyrenyl, have been synthesized in reasonable yield and high purity. These compounds... phenanthren yl group to produce (9 - phenanthrenyl)phenyl7Si8O12 (5) results in comparable solubility in THF to that of 2, as well as the highest solubility

  3. The influence of porosity on the hemocompatibility of polyhedral oligomeric silsesquioxane poly (caprolactone-urea) urethane.

    PubMed

    Zhao, Junjie; Farhatnia, Yasmin; Kalaskar, Deepak M; Zhang, Yanting; Bulter, Peter E M; Seifalian, Alexander M

    2015-11-01

    The physio-chemical properties of blood contacting biomaterials play an important role in determining their hemocompatibility. It is shown in literature that surface roughness and porosity have significant effect on hemocompatibility. In this study, we use a biocompatible, low thrombogenic nanocomposite polymer called POSS-PCU to test this hypothesis: would porosity compromise the hemocompatibility of POSS-PCU. We compared the hemocompatibility of POSS-PCU films of various pore sizes with PTFE, which is a commercially available material used in most blood contacting devices. Sterilized POSS-PCU films with different size pores were prepared as samples and porous PTFE film were selected as control. And all samples were subjected to SEM for topograpgy, mechanical test for characterization and hemocompatibility tests to evaluate contact activation, platelet adhesion and activation, as well as whole blood clotting response to the samples. WCA significantly increased with the pore size of POSS-PCU film, whereas both tensile stress and strain decreased significantly as the sizes of pores increased. However, when compared to PTFE film with same size pores, POSS-PCU films showed both higher tensile stress and strain. Pore size had little impact over POSS-PCU's surface chemistry groups as tested by FTIR analysis. Contact activation and platelet adhesion essay also showed no significant difference between different POSS-PCU samples. However, in whole blood reactions, POSS-PCU with pores size around 2-5μm showed higher BCI than plain films and those with pores size around 35-45μm. POSS-PCU showed lower thrombogencity and higher hemocompatibility comparing with porous PTFE on the aspects of platelet activation, adhesion and whole blood reaction. POSS-PCU polymer films as a biomaterial in chronic blood contacting implants show significant lower thrombogencity and higher hemocompatibility than porous PTFE film. It is desirable as a coating or covering material in small diameter stents for treating cardiovascular diseases, cerebral vascular diseases and peripheral arterial diseases. Copyright © 2015. Published by Elsevier Ltd.

  4. Synthesis of Aromatic Polyhedral Oligomeric Silsesquioxane (POSS) Dianilines for Use in High-Temperature Polyimides

    DTIC Science & Technology

    2012-05-01

    thermosetting resins, the difunctional compounds possess well- defined structure and stereochemistry , and can be utilized to improve properties in a...that this linkage was not a thermal weak point. Additionally, the stereochemistry of the aniline functionality has been varied to produce both meta...POSS cage in order to ensure that this linkage was not a thermal weak point.   Additionally, the  stereochemistry  of the aniline functionality has been

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Thermodynamic Stability and Kinetic Lability of Fully-Condensed Fluorinated Polyhedral Oligomeric Silsesquioxane (POSS) Cages (Preprint)

    DTIC Science & Technology

    2009-03-26

    Ttrno~hy 5 ~oddarp’. Jeny EM$, Suruh webeg andJoseph M ~ a b v ’ IERC Inc., ’ A I ~ Forcc Rcscarch Laboratory Building 845 1. 10 East Saturn Boulcvanl...Klcmpcm. W.G, J. A. Chem. Sor 1987,109,5554. (4) Rikowski. E.; Marsmann. H.C. Polb*hedrun 1997, 16,3357. ( 5 ) Xiang. K.-H.; Pan &y,R.:Pcrnisz. U.C

  7. Branched Polyhedral Oligomeric Silsesquioxane Nanoparticles Prepared via Strain-Promoted 1,3-Dipolar Cycloadditions

    PubMed Central

    Ledin, Petr A.; Xu, Weinan; Friscourt, Frédéric; Boons, Geert-Jan; Tsukruk, Vladimir V.

    2016-01-01

    Conjugation of small organic molecules and polymers to polyhedral oligosilsesquioxane (POSS) cores results in novel hybrid materials with unique physical characteristics. We report here an approach in which star-shaped organic–inorganic scaffolds bearing eight cyclooctyne moieties can be rapidly functionalized via strain-promoted azide–alkyne cycloaddition (SPAAC) to synthesize a series of nearly monodisperse branched core–shell nanoparticles with hydrophobic POSS cores and hydrophilic arms. We established that SPAAC is a robust method for POSS core octafunctionalization with the reaction rate constant of 1.9 × 10−2 M−1 s−1. Functionalization with poly(ethylene glycol) (PEG) azide, fluorescein azide, and unprotected lactose azide gave conjugates which represent different classes of compounds: polymer conjugates, fluorescent dots, and bioconjugates. These resulting hybrid compounds were preliminarily tested for their ability to self-assemble in solution and at the air–water interface. We observed the formation of robust smooth Langmuir monolayers with diverse morphologies. We found that polar lactose moieties are completely submerged into the subphase whereas the relatively hydrophobic fluorescein arms had extended conformation at the interface, and PEG arms were partially submerged. Finally, we observed the formation of stable micelles with sizes between 70 and 160 nm in aqueous solutions with size and morphology of the structures dependent on the molecular weight and the type of the peripheral hydrophilic moieties. PMID:26131712

  8. Properties and Improved Space Survivability of POSS (Polyhedral Oligomeric Silsesquioxane) Polyimides

    DTIC Science & Technology

    2004-11-01

    Resins,” Chemistry of Materials. 2003, 15, 264-268 10. Feher, F.J., Nguyen, F., Soulivong , D., and Ziller, J.W., "A New Route to Incompletely Condensed...Feher, F.J., Soulivong , D., and Eklund, A.G., "Controlled Cleavage of R8Si8O12 Frameworks: A Revolutionary New Method for Manufacturing Precursors to

  9. Cubic Silsesquioxanes as a Green, High-Performance Mold Material for Nanoimprint Lithography

    SciTech Connect

    Ro, Hyun W.; Popova, Vera; Chen, Lei; Forster, Aaron M.; Ding, Yifu; Alvine, Kyle J.; Krug, Dave J.; Laine, Richard M.; Soles, Christopher L.

    2010-08-16

    Optical lithography deep in the UV spectrum is the predominate route for high-resolution, high-volume nanoscale pattering. However, state-of-the-art optical lithography tools are exceedingly expensive and this places serious limitations on the applications, technical sectors, and markets where highresolution patterning can be implemented. To date the only substantial market for high-end optical lithography tools has been semiconductor fabrication. Nanoimprint lithography (NIL) has recently emerged as an alternative to optical lithography and combines the potential of sub-fi ve-nanometer patterning resolution with the low cost and simplicity of a stamping process. [ 1–4 ] This has led to signifi cant efforts to implement NIL methods, not only for semiconductor logic devices, but also in fi elds as diverse as the direct patterning of interlayer dielectrics (ILDs) for back-end-of-line (BEOL) interconnect structures, [ 5–7 ] bitpatterned magnetic media for data storage, [ 8 , 9 ] and high-brightness light-emitting diodes (LEDs). [ 10 ] Some of these are new areas where nanoscale patterning has previously not been considered, and are made possible here by the low cost and simplicity of the NIL stamping processes.

  10. NEW FE(III) AND OS(VI) SILSESQUIOXANES. (R829553)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  11. Styrene-butadiene-styrene Tri-block Copolymers Modified wit Polyhedral Oligomeric Silsesquioxanes

    DTIC Science & Technology

    2006-05-31

    morphology.1-6 Polymer nano -composites are a new and active research area in the field of block copolymers. Block copolymers reinforced by various nano -sized...fillers have been prepared and studied; layered silicates-based nano -composites have drawn the most attention thus far. 7- 9 Although domain...morphology is not strongly influenced by the blending of layered- silicates, these nano -reinforced block copolymers have shown promising property enhancements

  12. Comparisons of Polyhedral Oligomeric Silsesquioxane (POSS) Polyimides as Space-Survivable Materials (Postprint)

    DTIC Science & Technology

    2006-11-15

    AFRL/PRSM); Vandana Vij (ERC); 5d. PROJECT NUMBER DARPA443 Timothy Minton & Amy Brunsvold (Montana State Univ.); Michael Wright, Brian Petteys...8.75 % Si8O11 MC-POSS PI, and silica-coated Kapton HN® (provided by Astral Technology Unlimited, Inc. Lot No. 00625-007, with a 130 nm SiO2 coating...images of results from a self-passivation experiment. (a.) Kapton H®, (b.) SiO2 coated Kapton HN® (Provided by Astral Industries Inc.), and (c.) 8.75 wt

  13. Polyhedral Oligomeric Silsesquioxane (POSS) Polyimides as Space-Survivable Materials (Preprint)

    DTIC Science & Technology

    2006-07-27

    Survivable Materials (Preprint) 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER Sandra J. Tomczak (AFRL/PRSM...Multiple samples of Kapton H®, 8.75 % Si8O11 MC-POSS PI, and silica-coated Kapton HN® (provided by Astral Technology Unlimited, Inc. Lot No. 00625-007...self-passivation experiment. (a.) Kapton H®, (b.) SiO2 coated Kapton HN® (Provided by Astral Industries Inc.), and (c.) 8.75 wt % Si8O11 cage MC

  14. Fluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS) Based Monomers and Polymers

    DTIC Science & Technology

    2011-04-04

    Joseph M. Mabry 5d. PROJECT NUMBER 5f. WORK UNIT NUMBER 23030521 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING... ORGANIZATION REPORT NUMBER Air Force Research Laboratory (AFMC) AFRL/RZSM 9 Antares Road Edwards AFB CA 93524-7401 AFRL-RZ-ED-TP-2011-120 9...monomers (F-POSS-MMA and F-POSS-A). Structures were confirmed with multinuclear NMR (1H, 13C, and 29Si) and found to be soluble in non-fluorinated

  15. The pharmacokinetics of pyridostigmine and 3-hydroxy-N-methylpyridinium in the rat: dose-dependent effects after portal vein administration.

    PubMed Central

    Barber, H E; Bourne, G R; Calvey, T N; Muir, K T

    1975-01-01

    1 The elimination kinectis of [14C]-pyridostigmine iodine and [14-C-methyl]-3-hydroxypyridinium bromide (3-OH NMP) have been studied in the rat. 2 For pyridostigmine, at a given dose level, the fraction of the dose eliminated unchanged was reduced and the metabolite fraction was increased after portal vein administration when compared to jugular vein administration. This indicates that pyridostigmine is subject to metabolism during the first passage through the liver. 3 When doses of pyridostigmine 1.25 mumol/kg and higher were injected via the portal vein, the proportion excreted in urine as unchanged drug remained constant; in contrast, the percentage of the dose eliminated as the metabolite was significantly reduced. This indicates that a dose-dependent process is involved in the urinary excretion of 3-OH NMP. 4 This conclusion was supported by studies involving the portal and systemic venous injection of 3-OH NMP at different dose levels. After 4 h, approximately85% of the lowest dose was eliminated unchanged in ug this period. The proportion of the dose eliminated in urine was not related to the route of administration. 5 After the injection of pyridostigmine into the jugular vein, the initial rate of drug excretion fell rapidly for approximately 10 min; in contrast, after injection into the portal vein, the rate of excretion of the drug rose to a maximum at 30 minutes. This suggests that the hepatoportal system behaves as a distinct region during the distribution of this drug. PMID:173444

  16. 2-[(E)-2-(4-Hy-droxy-3-meth-oxy-phen-yl)ethen-yl]-1-methylpyridinium 4-bromo-benzene-sulfonate monohydrate.

    PubMed

    Chantrapromma, Suchada; Boonnak, Nawong; Jindawong, Boonwasana; Fun, Hoong-Kun

    2013-11-30

    The title salt crystallized as the monohydrate C15H16NO2 (+)·C6H4BrSO3 (-)·H2O. The cation exists in an E conformation with respect to the ethynyl bond and is essentially planar, with a dihedral angle of 6.52 (14)° between the pyridinium and the benzene rings. The hy-droxy and meth-oxy substituents are coplanar with the benzene ring to which they are attached, with an r.m.s. deviation of 0.0116 (3) Å for the nine non-H atoms [Cmeth-yl-O-C-C torsion angle = -0.8 (4)°]. In the crystal, the cations and anions are stacked by π-π inter-actions, with centroid-centroid distances of 3.7818 (19) and 3.9004 (17) Å. The cations, anions and water mol-ecules are linked by O-H⋯O hydrogen bonds and weak C-H⋯O inter-actions, forming a three-dimensional network.

  17. Polyhedral Oligomeric Silsesquioxane-Functionalized Perfluorocyclobutyl Aryl Ether Polymers: An Overview of the Synthesis and Properties of Polyhedral Oligomeric Silsesquioxanes (POSS) Functionalized with Perfluorocyclobutyl (PFCB) Aryl Ether Polymer Blends and Copolymers (Preprint)

    DTIC Science & Technology

    2007-10-17

    Polymer Blends Fluorinated POSS (F-POSS) compounds were blended into PFCB polymer poly5 (Man = 22000 , PDI = 2.2; GPC in CHCl3 using PS as standard) by...transition temperature (Tg) with POSS copolymers. The decrease was most noticeable for copolymers with iso -butyl groups (R = i-Bu) and further...Surface Analysis. Copolymers with up to 20 wt% iso -butyl functionalized POSS produced solution processable, optically transparent, semi-flexible films

  18. Reversible Addition-Fragmentation Chain Transfer (RAFT) Copolymerization of Fluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS) Macromers (Postprint)

    DTIC Science & Technology

    2013-02-25

    improved surface robustness. These F-POSS/MMA copolymers have also been used to coat cotton fabrics, resulting in both superhydrophobic and oleophobic...resulting in both superhydrophobic and oleophobic behaviour. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18...These F-POSS/MMA copolymers have also been used to coat cotton fabrics, resulting in both superhydrophobic and oleophobic behaviour.Low surface energy

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

    DTIC Science & Technology

    2016-08-22

    the final product. Processing treatments can be slightly varied at this point depending on the final product, but heat and pressure are typically...thickness and cured under pressure in a hot press. A known cure cycle for PMR-15 has been well established, but for new oligomers an appropriate cure...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

  20. Miniaturized catalysis: monolithic, highly porous, large surface area capillary flow reactors constructed in situ from polyhedral oligomeric silsesquioxanes (POSS).

    PubMed

    Scholder, P; Nischang, I

    2015-08-21

    A single-step molding process utilizing free-radical cross-linking reaction of vinyl POSS in microliter-sized dimensions leads to hierarchically-structured, mechanically robust, porous hybrid structures. Functional variants show excellent performance in Suzuki-type coupling reactions. Due to their small volume, long-term operational robustness, and potential chemical diversity, these materials are promising candidates for catalyst screening applications.

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

    DTIC Science & Technology

    2006-11-07

    studied because of their similar stereochemistry , similar molecular weight, and contrasting electronic properties. It was shown that the morphology...butadiene domain is a continuous phase. Hence, the addition of dimensionally well- defined nano-structured chemicals such as POSS to the continuous...precisely define the phase space of the POSS-SBS grafts, but to put the TODT changes in the context of the reduction of polystyrene content by

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

    DTIC Science & Technology

    2007-01-01

    cyclohexenyl (Cye), and phenyl (Ph)) were studied because of their similar stereochemistry , similar molecular weight, and contrasting electronic...significantly affected after grafting. The purpose of this plot is not to precisely define the phase space of the POSS-SBS grafts, but to put the TODT changes

  3. From Nanoscience to Nanotechnology: The Development and Application of Polyhedral Oligomeric Silsesquioxanes (POSS) as Versatile, Engineering Nanomaterials

    DTIC Science & Technology

    2004-09-21

    Nanomaterials. 21 September 04 j Dr. Shawn H. Phillips Chief, Propulsion Materials Applications Branch AFRL/PRSM shawn.phillips@edwards.af.mil Si...name Coughlin Building Block Model (POSS Blends & Copolymers) Bryan Coughlin-UMass DISTRIBUTION A. Approved for public release; distribution unlimited...8 File name Coughlin Model Continued ( building from the ground up) 1. As a solid, POSS crystallizes DISTRIBUTION A. Approved for public release

  4. Superhydrophobic-superhydrophilic binary micropatterns by localized thermal treatment of polyhedral oligomeric silsesquioxane (POSS)-silica films

    NASA Astrophysics Data System (ADS)

    Schutzius, Thomas M.; Bayer, Ilker S.; Jursich, Gregory M.; Das, Arindam; Megaridis, Constantine M.

    2012-08-01

    Surfaces patterned with alternating (binary) superhydrophobic-superhydrophilic regions can be found naturally, offering a bio-inspired template for efficient fluid collection and management technologies. We describe a simple wet-processing, thermal treatment method to produce such patterns, starting with inherently superhydrophobic polysilsesquioxane-silica composite coatings prepared by spray casting nanoparticle dispersions. Such coatings become superhydrophilic after localized thermal treatment by means of laser irradiation or open-air flame exposure. When laser processed, the films are patternable down to ~100 μm scales. The dispersions consist of hydrophobic fumed silica (HFS) and methylsilsesquioxane resin, which are dispersed in isopropanol and deposited onto various substrates (glass, quartz, aluminum, copper, and stainless steel). The coatings are characterized by advancing, receding, and sessile contact angle measurements before and after thermal treatment to delineate the effects of HFS filler concentration and thermal treatment on coating wettability. SEM, XPS and TGA measurements reveal the effects of thermal treatment on surface chemistry and texture. The thermally induced wettability shift from superhydrophobic to superhydrophilic is interpreted with the Cassie-Baxter wetting theory. Several micropatterned wettability surfaces demonstrate potential in pool boiling heat transfer enhancement, capillarity-driven liquid transport in open surface-tension-confined channels (e.g., lab-on-a-chip), and select surface coating applications relying on wettability gradients. Advantages of the present approach include the inherent stability and inertness of the organosilane-based coatings, which can be applied on many types of surfaces (glass, metals, etc.) with ease. The present method is also scalable to large areas, thus being attractive for industrial coating applications.Surfaces patterned with alternating (binary) superhydrophobic-superhydrophilic regions can be found naturally, offering a bio-inspired template for efficient fluid collection and management technologies. We describe a simple wet-processing, thermal treatment method to produce such patterns, starting with inherently superhydrophobic polysilsesquioxane-silica composite coatings prepared by spray casting nanoparticle dispersions. Such coatings become superhydrophilic after localized thermal treatment by means of laser irradiation or open-air flame exposure. When laser processed, the films are patternable down to ~100 μm scales. The dispersions consist of hydrophobic fumed silica (HFS) and methylsilsesquioxane resin, which are dispersed in isopropanol and deposited onto various substrates (glass, quartz, aluminum, copper, and stainless steel). The coatings are characterized by advancing, receding, and sessile contact angle measurements before and after thermal treatment to delineate the effects of HFS filler concentration and thermal treatment on coating wettability. SEM, XPS and TGA measurements reveal the effects of thermal treatment on surface chemistry and texture. The thermally induced wettability shift from superhydrophobic to superhydrophilic is interpreted with the Cassie-Baxter wetting theory. Several micropatterned wettability surfaces demonstrate potential in pool boiling heat transfer enhancement, capillarity-driven liquid transport in open surface-tension-confined channels (e.g., lab-on-a-chip), and select surface coating applications relying on wettability gradients. Advantages of the present approach include the inherent stability and inertness of the organosilane-based coatings, which can be applied on many types of surfaces (glass, metals, etc.) with ease. The present method is also scalable to large areas, thus being attractive for industrial coating applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr30979c

  5. Superhydrophobic-superhydrophilic binary micropatterns by localized thermal treatment of polyhedral oligomeric silsesquioxane (POSS)-silica films.

    PubMed

    Schutzius, Thomas M; Bayer, Ilker S; Jursich, Gregory M; Das, Arindam; Megaridis, Constantine M

    2012-09-07

    Surfaces patterned with alternating (binary) superhydrophobic-superhydrophilic regions can be found naturally, offering a bio-inspired template for efficient fluid collection and management technologies. We describe a simple wet-processing, thermal treatment method to produce such patterns, starting with inherently superhydrophobic polysilsesquioxane-silica composite coatings prepared by spray casting nanoparticle dispersions. Such coatings become superhydrophilic after localized thermal treatment by means of laser irradiation or open-air flame exposure. When laser processed, the films are patternable down to ∼100 μm scales. The dispersions consist of hydrophobic fumed silica (HFS) and methylsilsesquioxane resin, which are dispersed in isopropanol and deposited onto various substrates (glass, quartz, aluminum, copper, and stainless steel). The coatings are characterized by advancing, receding, and sessile contact angle measurements before and after thermal treatment to delineate the effects of HFS filler concentration and thermal treatment on coating wettability. SEM, XPS and TGA measurements reveal the effects of thermal treatment on surface chemistry and texture. The thermally induced wettability shift from superhydrophobic to superhydrophilic is interpreted with the Cassie-Baxter wetting theory. Several micropatterned wettability surfaces demonstrate potential in pool boiling heat transfer enhancement, capillarity-driven liquid transport in open surface-tension-confined channels (e.g., lab-on-a-chip), and select surface coating applications relying on wettability gradients. Advantages of the present approach include the inherent stability and inertness of the organosilane-based coatings, which can be applied on many types of surfaces (glass, metals, etc.) with ease. The present method is also scalable to large areas, thus being attractive for industrial coating applications.

  6. Synthesis, Characterization and Properties of Chain Terminated Polyhedral Oligomeric Silsesquioxane-Functionalized Perfluorocyclobutyl Aryl Ether Copolymers (Preprint)

    DTIC Science & Technology

    2007-10-17

    Journal Article 3. DATES COVERED (From - To) 4 . TITLE AND SUBTITLE 5a. CONTRACT NUMBER Synthesis, Characterization and Properties of Chain Terminated...deprotection and coupling with 4 -(trifluorovinyloxy)benzoic acid. TFVE functionalized POSS monomers were thermally polymerized with 4,4’-bis( 4 ...trifluorovinyloxy)biphenyl or 2,2-bis( 4 -trifluorovinyloxybiphenyl)-1,1,1,3,3,3-hexafluoropropane monomers via a condensate-free, [2+2] step-growth

  7. Synthesis, Characterization and Properties of Chain Terminated Polyhedral Oligomeric Silsesquioxane-Functionalized Perfluorocyclobutyl Aryl Ether Copolymers (Postprint)

    DTIC Science & Technology

    2007-01-01

    Journal Article 3. DATES COVERED (From - To) 4 . TITLE AND SUBTITLE 5a. CONTRACT NUMBER Synthesis, Characterization and Properties of Chain Terminated...acetoxyethyltrichlorsilane followed by sequential acid-catalyzed deprotection and coupling with 4 -(trifluorovinyloxy)benzoic acid. TFVE functionalized POSS monomers...were thermally polymerized with 4,4’-bis( 4 -trifluorovinyloxy)biphenyl or 2,2-bis( 4 -trifluorovinyloxybiphenyl)-1,1,1,3,3,3-hexafluoropropane monomers

  8. 2-[(E)-2-(4-Hy­droxy-3-meth­oxy­phen­yl)ethen­yl]-1-methylpyridinium 4-bromo­benzene­sulfonate monohydrate

    PubMed Central

    Chantrapromma, Suchada; Boonnak, Nawong; Jindawong, Boonwasana; Fun, Hoong-Kun

    2013-01-01

    The title salt crystallized as the monohydrate C15H16NO2 +·C6H4BrSO3 −·H2O. The cation exists in an E conformation with respect to the ethynyl bond and is essentially planar, with a dihedral angle of 6.52 (14)° between the pyridinium and the benzene rings. The hy­droxy and meth­oxy substituents are coplanar with the benzene ring to which they are attached, with an r.m.s. deviation of 0.0116 (3) Å for the nine non-H atoms [Cmeth­yl—O—C—C torsion angle = −0.8 (4)°]. In the crystal, the cations and anions are stacked by π–π inter­actions, with centroid–centroid distances of 3.7818 (19) and 3.9004 (17) Å. The cations, anions and water mol­ecules are linked by O—H⋯O hydrogen bonds and weak C—H⋯O inter­actions, forming a three-dimensional network. PMID:24454267

  9. Properties of POSS-Modified Oligoimide Resins

    DTIC Science & Technology

    2011-08-19

    as a foundation, the objective of this work is to examine the effects of incorporating silsesquioxane anilines into the backbones of thermosetting...work is to examine the effects of incorporating silsesquioxane anilines into the backbones of thermosetting polyimides, particularly elucidating...that copolymerization of polyhedral oligomeric silsesquioxane (POSS) diamines into thermoplastic pyromellitic dianhydride-oxydiphenylene aniline

  10. Conceptual Design of Large Surface Area Porous Polymeric Hybrid Media Based on Polyhedral Oligomeric Silsesquioxane Precursors: Preparation, Tailoring of Porous Properties, and Internal Surface Functionalization

    PubMed Central

    2013-01-01

    We report on the preparation of hybrid, organic–inorganic porous materials derived from polyhedral oligomeric vinylsilsesquioxanes (vinylPOSS) via a single-step molding process. The monolithic, large surface area materials are studied with a particular focus on morphology and porous properties. Radical vinyl polymerization of the nanometer-sized POSS building blocks is therefore utilized via a thermally initiated route and in porogenic diluents such as tetrahydrofuran and polyethylene glycols of varying composition. Careful choice of these porogenic solvents and proper choice of initiator concentration lead to highly porous monolithic building entities which show a rigid, 3D-adhered, porous structure, macroscopically adapting the shape of a given mold. The described materials reflect Brunauer–Emmett–Teller (BET) surface areas of 700 m2/g or more and maximum tunable mesopore volumes of up to 2 cm3/g. Experimental investigations demonstrate the option to tailor nanoporosity and macroporosity in the single-step free-radical polymerization process. While studies on the influence of the used porogenic solvents reveal tuneability of pore sizes due to the unique pore formation process, tailored existence of residual vinyl groups allows facile postpolymerization modification of the highly porous, large surface area hybrid materials exploited via thiol–ene “click” chemistry. Our developed, simply realizable preparation process explores a new route to derive porous organic–inorganic hybrid adsorbents for a wide variety of applications such as extraction, separation science, and catalysis. PMID:23489022

  11. A Filled-Honeycomb-Structured Crystal Formed by Self-Assembly of a Janus Polyoxometalate-Silsesquioxane (POM-POSS) Co-Cluster.

    PubMed

    Ma, Chi; Wu, Han; Huang, Zi-Han; Guo, Ruo-Hai; Hu, Min-Biao; Kübel, Christian; Yan, Li-Tang; Wang, Wei

    2015-12-21

    Clusters with diverse structures and functions have been used to create novel cluster-assembled materials (CAMs). Understanding their self-assembly process is a prerequisite to optimize their structure and function. Herein, two kinds of unlike organo-functionalized inorganic clusters are covalently linked by a short organic tether to form a dumbbell-shaped Janus co-cluster. In a mixed solvent of acetonitrile and water, it self-assembles into a crystal with a honeycomb superstructure constructed by hexagonal close-packed cylinders of the smaller cluster and an orderly arranged framework of the larger cluster. Reconstruction of these structural features via coarse-grained molecular simulations demonstrates that the cluster crystallization and the nanoscale phase separation between the two incompatible clusters synergistically result in the unique nano-architecture. Overall, this work opens up new opportunities for generating novel CAMs for advanced future applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Synthesis and Free Radical Polymerization of Fluorinated Polyhedral Oligomeric Silsesquioxane (F-POSS) Macromers: Precursors for Low Surface Energy Materials and Devices

    DTIC Science & Technology

    2012-10-01

    door for use a building block material for low surface energy materials • Applications – Mechanical robust superhydrophobic /oleophobic/omniphobic...other applications Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Chem. Rev. 2010, 110, 2081. Phillips, S. H.; Haddad, T. S.; Tomczak, S. J. Current...Methylene Iodide Water Superhydrophobic /oleophilic dip-coated fabric Tuteja et al, Science, 2007, 318, 1618 Superamphiphobic electrospun surfaces

  13. Characterization of Hybrid Polyhedral Oligomeric Silsesquioxane (POSS)-Polybenzimidazole (PBI)-Phosphoric Acid (PA) Materials Intended for Proton Exchange Membranes (PEM)

    NASA Astrophysics Data System (ADS)

    Bubeck, Robert; Stark, Edmund; Decker, Berryinne; Hartmann-Thompson, Claire

    2013-03-01

    Isophthalic acid and 3,3'-diaminobenzidine (DAB) were polymerized in the presence of polyphosphoric acid (PPA) and various additives, degree of polymerization was monitored by viscosity and torque change measurements, and membranes were prepared by casting the reaction solution and allowing PPA to hydrolyze to PA under ambient conditions. As a function of relative humidity, the membranes were characterized for (1) acid content, (2) in-plane conductivity and (3) complex shear modulus G* obtained via oscillatory parallel plate dynamic mechanical spectroscopy. The addition of sulfonated octaphenyl polyhedral oligomeric silsesquixane (S-POSS) to m-polybenzimidazole (PBI)-phosphoric acid (PA) membranes resulted in increased in-plane proton conductivity at high temperatures (120-150 °C) and increased G* relative to a m-PBI control membrane and to m-PBI control membranes carrying comparable weight loadings of non-proton conducting octaphenyl-POSS nanoadditive or silica.

  14. Synthesis and Free Radical Polymerization of Fluorinated Polyhedral Oligomeric Silsesquioxane (F-POSS) Macromers: Precursors for Low Surface Energy Materials and Devices

    DTIC Science & Technology

    2012-04-01

    Molecular Weight Ethylene glycol (monomer) (antifreeze) Polyethylene glycol Low MW (laxatives, lubricants, toothpaste binder) Higher MW (medical uses...methacrylate, CPD, and MMA-F-POSS monomers: – Promising results with molecular weights ranging from 20-40,000 gm/mol – Narrow polydispersity indices (1.04

  15. Tetraphenylethene (TPE) modified polyhedral oligomeric silsesquioxanes (POSS): unadulterated monomer emission, aggregation-induced emission and nanostructural self-assembly modulated by the flexible spacer between POSS and TPE.

    PubMed

    Zhou, Hui; Li, Jiesheng; Chua, Ming Hui; Yan, Hong; Ye, Qun; Song, Jing; Lin, Ting Ting; Tang, Ben Zhong; Xu, Jianwei

    2016-10-13

    Mono-TPE modified POSS molecules, in which the flexible spacers between TPE and POSS moieties control their self-assembly and aggregation, exhibit a unique unadulterated monomer emission in organic solvents as well as an AIE emission in THF/water.

  16. Lasing characteristics of difluoroborates of 2,2'-dipyrromethene derivatives in solid matrices

    SciTech Connect

    Kuznetsova, R T; Aksenova, Yu V; Solodova, T A; Kopylova, T N; Tel'minov, E N; Mayer, G V; Berezin, M B; Antina, E V; Burkova, S L; Semeikin, A S

    2014-03-28

    The luminescence-spectral, lasing and photochemical characteristics of laser media based on boron fluoride complexes of dipyrromethenes, embedded into solid bulk matrices of polymethylmethacrylate and its modifications (obtained by adding polyhedral oligomeric silsesquioxane during polymerisation) and into polymer films, in which polyhedral silsesquioxane enters the composition of monomeric unit, have been investigated. (lasers)

  17. Synthesis of a Nanostructured Composite: Octakis(1-propyl-1H-1,2,3-triazole-4-yl(methyl 2-chlorobenzoate))octasilsesquioxane via Click Reaction.

    PubMed

    Ghodsi, Mohammadi Ziarani; Shakiba Nahad, Monireh; Lashgari, Negar; Alireza, Badiei

    2015-01-01

    Octakis(1-propyl-1H-1,2,3-triazole-4-yl(methyl 2-chlorobenzoate))octasilsesquioxanes as functionalized silsesquioxanes were synthesized via click reaction (copper-catalyzed Huisgen 1,3-dipolar cycloaddition reaction) between azidemoiety functionalized silsesquioxane and prop-2-ynyl 2-chlorobenzoate. The latter one was synthesized via the condensation reaction of propargyl alcohol and 2-chlorobenzoyl chloride in the presence of SBA-Pr-NH(2) (Santa Barbara Amorphous type material) as a nano basic catalyst. This approach provides a simple and convenient route to efficiently functionalize a wide range of new structures on the surface of silsesquioxanes.

  18. Atropine Absorption after Administration with 2-Pralidoxime Chloride by Automatic Injector.

    DTIC Science & Technology

    1987-12-01

    mesylate (methylpyridinium 2- aldoxime methane sulfonate; pralidoxime methylsulfonate) SALIVARY SECRETION - refers here to stimulated secretion measured by...radioreceptor method of Metcalfe (1981). Tritiated quinuclidinyl benzylate (specific activity, 30.1 Ci/mmole; New England Nuclear, Boston, MA) was used

  19. PRO-2-PAM: The First Therapeutic Drug for Reactivation of Organo-Phosphate-Inhibited Central (Brain) and Peripheral Cholinesterases

    DTIC Science & Technology

    2008-12-01

    1. Synthesis and Properties of 1-Methyl- 1,6- dihydropyridine -2-carbaldoxime, a Pro-Drug of N- Methylpyridinium-2-carbaldoxime Chloride, J. Med... Synthesis of pro-2-PAM (Fig. 1). We synthesized the pro-drug, pro-2-PAM, as previously described (Bodor, 1976). However, the final step, the E1

  20. Miniaturized catalysis: monolithic, highly porous, large surface area capillary flow reactors constructed in situ from polyhedral oligomeric silsesquioxanes (POSS)† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5cy00510h Click here for additional data file.

    PubMed Central

    Scholder, P.

    2015-01-01

    A single-step molding process utilizing free-radical cross-linking reaction of vinyl POSS in microliter-sized dimensions leads to hierarchically-structured, mechanically robust, porous hybrid structures. Functional variants show excellent performance in Suzuki-type coupling reactions. Due to their small volume, long-term operational robustness, and potential chemical diversity, these materials are promising candidates for catalyst screening applications. PMID:26322221

  1. Symmetric functionalization of polyhedral phenylsilsesquioxanes as a route to nano-building blocks

    NASA Astrophysics Data System (ADS)

    Roll, Mark Francis

    The design and synthesis of nanometer scale structures is of intense current interest. Herein we report on the ability to use symmetric, robust, mutable silsesquioxane ([RSiO3/2]n) nano-building blocks to produce well-defined 3-D structures for electronic or adsorption applications. We are able to show the systematic effects of supermolecular coordination to modulate the density of the molecular packing. This dissertation first describes the synthesis of the elusive decaphenylsilsesquioxane, and the exploration of the substitutionally specific para iodination of the octa-, deca- and dodeca-(p-iodophenyl)-silsesquioxanes, whose single-crystal X-ray diffraction structures are reported. Octa( p-iodophenyl)-silsesquioxane shows supermolecular coordination via Desiraju's halogen-halogen short-contact synthon, forming an open structure with a solvent accessible cavity comprising 40% of the unit cell. The application of palladium, nickel and copper catalyzed cross-coupling techniques using the carbon-iodine bond is explored in order to divergently synthesize crystalline derivatives. These derivatives include the octa(diphenylacetylene)-silsesquioxane and the octa(hexaphenylbenzene)silsesquioxane (56 Aryl), whose single-crystal X-ray diffraction structures are reported. We show that 56 Aryl, which contains more carbon atoms than any other discrete molecule in the Cambridge Structural Database, crystallizes into an extremely open structure with a solvent accessible cavity comprising 55% of the total volume. The supermolecular ordering driven by the bulky hexaphenylbenzene moieties gives nanometer-scale channels along the ab plane. Substitutional specificity is explored in the bromination of octaphenylsilsesquioxane (OPS), and single-crystal X-ray diffraction structures are reported for the octa-, hexadeca- and tetraicosa-brominated derivatives. Precise synthetic control is demonstrated by the unique catalyst-free bromination of OPS, providing the octa(o-bromophenyl)-silsesquioxane

  2. Molecular composites from hydrido and vinyl functionalized silsequioxanes

    SciTech Connect

    Zhang, C.; Baranwal, R.; Laine, R.M.

    1995-12-31

    Hydrido and vinyl functionalized silsesquioxanes [RSiO{sub 1.5}]{sub 8} (R=H, 1; R=vinyl, 2; R=OSi(CH{sub 3}){sub 2}H, 3; R=OSi(CH{sub 3}){sub 2}-vinyl, 4.) can be synthesized through rather simple processes from fairly inexpensive starting materials. The rigid caged silsesquioxane (cube) structures are very similar to those found in zeolites and may lead to highly porous materials with high surface areas. In this study, the hydrido and vinyl silsesquioxanes 1-4 were cross-coupled via {open_quote}Pt{close_quote} catalyzed hydrosilylation. The resultant polymeric materials showed good thermal stability and high surface area as found by TGA and porosimetry studies. DSC and FTIR studies indicate that on beating, further curing of the residual reactive functional groups occurs. These high surface area materials may have potential applications as insulating and low dielectric materials.

  3. Bridged polysilsesquioxane-polydimethylsiloxane nanocomposites: A reactivity study

    SciTech Connect

    Ulibarri, T.A.; Loy, D.A.; Bates, S.E.; Black, E.P.; Jamison, G.M.

    1996-10-01

    It has been demonstrated that increased strength and extensibility can be obtained in polydimethylsiloxane (PDMS) systems through the use of bimodal polymer distributions. In order to further probe short chain and linkage effects in bimodal polymer networks, we are interested in a new class of nanocomposites based on hydroxy-terminated PDMS as the long chain segments and alkylene- or arylene-bridged silsesquioxanes as the short chain segments. We have investigated tin-catalyzed coupling of the terminal hydroxy groups of the PDMS segments with bis(triethoxysilyl)arylene and alkylene monomers. The compatibility of the different silsesquioxane monomers with PDMS, and their activity with the tin-based catalyst, has been explored. A number of different hydrocarbon bridged silsesquioxane monomers have been used to determine the effect that the short segment flexibility and length, and the degree of crosslinking have on the final material properties. Findings from this study will be reported.

  4. Effect of SO2 Dry Deposition on Porous Dolomitic Limestones

    PubMed Central

    Olaru, Mihaela; Aflori, Magdalena; Simionescu, Bogdana; Doroftei, Florica; Stratulat, Lacramioara

    2010-01-01

    The present study is concerned with the assessment of the relative resistance of a monumental dolomitic limestone (Laspra – Spain) used as building material in stone monuments and submitted to artificial ageing by SO2 dry deposition in the presence of humidity. To investigate the protection efficiency of different polymeric coatings, three commercially available siloxane-based oligomers (Lotexan-N, Silres BS 290 and Tegosivin HL 100) and a newly synthesized hybrid nanocomposite with silsesquioxane units (TMSPMA) were used. A comparative assessment of the data obtained in this study underlines that a better limestone protection was obtained when treated with the hybrid nanocomposite with silsesquioxane units.

  5. Electrorheological fluids and methods

    DOEpatents

    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.

  6. Modification of the Surface Properties of Polyimide Films using POSS Deposition and Oxygen Plasma Exposure

    NASA Technical Reports Server (NTRS)

    Wohl, Christopher J.; Belcher, Marcus A.; Ghose, Sayata; Connell, John W.

    2008-01-01

    Topographically rich surfaces were generated by spray-coating organic solutions of a polyhedral oligomeric silsesquioxane, octakis (dimethylsilyloxy) silsesquioxane (POSS), on Kapton HN films and exposing them to radio frequency generated oxygen plasma. Changes in both surface chemistry and topography were observed. High-resolution scanning electron microscopy indicated substantial modification of the POSS-coated polyimide surface topographies as a result of oxygen plasma exposure. Water contact angles varied from 104 deg for unexposed POSS-coated surfaces to approximately 5 deg, for samples exposed for 5 h. Modulation of the dispersive and polar contributions to the surface energy was determined using van Oss Good Chaudhury theory.

  7. Fluorescent cyanine probe for DNA detection and cellular imaging

    NASA Astrophysics Data System (ADS)

    Zheng, Yong-Chao; Zheng, Mei-Ling; Zhao, Zhen-Sheng; Duan, Xuan-Ming

    2014-03-01

    In our study, two carbazole-based cyanines, 3,6-bis[2-(1-methylpyridinium)vinyl]-9-methyl carbazole diiodide (A) and 6,6'-bis[2-(1-methylpyridinium)vinyl]-bis(9-methyl-carbazol-3yl)methane diiodide (B) were synthesized and employed as light-up probes for DNA and cell imaging. Both of the cyanine probes possess a symmetric structure and bis-cationic center. The obvious induced circular dichroism signals in circular dichroism spectra reveal that the molecules can specifically interact with DNA. Strong fluorescence enhancement is observed when these two cyanines are bound to DNA. These cyanine probes show high binding affinity to oligonucleotides but different binding preferences to various secondary structures. Confocal microscopy images of fixed cell stained by the probes exhibit strong brightness and high contrast in nucleus with a very low cytoplasmic background.

  8. Quantitative studies on roast kinetics for bioactives in coffee.

    PubMed

    Lang, Roman; Yagar, Erkan Firat; Wahl, Anika; Beusch, Anja; Dunkel, Andreas; Dieminger, Natalie; Eggers, Rudolf; Bytof, Gerhard; Stiebitz, Herbert; Lantz, Ingo; Hofmann, Thomas

    2013-12-11

    Quantitative analysis of the bioactives trigonelline (1), N-methylpyridinium (2), caffeine (3), and caffeoylquinic acids (4) in a large set of roasted Arabica (total sample size n = 113) and Robusta coffees (total sample size n = 38) revealed that the concentrations of 1 and 4 significantly correlated with the roasting color (P < 0.001, two tailed), whereas that of 2 significantly correlated inversely with the color (P < 0.001, two tailed). As dark-roasted coffees were rich in N-methylpyridinium whereas light-roasted coffees were rich in trigonelline and caffeoylquinic acids, manufacturing of roast coffees rich in all four bioactives would therefore necessitate blending of two or even more coffees of different roasting colors. Additional experiments on the migration rates during coffee brewing showed that all four bioactives were nearly quantitatively extracted in the brew (>90%) when a water volume/coffee powder ratio of >16 was used.

  9. Influence of cation structure on binary liquid-liquid equilibria for systems containing ionic liquids based on trifluoromethanesulfonate anion with hydrocarbons.

    PubMed

    Marciniak, Andrzej; Karczemna, Ewa

    2010-04-29

    Binary liquid-liquid equilibria for 15 systems containing an ionic liquid (1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate) with a hydrocarbon (n-hexane, n-heptane, cyclohexane, benzene, toluene) were measured by the dynamic method. The influence of cation structure of trifluoromethanesulfonate anion based ionic liquids on solubility of aliphatic and aromatic hydrocarbons is discussed.

  10. Biomedical Effects of Chemical-Threat-Agent Antidote and Pretreatment Drugs. An Abstracted Bibliography. Volume 1.

    DTIC Science & Technology

    1986-04-01

    of the drug RRENCE: Journal of Pharmacy and Pharmacology, 1963, 15, 671-677. DRUM: Pralidoxime methane sulphonate (10 or 20 mg/kg i.m.) S3BJEMS: 24...TITLE: Concentrations of the oxime 2-hydroxyiminomethyl pyridinium methyl methane sulphonate (P2S) after intramuscular injection in humans REFERENCE...Sundwall, A. TITLE: Plasma concenLration curves of N-methylpyridinium-2- aldoxime methane sulphonate (P2S) after intravenous, intramuscular and oral

  11. Structural Elucidation of a Carnosine-Acrolein Adduct and its Quantification in Human Urine Samples.

    PubMed

    Bispo, Vanderson S; de Arruda Campos, Ivan P; Di Mascio, Paolo; Medeiros, Marisa H G

    2016-01-19

    Aldehydes accumulate in inflammation, during myocardial infarction and have been associated with pain symptoms. One pathway of aldehyde detoxification is the conjugation with carnosine. A 3-methylpyridinium carnosine adduct from the reaction of carnosine and acrolein was characterized using extensive spectroscopic measurements. The adduct with urinary concentrations of 1.82 ± 0.68 nmol/mg of creatinine is one of the most abundant acrolein metabolites in urine and opens promising therapeutic strategies for carnosine.

  12. Structural Elucidation of a Carnosine-Acrolein Adduct and its Quantification in Human Urine Samples

    PubMed Central

    Bispo, Vanderson S.; de Arruda Campos, Ivan P.; Di Mascio, Paolo; Medeiros, Marisa H. G.

    2016-01-01

    Aldehydes accumulate in inflammation, during myocardial infarction and have been associated with pain symptoms. One pathway of aldehyde detoxification is the conjugation with carnosine. A 3-methylpyridinium carnosine adduct from the reaction of carnosine and acrolein was characterized using extensive spectroscopic measurements. The adduct with urinary concentrations of 1.82 ± 0.68 nmol/mg of creatinine is one of the most abundant acrolein metabolites in urine and opens promising therapeutic strategies for carnosine. PMID:26783107

  13. Synthesis and evaluation of novel analogues of vitamin B6 as reactivators of tabun and paraoxon inhibited acetylcholinesterase.

    PubMed

    Gaso-Sokac, Dajana; Katalinić, Maja; Kovarik, Zrinka; Busić, Valentina; Kovac, Spomenka

    2010-09-06

    A series of novel pyridinium oximes was prepared by reactions of quaternization of pyridoxal oxime with substituted phenacyl bromides in acetone at room temperature. The structures of compounds were determined according to the data obtained by IR spectroscopy, mass spectrometry, (1)H and (13)C nuclear magnetic resonance spectroscopy as well as by elemental analysis. We tested pyridoxal oxime (1) and five prepared oximes in 1mM concentration as reactivators of human erythrocytes acetylcholinesterase (AChE) inhibited by organophosphorus compounds tabun and paraoxon: 1-phenacyl-3-hydroxy-4-hydroxyiminomethyl-5-hydroxymethyl-2-methylpyridinium bromide (2), 1-(4'-chlorophenacyl)-3-hydroxy-4-hydroxyiminomethyl-5-hydroxymethyl-2-methylpyridinium bromide (3), 1-(4'-fluorophenacyl)-3-hydroxy-4-hydroxyiminomethyl-5-hydroxymethyl-2-methylpyridinium bromide (4), 3-hydroxy-4-hydroxyiminomethyl-5-hydroxymethyl-2-methyl-1-(4'-methylphenacyl)pyridinium bromide (5), 3-hydroxy-4-hydroxyiminomethyl-5-hydroxymethyl-2-methyl-1-(4'-methoxyphenacyl)pyridinium bromide (6). However, tested oximes were not efficient in reactivation of either tabun or paraoxon inhibited AChE. The maximum restored enzyme activity in 24h was below 25%. Therefore, this class of compounds cannot be considered as potential improvement in a search for new and more efficient antidotes against OP poisoning.

  14. Nanomodified Carbon/Carbon Composites for Intermediate Temperature

    DTIC Science & Technology

    2007-08-31

    hour per response, including the time for reviewing instructions searching existing data sources, gathering and maintaining the data needed, and...completing and reviewing this collection of information, Send comments regarding this burden estimate or any other aspect of this collection of information...and several types of nanoparticles: chemically modified montmorillonite (MMT) organoclays , polyhedral oligomeric silsesquioxanes (POSS®), carbon

  15. Development of Sorbents for Extraction and Stabilization of Nucleic Acids

    DTIC Science & Technology

    2016-09-13

    particles, mesoporous silica nanoparticles (MSNs), polymers , potato starch, silk fibron, and surfactants, have been developed with these...considered here are comprised of condensed silsesquioxane precursors that produce mesoporous materials, including MSNs, mesoporous silica nanoparticles ...a physical barrier by employing materials similar to those used in DNA encapsulation: liposomes, micelles, or polymers [3–6]. RNA encapsulation

  16. Polymethylsilsesquioxanes through base-catalyzed redistribution of oligomethylhydridosiloxanes

    SciTech Connect

    RAHIMIAN,KAMYAR; ASSINK,ROGER A.; LOY,DOUGLAS A.

    2000-04-04

    There has been an increasing amount of interest in silsesquioxanes and polysilsesquioxanes. They have been used as models for silica surfaces and have been shown to have great potential for several industrial applications. Typical synthesis of polysilsesquioxanes involves the hydrolysis of organotricholorosilanes and/or organotrialkoxysilanes in the presence of acid or base catalysts, usually in the presence of organic solvents.

  17. Weathering characteristics and moisture uptake properties of wood coated with water-borne sol-gel thin films

    Treesearch

    M. A. Tshabalala; C. Starr; N. R. Sutherland

    2010-01-01

    In this study, wood specimens were coated with water-borne silsesquioxane oligomers by an in situ sol-gel deposition process. The effect of these water-borne sol-gel thin films on weathering characteristics and moisture-uptake properties of the wood specimens were investigated. The weathering characteristics were investigated by exposure of the specimens to artificial...

  18. Combination of inverse electron-demand Diels-Alder reaction with highly efficient oxime ligation expands the toolbox of site-selective peptide conjugations.

    PubMed

    Hörner, S; Uth, C; Avrutina, O; Frauendorf, H; Wiessler, M; Kolmar, H

    2015-07-14

    A modular approach combining inverse electron-demand Diels-Alder coupling (DARinv) and oxime ligation expands the toolbox of bioorthogonal peptide chemistry. Applicability of versatile site-specific bifunctional building blocks is demonstrated by generation of defined conjugates comprising linear, cystine-bridged and multi-disulfide functional peptides as well as their conjugation with hybrid silsesquioxane nanoparticles.

  19. LDRD final report on nanocomposite materials based on hydrocarbon-bridged siloxanes

    SciTech Connect

    Ulibarri, T.A.; Bates, S.E.; Loy, D.A.; Jamison, G.M.; Emerson, J.A.; Curro, J.G.

    1997-05-01

    Silicones [polydimethylsiloxane (PDMS) polymers] are environmentally safe, nonflammable, weather resistant, thermally stable, low T{sub g} materials which are attractive for general elastomer applications because of their safety and their performance over a wide temperature range. However, PDMS is inherently weak due to its low glass transition temperature (T{sub g}) and lack of stress crystallization. The major goal of this project was to create a family of reinforced elastomers based on silsesquioxane/PDMS networks. Polydimethylsiloxane-based (PDMS) composite materials containing a variety of alkylene-arylene-bridged polysilsesquioxanes were synthesized in order to probe short chain and linkage effects in bimodal polymer networks. Monte Carlo simulations on the alkylene-bridged silsesquioxane/PDMS system predicted that the introduction of the silsesquioxane short chains into the long chain PDMS network would have a significant reinforcing effect on the elastomer. The silsesquioxane-PDMS networks were synthesized and evaluated. Analysis of the mechanical properties of the resulting materials indicated that use of the appropriate silisesquioxane generated materials with greatly enhanced properties. Arylene and activated alkylene systems resulted in materials that showed superior adhesive strength for metal-to-metal adhesion.

  20. Comparison of 5-HT1A and dopamine D2 pharmacophores. X-ray structures and affinities of conformationally constrained ligands.

    PubMed

    Chidester, C G; Lin, C H; Lahti, R A; Haadsma-Svensson, S R; Smith, M W

    1993-05-14

    Conformational and molecular mechanics studies of a new series of tricyclic ligands with affinity for either the dopamine D2 receptor or the 5-HT1A receptor, or both, has enabled us to elaborate considerably on previous pharmacophore models for these receptors. The new tricyclic ligands are either angular, 2,3,3a,4,5,9b-hexahydro-1H-benz[e]indole derivatives, or linear, 2,3,3a,4,5,9a-hexahydro-1H-benz[f]indole derivatives; they have either cis or trans ring junctions, and many of the ligands are resolved. In order to have X-ray crystal coordinates for every structural type, two additional crystal structures were determined: 14a, the trans-(+-)-6-hydroxy-3-(n-propyl) angular derivative as the hydrochloride, and (+-)-1,2,2a,3,4,8b-hexahydro-8-methoxy-2-(2-propenyl)-naphth[2,1- b]azetidine hydrochloride (16d). Several recently reported imidazoquinolinones with dopaminergic and serotonergic activities were also used in developing the models as were other known ligands which are conformationally constrained. A new method for determining intrinsic activity at the D2 receptor made consistent and reliable estimates of dopamine agonist, partial agonist, and antagonist activities available. The models explain these activities in terms of the 3-dimensional structural features of the ligands and their probable orientations at the D2 receptor site. They also explain why allyl and propyl analogs of some structures have very different affinities while affinities are quite similar for allyl and propyl analogs of other structures; at both receptors a particular orientation of the amine substituent in the binding site correlates with preference for allyl over propyl derivatives. Suggestions are made for enhancing selectivity at the 5-HT1A receptor or at the dopamine D2 receptor. An angular, cis, (3aR,9bS), 2-propyl, 9-hydroxy, 3-(n-propyl) analog should be selective for the 5-HT1A receptor. A linear, trans, (3aR,9aS), 7-hydroxy, 1-(2-propenyl) analog should be selective for the

  1. Novel syntheses, functionalization, and applications of octa-, deca-, and dodecasilsesquioxanes

    NASA Astrophysics Data System (ADS)

    Asuncion, Michael Z.

    The construction of materials nanometer-by-nanometer in principle leads to the controlled design of a variety of materials with well-defined nanometer-sized architectures and novel yet predictable behaviors. Polyhedral silsesquioxanes of the formula (RSiO1.5)n, where n = 8, 10, or 12 and R is an organic functionality, represent "ideal" nanometer-sized building blocks that allow for subsequent and selective chemical modification to provide a wide variety of derivatives. This permits the specific assembly of these molecular components into larger, well-defined structures with tailorable properties. This dissertation is dedicated to the syntheses, functionalization, and applications of octa-, deca-, and dodecasilsesquioxanes. The objectives of this work were to develop simple, effective routes to nanoscale composite precursors based on silsesquioxanes with tunable properties for use in a variety of applications. These properties were readily achieved by direct chemical modification of the organic periphery. Our investigations demonstrate that octasilsesquioxane-based nanocomposites can be tailored to exhibit barrier properties with very low permeability to oxygen or employed as high temperature, thermal cross-linking agents and/or potential platforms to supramolecular structures. The use of incompletely condensed, cyclic silsesquioxane tetramers as possible precursors to fully condensed two-faced "Janus" octamers was also explored. Finally, we report the novel fluoride-mediated synthesis of functionalized deca- and dodecameric silsesquioxane cages from random-structured and generally "useless" polymeric silsesquioxane precursors. Statistical control of the numbers and types of moieties on the cages is achieved simply by altering the ratio of starting materials. The utility of these types of reactions is demonstrated in the modification of vinylxPh10-x T10 and vinylxPh 12-x T12 cages (x˜2) with 4-bromostyrene using simple metathesis chemistry. Subsequent Heck coupling

  2. Short-Range Interaction Energies and Forces Between Glucose and Silica

    NASA Astrophysics Data System (ADS)

    Kwon, K.; Kubicki, J. D.

    2002-12-01

    Many researchers have attempted to explain bacterial adhesion with DLVO theory and have had some success in describing long-range interactions. However, DLVO theory cannot properly explain the energetics of adhesion on a short-range scale (less than 1 nm). To understand short-range interactions of bacterial lipopolysaccharides (LPS) with mineral surfaces, we have calculated the structure and energetics of a glucose monomer interacting with a model silica surface (silsesquioxane). Glucose was chosen because it is the monomeric unit of the polymer Dextran which has been used as a model LPS. Silsesquioxane was selected because it is a convenient molecule that captures the most important silanol functional groups of the silica surface. Ab initio calculations were carried out with Gaussian 98 using both the HF/3-21G(d,p) and B3LYP/6-311++G(d,p) methods. The former basis set was used to generate approximations for the structure of the glucose-silsesquioxane dimer and the latter was used to calculate potential energies. A full energy minimization without any constraints was conducted to determine the most stable configuration of the dimer. Constrained energy minimizations were then conducted based on the optimized structure with the atoms of the silsesquioxane constrained. In addition, the interatomic distances between four atoms in the glucose molecule and four atoms in the silsesquioxane were also constrained to mimic the approach of the end of a LPS to a silica surface. The derivatives of the calculated potential energy were used to predict a force versus distance curve for these two molecules. The model predicts the formation of four H-bonds between the glucose and silsesquioxane that result in a minimum energy distance of approximately 2.4 Angstroms between the two molecules. The total interaction energy is close to -40 kJ/mol, which is reasonable based on experimental H-bond energies. The maximum attractive force predicted at 2.8 Angstroms is -0.24 nN, and the

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

    NASA Technical Reports Server (NTRS)

    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.

  4. Tailoring the hydrophilic/lipophilic balance of clickable mesoporous organosilicas by the copper-catalyzed azide-alkyne cycloaddition click-functionalization.

    PubMed

    Noureddine, Achraf; Trens, Philippe; Toquer, Guillaume; Cattoën, Xavier; Man, Michel Wong Chi

    2014-10-21

    We have designed and synthesized a clickable bridged silsesquioxane material featuring pendant alkyne chains as an aggregate of golf-ball-like nanoparticles, as evidenced by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and small- and wide-angle X-ray scattering (SWAXS). Using the copper-catalyzed azide-alkyne cycloaddition reaction with a range of organic azides of variable characteristics, we transformed this parent bridged silsesquioxane into new materials with tunable hydrophilic/lipophilic balance in high conversions while preserving the original morphology. N2, cyclohexane, and water sorption experiments were used to quantify the affinity of these materials toward the sorbates through the determination of their Henry's constants. This resulted in the following hydrophilic scale: M-OH > M-PEG > M-C6 > M-Ph > M-F > M-C16, which was mostly confirmed by SWAXS measurements.

  5. Photodynamic and Nail Penetration Enhancing Effects of Novel Multifunctional Photosensitizers Designed for The Treatment of Onychomycosis.

    PubMed

    Smijs, Threes; Dame, Zoë; de Haas, Ellen; Aans, Jan-Bonne; Pavel, Stan; Sterenborg, Henricus

    2014-01-01

    Novel multifunctional photosensitizers (MFPSs), 5,10,15-tris(4-N-methylpyridinium)-20-(4-phenylthio)-[21H,23H]-porphine trichloride (PORTH) and 5,10,15-tris(4-N-methylpyridinium)-20-(4-(butyramido-methylcysteinyl)-hydroxyphenyl)-[21H,23H]-porphine trichloride (PORTHE), derived from 5,10,15-Tris(4-methylpyridinium)-20-phenyl-[21H,23H]-porphine trichloride (Sylsens B) and designed for treatment of onychomycosis were characterized and their functionality evaluated. MFPSs should function as nail penetration enhancer and as photosensitizer for photodynamic treatment (PDT) of onychomycosis. Spectrophotometry was used to characterize MFPSs with and without 532 nm continuous-wave 5 mW cm(-2) laser light (± argon/mannitol/NaN3 ). Nail penetration enhancement was screened (pH 5, pH 8) using water uptake in nails and fluorescence microscopy. PDT efficacy was tested (pH 5, ± argon/mannitol/NaN3 ) in vitro with Trichophyton mentagrophytus microconida (532 nm, 5 mW cm(-2) ). A light-dependent absorbance decrease and fluorescence increase were found, PORTH being less photostable. Argon and mannitol increased PORTH and PORTHE photostability; NaN3 had no effect. PDT (0.6 J cm(-2) , 2 μm) showed 4.6 log kill for PORTH, 4.4 for Sylsens B and 3.2 for PORTHE (4.1 for 10 μm). Argon increased PORTHE, but decreased PORTH PDT efficacy; NaN3 increased PDT effect of both MFPSs whereas mannitol increased PDT effect of PORTHE only. Similar penetration enhancement effects were observed for PORTH (pH 5 and 8) and PORTHE (pH 8). PORTHE is more photostable, effective under low oxygen conditions and thus realistic candidate for onychomycosis PDT.

  6. Mesoporous polyoxometalate cluster-crosslinked organosilica frameworks delivering exceptionally high photocatalytic activity.

    PubMed

    Koutsouroubi, Eirini D; Xylouri, Alexandra K; Armatas, Gerasimos S

    2015-03-14

    Mesoporous framework materials comprising lacunary [SiW11O39](8-) polyoxometalate clusters covalently connected by ethane-bridged silsesquioxane linkers were synthesized through a block copolymer-templated cross-linking polymerization of 1,2-bis(triethoxysilyl)ethane in acid solution. These new hybrid materials, which exhibit a high density of catalytic sites, large pore surface and ordered pore structure, are shown to be highly effective in the photocatalytic oxidation of aryl alcohols with molecular oxygen.

  7. Engineered liquid crystal anchoring energies with nanopatterned surfaces.

    PubMed

    Gear, Christopher; Diest, Kenneth; Liberman, Vladimir; Rothschild, Mordechai

    2015-01-26

    The anchoring energy of liquid crystals was shown to be tunable by surface nanopatterning of periodic lines and spaces. Both the pitch and height were varied using hydrogen silsesquioxane negative tone electron beam resist, providing for flexibility in magnitude and spatial distribution of the anchoring energy. Using twisted nematic liquid crystal cells, it was shown that this energy is tunable over an order of magnitude. These results agree with a literature model which predicts the anchoring energy of sinusoidal grooves.

  8. Next Generation Proton Beam Writing: A Platform Technology for Nanowire Integration

    DTIC Science & Technology

    2010-06-01

    silsesquioxane (HSQ) nanostructures for Nickel electroplating, S. Gorelick, F. Zhang, P.G. Shao, J.A. van Kan, Harry J . Whitlow, F. Watt, Nuclear...Yaping Ren, Jeroen Anton van Kan, Sher-Yi Chiam, Linke Jian, Herbert O. Moser, Thomas Osipowicz, Frank Watt, Nuclear Instruments & Methods in Physics...Research Section B Volume 267 (2009) 2376-2380 2 Proton beam writing: a platform technology for nanowire production, J . A. van Kan F. Zhang S. Y

  9. Preparation of polysilsesquioxane-urethaneacrylate copolymer film reinforced with chitin nanofibers.

    PubMed

    Ifuku, Shinsuke; Ikuta, Akiko; Hosomi, Tetsuya; Kanaya, Shingo; Shervani, Zameer; Morimoto, Minoru; Saimoto, Hiroyuki

    2012-07-01

    Chitin nanofibers (CNFs) reinforced silsesquioxane-urethaneacrylate (SSQ-UA) copolymer films were prepared. CNFs-SSQ-UA nanocomposite films were highly transparent due to the filling of nanometer sized (10-20 nm) CNFs inside the hybrid organic-inorganic SSQ-UA copolymer. CNFs due to their crystalline structure drastically increased Young's moduli and the tensile strengths of the composite and decreased the thermal expansion. High thermal stability of polysilsesquioxane improved heat resistance of CNFs.

  10. Nanostructured Materials

    DTIC Science & Technology

    2012-08-30

    resolution (0.75 Å) X-ray diffraction studies (Figure 4). Both FH and FD are triclinic (P1) showing the presence of one and two crystallographically...polymer system. Additional 60 processing/compounding effort is normally required to force compatibilization between a filler and a polymer system...polymers from the chemical 45 classes of polyhedral oligomeric silsesquioxanes, polysils- esquioxanes, polyhedral oligomeric silicates, polysilicates

  11. Ceramic matrix and resin matrix composites: A comparison

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.

    1987-01-01

    The underlying theory of continuous fiber reinforcement of ceramic matrix and resin matrix composites, their fabrication, microstructure, physical and mechanical properties are contrasted. The growing use of organometallic polymers as precursors to ceramic matrices is discussed as a means of providing low temperature processing capability without the fiber degradation encountered with more conventional ceramic processing techniques. Examples of ceramic matrix composites derived from particulate-filled, high char yield polymers and silsesquioxane precursors are provided.

  12. Rare Earth Doped Silica Nanoparticles via Thermolysis of a Single Source Metallasilsesquioxane Precursor

    PubMed Central

    Davies, Gemma-Louise; O’Brien, John; Gun’ko, Yurii K.

    2017-01-01

    Rare earth metal doped silica nanoparticles have significant advantages over traditional organic dyes and quantum dots. Silsesquioxanes are promising precursors in the production of silica nanoparticles by thermolysis, due to their structural similarities with silica materials. This manuscript describes the production of a new Eu3+-based metallasilsesquioxane species and its use as a single source precursor in the thermolytic production of luminescent rare earth metal doped silica nanoparticles with characteristic emission in the visible region of the spectrum. PMID:28378754

  13. Rare Earth Doped Silica Nanoparticles via Thermolysis of a Single Source Metallasilsesquioxane Precursor

    NASA Astrophysics Data System (ADS)

    Davies, Gemma-Louise; O'Brien, John; Gun'Ko, Yurii K.

    2017-04-01

    Rare earth metal doped silica nanoparticles have significant advantages over traditional organic dyes and quantum dots. Silsesquioxanes are promising precursors in the production of silica nanoparticles by thermolysis, due to their structural similarities with silica materials. This manuscript describes the production of a new Eu3+-based metallasilsesquioxane species and its use as a single source precursor in the thermolytic production of luminescent rare earth metal doped silica nanoparticles with characteristic emission in the visible region of the spectrum.

  14. Rare Earth Doped Silica Nanoparticles via Thermolysis of a Single Source Metallasilsesquioxane Precursor.

    PubMed

    Davies, Gemma-Louise; O'Brien, John; Gun'ko, Yurii K

    2017-04-05

    Rare earth metal doped silica nanoparticles have significant advantages over traditional organic dyes and quantum dots. Silsesquioxanes are promising precursors in the production of silica nanoparticles by thermolysis, due to their structural similarities with silica materials. This manuscript describes the production of a new Eu(3+)-based metallasilsesquioxane species and its use as a single source precursor in the thermolytic production of luminescent rare earth metal doped silica nanoparticles with characteristic emission in the visible region of the spectrum.

  15. Two Phase Transitions of Octa(ethylsilsesquioxane) (C2H5SIO1.5)8 (PREPRINT)

    DTIC Science & Technology

    2006-05-30

    molecular motion in the crystal slows to a rigid limit. This transition from phase I to phase II lowers the symmetry from rhombohedral to triclinic ...per asymmetric unit in phase III, which is also triclinic . Even though the transition to phase III destroys the crystal, warming it to temperatures...E-mail: pmueller@mit.edu Synopsis Crystal structures of the ethyl substituted octa-silsesquioxane (C2H5SiO1.5)8 were determined at three different

  16. Nanostructured Materials

    DTIC Science & Technology

    2005-08-01

    technology transfers resulted from this work, including POSS-based dental adhesives, improved plastic food packaging, and fire-retardant plastics. Several... Polydimethylsiloxanes Modified With Polyhedral Oligomeric Silsesquioxanes: From Viscous Oils To Thermoplastics”, ACS National Conference, U.S.A, 1998, ADA397983...Cyclosiloxane”, American Chemical Society Conference, U.S.A, 2001, ADA410685. Haddad, T.S.; Lee, A.; Phillips, S.H., “ Polydimethylsiloxanes Modified With

  17. Fluorescent high-performance liquid chromatography assay for lipophilic alcohols.

    PubMed

    Nelson, Thomas J

    2011-12-01

    A new ultrasensitive fluorescent derivatization procedure for chromatographic analysis of primary, secondary, and nonpolar tertiary alcohols is described. The procedure uses Bodipy FL in basic dichloromethane solution with Mukaiyama's reagent (2-chloro-1-methylpyridinium iodide) to form highly fluorescent ester derivatives that can be separated by silica normal-phase high-performance liquid chromatography (HPLC). Rhodamine WT and Oregon green 488 were also useful derivatization reagents. The detection limit for detection of cholesterol and bryostatin by Bodipy FL was less than 1fmol. The reaction conditions are gentle enough that low concentrations of unstable alcohols such as bryostatin 1 can be measured. Copyright © 2011 Elsevier Inc. All rights reserved.

  18. Photo and Collision Induced Isomerization of a Cyclic Retinal Derivative: An Ion Mobility Study

    NASA Astrophysics Data System (ADS)

    Coughlan, Neville J. A.; Scholz, Michael S.; Hansen, Christopher S.; Trevitt, Adam J.; Adamson, Brian D.; Bieske, Evan J.

    2016-09-01

    A cationic degradation product, formed in solution from retinal Schiff base (RSB), is examined in the gas phase using ion mobility spectrometry, photoisomerization action spectroscopy, and collision induced dissociation (CID). The degradation product is found to be N- n-butyl-2-(β-ionylidene)-4-methylpyridinium (BIP) produced through 6π electrocyclization of RSB followed by protonation and loss of dihydrogen. Ion mobility measurements show that BIP exists as trans and cis isomers that can be interconverted through buffer gas collisions and by exposure to light, with a maximum response at λ = 420 nm.

  19. Red Light-Emitting-Diode Based on an Organic Salt

    NASA Astrophysics Data System (ADS)

    Meng, Rui-Ping; Xu, Hong-Guang; Xu, Chun-Xiang; Zhang, Jun-Xiang; He, Guo-Hua; Cui, Yi-Ping

    2003-06-01

    A novel organic salt trans-4-[P-(N-ethyl-N-(hydroxylethyl)-amino) styryl]-N-methylpyridinium tetraphenylborate (abbreviated as ASPT) has been employed as an active layer in an organic electroluminescent device. Bright red emission with high quantum efficiency has been obtained. The brightness of the ASPT device is one order magnitude higher than that of Alq3 devices at about 12 V. The device shows high thermal stability because of the ionic interaction within the organic salt molecules. It is assumed that the high performance of such a device is related to the formation of dipole moments in the ASPT layer.

  20. Aggregates of a cationic porphyrin as supramolecular probes for biopolymers.

    PubMed

    Occhiuto, Ilaria Giuseppina; Samperi, Mario; Trapani, Mariachiara; De Luca, Giovanna; Romeo, Andrea; Pasternack, Robert F; Scolaro, Luigi Monsù

    2015-12-01

    The copper(II) derivative of the dicationic trans-bis(N-methylpyridinium-4-yl)diphenylporphyrin (t-CuPagg) forms large fractal aggregates in aqueous solution under moderate ionic strength conditions. A kinetic investigation of the aggregation process allows for a choice of experimental conditions to quickly obtain stable assemblies in solution. These positively charged aggregates are able to interact efficiently with negatively charged chiral species, (including bacterial spores) leading to induced circular dichroism signals in the Soret region of the porphyrin, now acting as a sensitive chiroptical probe.

  1. Graphene Oxide Nanofiltration Membranes Stabilized by Cationic Porphyrin for High Salt Rejection.

    PubMed

    Xu, Xiao-Ling; Lin, Fu-Wen; Du, Yong; Zhang, Xi; Wu, Jian; Xu, Zhi-Kang

    2016-05-25

    Swelling has great influences on the structure stability and separation performance of graphene oxide laminate membranes (GOLMs) for water desalination and purification. Herein, we report cross-linked GOLMs from GO assembled with cationic tetrakis(1-methyl-pyridinium-4-yl)porphyrin (TMPyP) by a vacuum-assisted strategy. The concave nonoxide regions (G regions) of GO are used as cross-linking sites for the first time to precisely control the channel size for water permeation and salt ion retention. Channels around 1 nm are constructed by modulating the assembly ratio of TMPyP/GO, and these cross-linked GOLMs show high salt rejection.

  2. [Fluorescent energy transfer study of lysozyme complexes with liposomes].

    PubMed

    Gorbenko, G P

    1999-01-01

    The method of radiationless energy transfer was used to study the structure of lysozyme complexes with liposomes composed of phosphatidylcholine and diphosphatidylglycerol (4:3, mol:mol). 4-(n-Dimethylaminostyryl)-1-methylpyridinium n-toluenesulfonate, 4-(n-dimethylaminostyryl)-1-hexylpyridinium n-toluenesulfonate, 4-(n-dimethylaminostyryl)-1-dodecylpyridinium n-toluenesulfonate, and 3-metoxybenzanthrone were used as donors, and nile blue and rhodamine 6G, as acceptors. An increase in the surface area of model membranes upon binging of the protein to lipid bilayer was found.

  3. Efficacy of Pro-PAM (N-methyl-1,6-dihydropyridine-2-carbaldoxime Hydrochloride) as a Treatment for Organophosphate Poisoning

    DTIC Science & Technology

    1978-02-01

    described the synthesis , metabolism and disposition of N-methyl-l,6- dihydropyridine -2-carbaldoxime hydrochloride (Pro-PAM), a pro-drug 1 of PAM. The pKa of...Delivery Through Biological Membranes T. Synthesis and Properties of l-Methyl-l, 6- Dihydropyridine -2-Carbaldoxime, A Pro-Drug of N-Methylpyridinium- 2... DIHYDROPYRIDINE -2-CARBALDOXIME HYDROCHLORIDE AS A TREATMENT FOR ORGANOPHOSPHATE POISONING (U) by J.G. Clement PROJECT NO. 13D16 ... "_ A February 1978 DEFINCI

  4. High-resolution functional epoxysilsesquioxane-based patterning layers for large-area nanoimprinting.

    PubMed

    Pina-Hernandez, Carlos; Guo, L Jay; Fu, Peng-Fei

    2010-08-24

    Epoxysilsesquioxane (SSQ)-based materials have been developed as patterning layers for large-area and high-resolution nanoimprinting. The SSQ polymers, poly(methyl-co-3-glycidoxypropyl) silsesquioxanes (T(Me)T(Ep)), poly(phenyl-co-3-glycidoxypropyl) silsesquioxanes (T(Ph)T(Ep)), and poly(phenyl-co-3-glycidoxypropyl-co-perfluorooctyl) silsesquioxanes (T(Ph)T(Ep)T(Fluo)), were precisely designed and synthesized by incorporating the necessary functional groups onto the SSQ backbone. The materials possess a variety of characteristics desirable for NIL, such as great coatability, high modulus, good mold release, and excellent dry etch resistance. In particular, the presence of epoxy functional groups allows the resists to be solidified within seconds under UV exposure at room temperature, and the presence of the fluoroalkyl groups in the SSQ resins greatly facilitate mold release after the imprint process. In addition, the absence of metal in the resins makes the materials highly compatible with applications involving Si CMOS integrated circuits fabrication.

  5. UV surface modification of a new nanocomposite polymer to improve cytocompatibility.

    PubMed

    Olbrich, Michael; Punshon, Geoffrey; Frischauf, Irene; Salacinski, Henryk J; Rebollar, Esther; Romanin, Christoph; Seifalian, Alexander M; Heitz, Johannes

    2007-01-01

    A novel modified nanocomposite was studied for the adhesion and proliferation of the human umbilical vein endothelial cell (HUVEC) line EA.hy926. The nanocomposite under investigation was poly(carbonate-urea)urethane with silsesquioxane nano-cages, here in the form of a mixture of two polyhedral oligomeric silsesquioxanes. The nanocomposite surfaces were exposed to ultraviolet (UV) light of a Xe(*)(2)-excimer lamp at a wavelength of 172 nm in an ammonia atmosphere. The effects of the irradiation were characterized by atomic force and scanning electron microscopy (AFM, SEM), X-ray photo-electron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FT-IR) using an attenuated total reflection (ATR) device and measurements of advancing water contact angle (CA). The irradiation resulted in the introduction of new hydrophilic N- and O-containing groups into the surface, which was initially amphiphilic, while surface morphology remained mainly unchanged. Slight chemical changes were also observed for the silsesquioxane nano-cages at the surface. Onto the untreated and irradiated samples HUVECs were seeded and grown for various durations in culture. Standard tissue-culture polystyrene (PS) was employed as a positive control to check the efficiency of the cell-culture methods. Viability and proliferation of the cells were then assessed using a non-radioactive assay. Compared to the untreated nanocomposite polymer, irradiation times of at least 5 min resulted in a significantly increased cell proliferation between 3 and 8 days after seeding with the HUVEC line EA.hy926.

  6. Photophysical and (photo)electrochemical properties of a coumarin dye.

    PubMed

    Wang, Zhong-Sheng; Hara, Kohjiro; Dan-oh, Yasufumi; Kasada, Chiaki; Shinpo, Akira; Suga, Sadaharu; Arakawa, Hironori; Sugihara, Hideki

    2005-03-10

    A new coumarin dye, cyano-{5,5-dimethyl-3-[2-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)vinyl]cyclohex-2-enylidene}-acetic acid (NKX-2753), was prepared and characterized with respect to photophysical and electrochemical properties. It was employed as a dye sensitizer in dye-sensitized solar cells and showed efficient photon-to-electron conversion properties. The photocurrent action spectrum exhibited a broad feature with a maximum incident photon-to-electron conversion efficiency (IPCE) of 84% at 540 nm, which is comparable to that for the famous red dye RuL2(NCS)2 (known as N3), where L stands for 2,2'-bipyridyl-4,4'-dicarboxylic acid. The sandwich-type solar cell with NKX-2753, under illumination of full sun (AM1.5, 100 mW cm(-2)), produced 16.1 mA cm(-2) of short-circuit photocurrent, 0.60 V of open-circuit photovoltage, and 0.69 of fill factor, corresponding to 6.7% of overall energy conversion efficiency using 0.1 M LiI, 0.05 M I2, 0.1 M guanidinium thiocyanate, and 0.6 M 1,2-dimethyl-3-n-propyl-imidazolium iodide in dry acetonitrile as redox electrolyte. In comparison with its analogue NKX-2586 (Langmuir 2004, 20, 4205), NKX-2753 with an extra side ring on the alkene chain produced much higher IPCE values at the same conditions. The side ring acted as a spacer to efficiently prevent dye aggregation when adsorbed on the TiO2 surface, resulting in significant improvements of short-circuit photocurrent, open-circuit photovoltage, and fill factor compared with NKX-2586 that aggregated on the TiO2 surface.

  7. Novel C-1 Substituted Cocaine Analogs Unlike Cocaine or Benztropine

    PubMed Central

    Ali, Solav; Hashim, Audrey; Sheikh, Imran S.; Theddu, Naresh; Gaddiraju, Narendra V.; Mehrotra, Suneet; Schmitt, Kyle C.; Murray, Thomas F.; Sershen, Henry; Unterwald, Ellen M.; Davis, Franklin A.

    2012-01-01

    Despite a wealth of information on cocaine-like compounds, there is no information on cocaine analogs with substitutions at C-1. Here, we report on (R)-(−)-cocaine analogs with various C-1 substituents: methyl (2), ethyl (3), n-propyl (4), n-pentyl (5), and phenyl (6). Analog 2 was equipotent to cocaine as an inhibitor of the dopamine transporter (DAT), whereas 3 and 6 were 3- and 10-fold more potent, respectively. None of the analogs, however, stimulated mouse locomotor activity, in contrast to cocaine. Pharmacokinetic assays showed compound 2 occupied mouse brain rapidly, as cocaine itself; moreover, 2 and 6 were behaviorally active in mice in the forced-swim test model of depression and the conditioned place preference test. Analog 2 was a weaker inhibitor of voltage-dependent Na+ channels than cocaine, although 6 was more potent than cocaine, highlighting the need to assay future C-1 analogs for this activity. Receptorome screening indicated few significant binding targets other than the monoamine transporters. Benztropine-like “atypical” DAT inhibitors are known to display reduced cocaine-like locomotor stimulation, presumably by their propensity to interact with an inward-facing transporter conformation. However, 2 and 6, like cocaine, but unlike benztropine, exhibited preferential interaction with an outward-facing conformation upon docking in our DAT homology model. In summary, C-1 cocaine analogs are not cocaine-like in that they are not stimulatory in vivo. However, they are not benztropine-like in binding mechanism and seem to interact with the DAT similarly to cocaine. The present data warrant further consideration of these novel cocaine analogs for antidepressant or cocaine substitution potential. PMID:22895898

  8. Delineating solute-solvent interactions in binary mixtures of ionic liquids in molecular solvents and preferential solvation approach.

    PubMed

    Khupse, Nageshwar D; Kumar, Anil

    2011-02-03

    The effect of solute-solvent and solvent-solvent interactions on the preferential solvation of solvatochromic indicators in binary mixtures of ionic liquids with molecular solvents has been investigated. The binary mixtures of the pyridinium-based ionic liquids 1-butylpyridinium tetrafluoroborate ([BP][BF4]), 1-butyl-3-methylpyridinium tetrafluoroborate ([3-MBP][BF4]), and 1-butyl-4-methylpyridinium tetrafluoroborate ([4-MBP][BF4]) with molecular solvents like water, methanol, and dichloromethane have been selected for this investigation. The effect of addition of ionic liquids to molecular solvents on the polarity parameters E(T)(N), Kamlet-Taft parameters, hydrogen bond donor ability (HBD) (α), hydrogen bond acceptor ability (HBA) (β), and polarizability (π*) was obtained. The polarity parameters of the mixture display nonideality on addition of ionic liquids to water and dichloromethane. On the other hand, strong synergetic effects were seen in the ionic liquid-methanol binary mixtures. The preferential solvation models have been employed to analyze the collected data in order to achieve information on solute-solvent interactions in these binary mixtures.

  9. Presence of two emissive minima in the lowest excited state of a push-pull cationic dye unequivocally proved by femtosecond up-conversion spectroscopy and vibronic quantum-mechanical computations.

    PubMed

    Benassi, Enrico; Carlotti, Benedetta; Segado, Mireia; Cesaretti, Alessio; Spalletti, Anna; Elisei, Fausto; Barone, Vincenzo

    2015-05-14

    The long-standing controversy about the presence of two different emissive minima in the lowest excited state of the cationic push-pull dye o-(p-dimethylamino-styryl)-methylpyridinium (DASPMI) was definitively proved through the observation of dual emission, evidenced by both experimental (femtosecond up-conversion measurements) and theoretical (density functional theory calculations) approaches. From the fluorescence up-conversion data of DASPMI in water, the time resolved area normalized spectra (TRANES) were calculated, showing one isoemissive point and therefore revealing the presence of two distinct emissive minima of the excited state potential energy hypersurface with lifetimes of 0.51 and 4.8 ps. These spectroscopic techniques combined with proper data analysis allowed us to discriminate the sub-picosecond emitting state from the occurrence of ultrafast solvation dynamics and to disentangle the overlapping fluorescence (very close in energy) of the two components. Vibronic computations based on TD-DFT potential energy surfaces fully confirm those results and provide deeper insights about the key factors playing a role in determining the overall result. The two emissive minima have different structural and electronic characteristics: on one hand, the locally excited (LE) minimum has a flat geometry and an electric dipole moment smaller than the ground state; on the other hand, the twisted-intramolecular-charge-transfer (TICT) minimum shows a rotation of the methylpyridinium moiety with respect to the rest of the structure, and has an electric dipole moment significantly larger than the ground state.

  10. Synthesis and characterization of four organic-inorganic salts: sulfates of 2-aminopyridinium derivatives.

    PubMed

    Bednarchuk, Tamara J; Kinzhybalo, Vasyl; Pietraszko, Adam

    2016-11-01

    Hybrid materials, fabricated by the combination of inorganic and organic components, have potential applications in chemistry and are endowed with the advantages of both building elements. There are several types of intermolecular interactions present in these hybrid compounds, including electrostatic forces, π-π stacking and hydrogen-bonding interactions, the latter playing an important role in the construction of three-dimensional architectures and stabilizing supramolecular crystal structures. Analysis of the intermolecular interactions and their influence on packing modes therefore requires focused scientific attention. Four new organic-inorganic salts, namely 2-amino-4-methyl-3-nitropyridinium hydrogen sulfate, C6H8N3O2(+)·HSO4(-), bis(2-amino-4-methyl-3-nitropyridinium) sulfate, 2C6H8N3O2(+)·SO4(2-), 2-amino-3-methylpyridinium hydrogen sulfate, C6H9N2(+)·HSO4(-), and bis(2-amino-3-methylpyridinium) sulfate monohydrate, 2C6H9N2(+)·SO4(2-)·H2O, have been synthesized and characterized by X-ray diffraction. The crystal structures are stabilized by intra- and intermolecular hydrogen bonds, as well as by weak π-π stacking and lp-π (lp is lone pair) interactions. Hirshfeld surface analysis was employed in order to study intermolecular interactions.

  11. Identification of coffee components that stimulate dopamine release from pheochromocytoma cells (PC-12).

    PubMed

    Walker, J; Rohm, B; Lang, R; Pariza, M W; Hofmann, T; Somoza, V

    2012-02-01

    Coffee and caffeine are known to affect the limbic system, but data on the influence of coffee and coffee constituents on neurotransmitter release is limited. We investigated dopamine release and Ca(2+)-mobilization in pheochromocytoma cells (PC-12 cells) after stimulation with two lyophilized coffee beverages prepared from either Coffea arabica (AR) or Coffea canephora var. robusta (RB) beans and constituents thereof. Both coffee lyophilizates showed effects in dilutions between 1:100 and 1:10,000. To identify the active coffee compound, coffee constituents were tested in beverage and plasma representative concentrations. Caffeine, trigonelline, N-methylpyridinium, chlorogenic acid, catechol, pyrogallol and 5-hydroxytryptamides increased calcium signaling and dopamine release, although with different efficacies. While N-methylpyridinium stimulated the Ca(2+)-mobilization most potently (EC(200): 0.14±0.29μM), treatment of the cells with pyrogallol (EC(200): 48±14nM) or 5-hydroxytryptamides (EC(200): 10±3nM) lead to the most pronounced effect on dopamine release. In contrast, no effect was seen for the reconstituted biomimetic mixture. We therefore conclude that each of the coffee constituents tested stimulated the dopamine release in PC-12 cells. Since no effect was found for their biomimetic mixture, we hypothesize other coffee constituents being responsible for the dopamine release demonstrated for AR and RB coffee brews. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Acid-base strength and acidochromism of some dimethylamino-azinium iodides. An integrated experimental and theoretical study.

    PubMed

    Benassi, Enrico; Carlotti, Benedetta; Fortuna, Cosimo G; Barone, Vincenzo; Elisei, Fausto; Spalletti, Anna

    2015-01-15

    The effects of pH on the spectral properties of stilbazolium salts bearing dimethylamino substituents, namely, trans isomers of the iodides of the dipolar E-[2-(4-dimethylamino)styryl]-1-methylpyridinium, its branched quadrupolar analogue E,E-[2,6-di-(p-dimethylamino)styryl]-1-methylpyridinium, and three analogues, chosen to investigate the effects of the stronger quinolinium acceptor, the longer butadiene π bridge, or both, were investigated through a joint experimental and computational approach. A noticeable acidochromism of the absorption spectra (interesting for applications) was observed, with the basic and protonated species giving intensely colored and transparent solutions, respectively. The acid–base equilibrium constants for the protonation of the dimethylamino group in the ground state (pKa) were experimentally derived. Theoretical calculations according to the thermodynamic Born-Haber cycle provided pKa values in good agreement with the experimental values. The very low fluorescence yield did not allow a direct investigation of the changes in the acid-base properties in the excited state (pKa*) by fluorimetric titrations. Their values were derived by quantum-mechanical calculations and estimated experimentally on the basis of the Förster cycle.

  13. Phototoxic Activity and DNA Interactions of Water-Soluble Porphyrins and Their Rhenium(I) Conjugates.

    PubMed

    Mion, Giuliana; Gianferrara, Teresa; Bergamo, Alberta; Gasser, Gilles; Pierroz, Vanessa; Rubbiani, Riccardo; Vilar, Ramon; Leczkowska, Anna; Alessio, Enzo

    2015-11-01

    In the search for alternative photosensitizers for use in photodynamic therapy (PDT), herein we describe two new water-soluble porphyrins, a neutral fourfold-symmetric compound and a +3-charged tris-methylpyridinium derivative, in which either four or one [1,4,7]-triazacyclononane (TACN) units are connected to the porphyrin macrocycle through a hydrophilic linker; we also report their corresponding tetracationic Re(I) conjugates. The in vitro (photo)toxic effects of the compounds toward the human cell lines HeLa (cervical cancer), H460M2 (non-small-cell lung carcinoma), and HBL-100 (non-tumorigenic epithelial cells) are reported. Three of the compounds are not cytotoxic in the dark up to 100 μm, and the fourfold-symmetric couple revealed very good phototoxic indexes (PIs). The intracellular localization of all derivatives was studied in HeLa cells by confocal fluorescence microscopy. Although low nuclear localization was observed for some of them, it still prompted us to investigate their capacity to bind both quadruplex and duplex DNA; we observed significant selectivity in the tris-methylpyridinium derivatives for G-quadruplex interactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Phase equilibria and modeling of pyridinium-based ionic liquid solutions.

    PubMed

    Domańska, Urszula; Królikowski, Marek; Ramjugernath, Deresh; Letcher, Trevor M; Tumba, Kaniki

    2010-11-25

    The phase diagrams of the ionic liquid (IL) N-butyl-4-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide ([BM(4)Py][NTf(2)]) with water, an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol), an aromatic hydrocarbon (benzene, toluene, ethylbenzene, n-propylbenzene), an alkane (n-hexane, n-heptane, n-octane), or cyclohexane have been measured at atmospheric pressure using a dynamic method. This work includes the characterization of the synthesized compound by water content and also by differential scanning calorimetry. Phase diagrams for the binary systems of [BM(4)Py][NTf(2)] with all solvents reveal eutectic systems with regards to (solid-liquid) phase equilibria and show immiscibility in the liquid phase region with an upper critical solution temperature (UCST) in most of the mixtures. The phase equilibria (solid, or liquid-liquid) for the binary systems containing aliphatic hydrocarbons reported here exhibit the lowest solubility and the highest immiscibility gap, a trend which has been observed for all ILs. The reduction of experimental data has been carried out using the nonrandom two-liquid (NRTL) correlation equation. The phase diagrams reported here have been compared with analogous phase diagrams reported previously for systems containing the IL N-butyl-4-methylpyridinium tosylate and other pyridinium-based ILs. The influence of the anion of the IL on the phase behavior has been discussed.

  15. Ionic liquid biodegradability depends on specific wastewater microbial consortia.

    PubMed

    Docherty, Kathryn M; Aiello, Steven W; Buehler, Barbara K; Jones, Stuart E; Szymczyna, Blair R; Walker, Katherine A

    2015-10-01

    Complete biodegradation of a newly-synthesized chemical in a wastewater treatment plant (WWTP) eliminates the potential for novel environmental pollutants. However, differences within- and between-WWTP microbial communities may alter expectations for biodegradation. WWTP communities can also serve as a source of unique consortia that, when enriched, can metabolize chemicals that tend to resist degradation, but are otherwise promising green alternatives. We tested the biodegradability of three ionic liquids (ILs): 1-octyl-3-methylpyridinium bromide (OMP), 1-butyl-3-methylpyridinium bromide (BMP) and 1-butyl-3-methylimidazolium chloride (BMIM). We performed tests using communities from two WWTPs at three time points. Site-specific and temporal variation both influenced community composition, which impacted the success of OMP biodegradability. Neither BMP nor BMIM degraded in any test, suggesting that these ILs are unlikely to be removed by traditional treatment. Following standard biodegradation assays, we enriched for three consortia that were capable of quickly degrading OMP, BMP and BMIM. Our results indicate WWTPs are not functionally redundant with regard to biodegradation of specific ionic liquids. However, consortia can be enriched to degrade chemicals that fail biodegradability assays. This information can be used to prepare pre-treatment procedures and prevent environmental release of novel pollutants.

  16. Quantification of free fatty acids in human stratum corneum using tandem mass spectrometry and surrogate analyte approach.

    PubMed

    Dapic, Irena; Kobetic, Renata; Brkljacic, Lidija; Kezic, Sanja; Jakasa, Ivone

    2017-07-29

    The free fatty acids (FFAs) are one of the major components of the lipids in the stratum corneum (SC), the uppermost layer of the skin. Relative composition of FFAs has been proposed as a biomarker of the skin barrier status in patients with atopic dermatitis (AD). Here, we developed an LC-ESI-MS/MS method for simultaneous quantification of a range of FFAs with long and very long chain length in the SC collected by adhesive tape (D-Squame). The method, based on derivatization with 2-bromo-1-methylpyridinium iodide and 3-carbinol-1-methylpyridinium iodide, allowed highly sensitive detection and quantification of FFAs using multiple reaction monitoring. For the quantification, we applied a surrogate analyte approach and internal standardization using isotope labeled derivatives of FFAs. Adhesive tapes showed the presence of several FFAs, which are also present in the SC, a problem encountered in previous studies. Therefore, the levels of FFAs in the SC were corrected using C12:0, which was present on the adhesive tape, but not detected in the SC. The method was applied to SC samples from patients with atopic dermatitis and healthy subjects. Quantification using multiple reaction monitoring allowed sufficient sensitivity to analyze FFAs of chain lengths C16-C28 in the SC collected on only one tape strip. Copyright © 2017 John Wiley & Sons, Ltd.

  17. Alumina-supported oxime for the degradation of sarin and diethylchlorophosphate.

    PubMed

    Verma, Aniza K; Srivastava, Avanish K; Singh, Beer; Shah, Dilip; Shrivastava, Smriti; Shinde, Chandra Kant P

    2013-02-01

    1-(4-Chlorophenyl))-N-hydroxymethanimine and cyclohexyl-N-hydroxymethanimine were synthesized and a well-established oxime, i.e., 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride was purchased. Thereafter; all were loaded over Al(2)O(3) using incipient wetness technique. The prepared systems were characterized using surface area analyzer, scanning electron microscope, energy dispersive X-ray spectrophotometer, Fourier transform infrared spectrophotometer and thermogravimetric analyzer. Kinetics of the degradation of sarin (GB) and simulant, i.e. diethylchlorophosphate (DEClP) was studied over synthesized oxime impregnated Al(2)O(3) and results were compared with well reported oxime impregnated Al(2)O(3). Kinetics of reaction was found to be following the pseudo first order reaction kinetics. The order of reactivity of the prepared systems was found to be cyclohexyl-N-hydroxymethanimine/Al(2)O(3)>1-(4-chlorophenyl)-N-hydroxymethanimine/Al(2)O(3)>2-[(hydroxyimino)methyl]-1-methylpyridinium chloride/Al(2)O(3)>Al(2)O(3). From the reaction kinetics it was observed that the reaction with DEClP was faster than with GB. Cyclohexyl-N-hydroxymethanimine/Al(2)O(3) was found to be the most reactive system with half-life of 0.94 and 15 h for DEClP and GB respectively.

  18. Deliberate design of an acentric diamondoid metal-organic network

    SciTech Connect

    Yang Caiqin; Wang Jing; Wang Wei; Zhan Wenhong

    2011-09-15

    Reaction of 2.5-dicarboxy-1-methylpyridinium (DCMP) chloride and Zn(NO{sub 3}){sub 2}.6H{sub 2}O in the presence of NaHCO{sub 3} in water gave an expected acentric diamondoid network [Zn(DCMP){sub 2}] with a three-fold interpenetration. With long Zn-Zn separations, very large cavities are formed within each diamondoid network with high propensity to interpenetration, which makes it show a promising non-linear optical property with SHG efficiency approximately 7 times higher than that of potassium dihydrogen phosphate (KDP). The design strategy of ligand through methylation of the corresponding pyrdinecarboxylic acid can be extended to other widely used carboxylic acids, more importantly, to lead to an unsymmetric bifunctional bridging ligand, which is essential for generating polar solids. - Graphical Abstract: Reaction of Zn(NO{sub 3}){sub 2}.6H{sub 2}O with a deliberately designed unsymmetrical ligand 2.5-dicarboxy-1-methylpyridinium (DCMP) chloride and in the presence of NaHCO{sub 3} gave an expected noncentric diamondoid network [Zn(DCMP){sub 2}], which has its SHG response approximately 7 times higher than that of potassium dihydrogen phosphate (KDP). Highlights: > DCMP as an unsymmetrical organic ligand to design metal organic framework. > Long Zn-Zn separations and very large cavities formed. > Diamondoid network with high propensity to interpenetration formed. > Bifunctional bridging ligand was used to generate polar solids with large SHG response.

  19. Polymerization of trialkoxysilanes. Effect of the organic substituent on the formation of gels

    SciTech Connect

    Loy, D.A.; Baugher, B.M.; Schneider, D.A.

    1998-09-01

    Hydrolysis and condensation of trialkoxysilanes, R-Si(OR{prime}){sub 3}, generally leads to the formation of silsesquioxane oligomers and polymers. These polymers are composed of a monomer repeat unit, [R-SiO{sub 1.5}]{sub n}, with a single silicon atom attached to other repeat units in the polymer through one to three siloxane bonds. The remaining substituent is an organic group attached to the silicon through a silicon-carbon single bond. Silsesquioxanes have been the subject of intensive study in the past and are becoming important again as a vehicle for introducing organic functionalities into hybrid organic-inorganic materials through sol-gel processing. Despite all of this interest, there has not been a systematic study of the ability of trialkoxysilanes to form gels through the sol-gel process. In fact, it has been noted that silsesquioxanes are generally isolated as soluble resins rather than the highly crosslinked network polymers (gels) one would expect from a tri-functional monomer. In this study, the authors have examined the sol-gel chemistry of a variety of trialkoxysilanes with different organic substituents (R = H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, t-Bu, n-octadecyl, n-dodecyl, cyclohexyl, vinyl, phenyl, benzyl, phenethyl), with methoxide or ethoxide substituents on silicon, at varying monomer concentrations ranging up to neat monomer, and with different catalysts (HCl, NaOH, formic acid, fluoride). Gels were prepared from tetramethoxysilane and tetraethoxysilane at identical concentrations for purposes of comparison.

  20. Effect of number and position of positive charges on the stacking of porphyrins along poly[d(A-T)(2)] at high binding densities.

    PubMed

    Jung, Jin-A; Lee, Sang Hwa; Jin, Biao; Sohn, Youngku; Kim, Seog K

    2010-06-10

    At high porphyrin densities, the effects of the number and position of the positive charges of the periphery ring on the stacking of the porphyrin on poly[d(A-T)(2)] was investigated using polarized spectroscopy, including circular and linear dichroism (CD and LD, respectively). The CD spectrum of meso-tetrakis(N-methylpyridinium-4-yl)porphyrin(TMPyP) consisted of two positive bands in the Soret absorption region at low [porphyrin]/[DNA base] ratios (R ratios) and changed to two distinguishable categories of the bisignate CD spectrum with increasing R ratio. These CD spectra were attributed to the monomeric groove binding, and the moderately and extensively stacked TMPyPs. In contrast, trans-bis(N-methylpyridinium-4-yl)porphyrin (trans-BMPyP) dominantly produced a CD spectrum that corresponded to the extensive stacking, except at the lowest R ratio that was used in this work (R = 0.04). However, for cis-bis(N-methylpyridinium-4-yl)porphyrin (cis-BMPyP), the intensity of the apparent bisignate CD signal was too small to assign it to the extensive stacking. Moreover, the shape of the CD spectrum in the DNA absorption region showed that the conformation of poly[d(A-T)(2)] was retained, in contrast to the extensively stacked TMPyP and trans-BMPyP. In the extensively stacked TMPyP- poly[d(A-T)(2)] assembly, the large negative LD signal in the Soret band was observed suggesting that the direction of the molecular planes of TMPyP was close to perpendicular with respect to the orientation axis (flow axis). In contrast, the LD spectrum of the trans-BMPyP-poly[d(A-T)(2)] complex produced positive LD signal in the same wavelength region, suggesting the orientation of the molecular plane was nearly parallel relative to the flow direction. Surprisingly, the LD signal in the DNA absorption region for both of the porphyrins was positive. Therefore, the helix axis of the DNA was near perpendicular relative to the flow direction in the porphyrin-polynucleotide assembly.

  1. Hybrid Materials Based on the Embedding of Organically Modified Transition Metal Oxoclusters or Polyoxometalates into Polymers for Functional Applications: A Review

    PubMed Central

    Carraro, Mauro; Gross, Silvia

    2014-01-01

    The covalent incorporation of inorganic building blocks into a polymer matrix to obtain stable and robust materials is a widely used concept in the field of organic-inorganic hybrid materials, and encompasses the use of different inorganic systems including (but not limited to) nanoparticles, mono- and polynuclear metal complexes and clusters, polyhedral oligomeric silsesquioxanes (POSS), polyoxometalates (POM), layered inorganic systems, inorganic fibers, and whiskers. In this paper, we will review the use of two particular kinds of structurally well-defined inorganic building blocks, namely transition metals oxoclusters (TMO) and polyoxometalates (POM), to obtain hybrid materials with enhanced functional (e.g., optical, dielectric, magnetic, catalytic) properties. PMID:28788659

  2. Reduced glutathione-resisting ¹⁹F NMR sensors for detecting HNO.

    PubMed

    Kitamura, Narufumi; Hiraoka, Tatsuhiro; Tanaka, Kazuo; Chujo, Yoshiki

    2012-08-01

    The (19)F NMR probes for the HNO detection are reported. We synthesized the probe molecules with the paramagnetic Cu(II) complex and fluorine atoms using a cubic silsesquioxane. By using the magnetism changes of the Cu(II) to Cu(I) in the complex by the reduction with HNO, the (19)F NMR signal intensities of the probe increased. Noteworthily, our probes have superior resistance to reduced glutathione which is the major intracellular molecule to maintain the reductive environment and the competitor in the reduction of Cu(II) against HNO. Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. US Japan Workshop. Hybrid 2000 Conference Held in Ithaca, New York on May 7-12, 2000

    DTIC Science & Technology

    2001-05-31

    University) 11:30-12:15 "Organic/inorganic Nanocomposites From Cubic Silsesquioxanes", Richard Laine (University of Michigan ) 12:30-2:00 LUNCH-family style...30) and Goosewatch (4:35 -5:05PM) wineries . Return to hotel by 6PM Thursday May 11th 8AM Registration Session Chair: R. Laine 9-9:45 "Mesoscopic...the Macromolecular Science and Eng. Center, University of Michigan , Ann Arbor, MI. Introduction: Our goal is to develop structure-property-processing

  4. Low-k periodic mesoporous organosilica with air walls: POSS-PMO.

    PubMed

    Seino, Makoto; Wang, Wendong; Lofgreen, Jennifer E; Puzzo, Daniel P; Manabe, Takao; Ozin, Geoffrey A

    2011-11-16

    Periodic mesoporous organosilica (PMO) with polyhedral oligomeric silsesquioxane (POSS) air pockets integrated into the pore walls has been prepared by a template-directed, evaporation-induced self-assembly spin-coating procedure to create a hybrid POSS-PMO thin film. A 10-fold increase in the porosity of the POSS-PMO film compared to a reference POSS film is achieved by incorporating ∼1.5 nm pores. The increased porosity results in a decrease in the dielectric constant, k, which goes from 2.03 in a reference POSS film to 1.73 in the POSS-PMO film.

  5. Hydrogen catalysis and scavenging action of Pd-POSS nanoparticles

    SciTech Connect

    Maiti, A; Gee, R H; Maxwell, R; Saab, A

    2007-02-01

    Prompted by the need for a self-supported, chemically stable, and functionally flexible catalytic nanoparticle system, we explore a system involving Pd clusters coated with a monolayer of polyhedral oligomeric silsesquioxane (POSS) cages. With an initial theoretical focus on hydrogen catalysis and sequestration in the Pd-POSS system, we report Density Functional Theory (DFT) results on POSS binding energies to the Pd(110) surface, hydrogen storing ability of POSS, and possible pathways of hydrogen radicals from the catalyst surface to unsaturated bonds away from the surface.

  6. Preparation of bio-compatible boron nanoparticles and novel mesoporous silica nanoparticles for bio-applications

    NASA Astrophysics Data System (ADS)

    Gao, Zhe

    This dissertation presents the synthesis and characterization of several novel inorganic and hybrid nanoparticles, including the bio-compatible boron nanoparticles (BNPs) for boron neutron capture therapy (BNCT), tannic acid-templated mesoporous silica nanoparticles and degradable bridged silsesquioxane silica nanoparticles. Chapter 1 provides background information of BNCT and reviews the development of design and synthesizing silica nanoparticles and the study of silica material degradability. Chapter 2 describes the preparation and characterization of dopamine modified BNPs and the preliminary cell study of them. The BNPs were first produced via ball milling, with fatty acid on the surface to stabilize the combustible boron elements. This chapter will mainly focus on the ligand-exchange strategy, in which the fatty acids were replaced by non-toxic dopamines in a facile one-pot reaction. The dopamine-coated BNPs (DA-BNPs) revealed good water dispersibility and low cytotoxicity. Chapter 3 describes the synthesis of tannic acid template mesoporous silica nanoparticles (TA-TEOS SiNPs) and their application to immobilize proteins. The monodispersed TA SiNPs with uniform pore size up to approximately 13 nm were produced by utilizing tannic acid as a molecular template. We studied the influence of TA concentration and reaction time on the morphology and pore size of the particles. Furthermore, the TA-TEOS particles could subsequently be modified with amine groups allowing them to be capable of incorporating imaging ligands and other guest molecules. The ability of the TA-TEOS particles to store biomolecules was preliminarily assessed with three proteins of different charge characteristics and dimensions. The immobilization of malic dehydrogenase on TA-TEOS enhanced the stability of the enzyme at room temperature. Chapter 4 details the synthesis of several bridged silsesquioxanes and the preparation of degradable hybrid SiNPs via co-condensation of bridged

  7. Plasmonic reflection color filters with metallic random nanostructures.

    PubMed

    Wu, Q J; Jia, H; Hu, X L; Sun, L B; Wang, L S; Yang, S M; Tai, R Z; Fecht, H J; Wang, L Q; Zhang, D X; Jiang, J Z

    2017-02-24

    We develop reflective color filters with randomly distributed nanodisks and nanoholes fabricated with hydrogen silsesquioxane and Ag films on silicon substrate. They exhibit high resolution, angle-independence and easily up-scalable fabrication, which are the most important factors for color filters for industrial applications. We uncover the underlying mechanism after systematically analyzing the localized surface plasmon polariton coupling in the electric-field distribution. The agreement of the experimental results with those from the simulation indicates that tunable colors across the visible spectrum can be obtained by simply varying the diameter of the nanodisks, promoting their applications.

  8. Plasmonic reflection color filters with metallic random nanostructures

    NASA Astrophysics Data System (ADS)

    Wu, Q. J.; Jia, H.; Hu, X. L.; Sun, L. B.; Wang, L. S.; Yang, S. M.; Tai, R. Z.; Fecht, H. J.; Wang, L. Q.; Zhang, D. X.; Jiang, J. Z.

    2017-02-01

    We develop reflective color filters with randomly distributed nanodisks and nanoholes fabricated with hydrogen silsesquioxane and Ag films on silicon substrate. They exhibit high resolution, angle-independence and easily up-scalable fabrication, which are the most important factors for color filters for industrial applications. We uncover the underlying mechanism after systematically analyzing the localized surface plasmon polariton coupling in the electric-field distribution. The agreement of the experimental results with those from the simulation indicates that tunable colors across the visible spectrum can be obtained by simply varying the diameter of the nanodisks, promoting their applications.

  9. Nanotechnology and bio-functionalisation for peripheral nerve regeneration

    PubMed Central

    Sedaghati, Tina; Seifalian, Alexander M.

    2015-01-01

    There is a high clinical demand for new smart biomaterials, which stimulate neuronal cell proliferation, migration and increase cell-material interaction to facilitate nerve regeneration across these critical-sized defects. This article briefly reviews several up-to-date published studies using Arginine-Glycine-Aspartic acid peptide sequence, nanocomposite based on polyhedral oligomeric silsesquioxane nanoparticle and nanofibrous scaffolds as promising strategies to enhance peripheral nerve regeneration by influencing cellular behaviour such as attachment, spreading and proliferation. The aim is to establish the potent manipulations, which are simple and easy to employ in the clinical conditions for nerve regeneration and repair. PMID:26487832

  10. Advances in the development and applications of organic-silica hybrid monoliths.

    PubMed

    Zajickova, Zuzana

    2017-01-01

    This review will concentrate on recent progress (since 2013) toward preparation of organic-silica hybrid monoliths and their latest applications as extraction and separation media largely focusing on capillary liquid chromatography and capillary electrochromatography. Main emphasis will be given to advancement of approaches relying on the sol-gel chemistry of tetra- and tri-alkoxysilanes, sol-gel chemistry of alkoxysilanes and free-radical copolymerization with organic monomers, and free radical and ring-opening copolymerization of polyhedral oligomeric silsesquioxanes with organic monomers. Hybrid molecularly-imprinted polymer monoliths and hybrid monoliths made with non-silica-based precursors or in combination with metal alkoxides will be included as well.

  11. Improved out-coupling efficiency of organic light emitting diodes fabricated on a TiO2 planarization layer with embedded Si oxide nanostructures

    NASA Astrophysics Data System (ADS)

    Sung, Young Hoon; Jung, Pil-Hoon; Han, Kyung-Hoon; Kim, Yang Doo; Kim, Jang-Joo; Lee, Heon

    2017-10-01

    In order to increase the out-coupling efficiency of organic light emitting diodes, conical Si oxide nanostructures were formed on a glass substrate using nanoimprint lithography with hydrogen silsesquioxane. Then, the substrate was planarized with TiO2 nanoparticles. Since TiO2 nanoparticles have a higher refractive index than Si oxide, the surface of substrate is physically flat, but optically undulated in a manner that enables optical scattering and suppression of total internal reflection. Subsequently, OLEDs formed on a substrate with nanostructured Si oxide and a TiO2 planarization layer exhibit a 25% increase in out-coupling efficiency by suppressing total internal reflection.

  12. Multifunctional imine-POSS as uncommon 3D nanobuilding blocks for supramolecular hybrid materials: synthesis, structural characterization, and properties.

    PubMed

    Janeta, Mateusz; John, Łukasz; Ejfler, Jolanta; Lis, Tadeusz; Szafert, Sławomir

    2016-08-02

    In this article, we report on the chemistry and the spectroscopic properties of well-defined imino-functionalized polyoctahedral oligomeric silsesquioxanes (imine-POSS) with various substitutions. Our efforts were mainly focused on side chains with sizable aryl groups possessing hydroxyl, nitro, and halide moieties. Such a choice enabled us to track their reduction abilities to secondary amine-POSS, tautomerization effects, and thermal properties. We also report for the first time the solid-state structures of five imino-functionalized cage-like octasilsesquioxanes. These structures provide unique examples of the complexities of three-dimensional packing motifs and their relationship with the assembly of tunable materials from nanobuilding blocks.

  13. Study of Positronium in Low-k Dielectric Films by means of 2D-Angular Correlation Experiments at a High-Intensity Slow-Positron Beam

    SciTech Connect

    Gessmann, T; Petkov, M P; Weber, M H; Lynn, K G; Rodbell, K P; Asoka-Kumar, P; Stoeffl, W; Howell, R H

    2001-06-20

    Depth-resolved measurements of the two-dimensional angular correlation of annihilation radiation (2D-ACAR) were performed at the high-intensity slow-positron beam of Lawrence Livermore National Laboratory. We studied the formation of positronium in thin films of methyl-silsesquioxane (MSSQ) spin-on glass containing open-volume defects in the size of voids. Samples with different average void sizes were investigated and positronium formation could be found in all cases. The width of the angular correlation related to the annihilation of parapositronium increased with the void size indicating the annihilation of non-thermalized parapositronium.

  14. Disordered microstructure polymer optical fiber for stabilized coherent random fiber laser.

    PubMed

    Hu, Zhijia; Miao, Bo; Wang, Tongxin; Fu, Qiang; Zhang, Douguo; Ming, Hai; Zhang, Qijin

    2013-11-15

    We have demonstrated the realization of a random polymer fiber laser (RPFL) based on laser dye Pyrromethene 597-doped one-dimensional disordered polymer optical fiber (POF). The stabilized coherent laser action for the disordered POF has been obtained by the weak optical multiple scattering of the polyhedral oligomeric silsesquioxanes nanoparticles in the core of the POF in situ formed during polymerization, which was enhanced by the waveguide confinement effect. Meanwhile, the threshold of our RPFL system is almost one order of magnitude lower than that of the liquid core random fiber laser reported previously, which promotes the development of random lasers.

  15. High-Performance Nano-Photoinitiators with Improved Safety for 3D Printing.

    PubMed

    Han, Yanyang; Wang, Fei; Lim, Chin Yan; Chi, Hong; Chen, Dairong; Wang, FuKe; Jiao, Xiuling

    2017-09-27

    In this work, we report the first hybrid nanosized photoinitiators with low cytotoxicity and migration by coupling of polyhedral oligomeric silsesquioxanes (POSS) to benzophenone derivatives. This new series of photoinitiators were fully characterized and showed many favorable properties such as uniform sizes, extremely low tendency to migrate, less effect on resin viscosity, enhanced thermal stability and mechanical strength, increased photoactivity, and significantly lower cell toxicity compared to their corresponding benzophenone molecules. The utility of these hybrid nanosized photoinitiators in 3D printing was demonstrated in printing of various 3D structures with high resolution and accuracy.

  16. An Electronic Structure Approach to Charge Transfer and Transport in Molecular Building Blocks for Organic Optoelectronics

    NASA Astrophysics Data System (ADS)

    Hendrickson, Heidi Phillips

    A fundamental understanding of charge separation in organic materials is necessary for the rational design of optoelectronic devices suited for renewable energy applications and requires a combination of theoretical, computational, and experimental methods. Density functional theory (DFT) and time-dependent (TD)DFT are cost effective ab-initio approaches for calculating fundamental properties of large molecular systems, however conventional DFT methods have been known to fail in accurately characterizing frontier orbital gaps and charge transfer states in molecular systems. In this dissertation, these shortcomings are addressed by implementing an optimally-tuned range-separated hybrid (OT-RSH) functional approach within DFT and TDDFT. The first part of this thesis presents the way in which RSH-DFT addresses the shortcomings in conventional DFT. Environmentally-corrected RSH-DFT frontier orbital energies are shown to correspond to thin film measurements for a set of organic semiconducting molecules. Likewise, the improved RSH-TDDFT description of charge transfer excitations is benchmarked using a model ethene dimer and silsesquioxane molecules. In the second part of this thesis, RSH-DFT is applied to chromophore-functionalized silsesquioxanes, which are currently investigated as candidates for building blocks in optoelectronic applications. RSH-DFT provides insight into the nature of absorptive and emissive states in silsesquioxanes. While absorption primarily involves transitions localized on one chromophore, charge transfer between chromophores and between chromophore and silsesquioxane cage have been identified. The RSH-DFT approach, including a protocol accounting for complex environmental effects on charge transfer energies, was tested and validated against experimental measurements. The third part of this thesis addresses quantum transport through nano-scale junctions. The ability to quantify a molecular junction via spectroscopic methods is crucial to their

  17. Intramolecular charge transfer of push-pull pyridinium salts in the singlet manifold.

    PubMed

    Carlotti, Benedetta; Consiglio, Giuseppe; Elisei, Fausto; Fortuna, Cosimo G; Mazzucato, Ugo; Spalletti, Anna

    2014-05-22

    The solvent effect on the photophysical and photochemical properties of the iodides of three trans (E) isomers of 2-D-vinyl,1-methylpyridinium, where D is a donor group (4-dimethylaminophenyl, 3,4,5-trimethoxyphenyl and 1-pyrenyl), was studied by stationary and transient absorption techniques. The results obtained allowed the negative solvatochromism and relaxation pathways of the excited states in the singlet manifold to be reasonably interpreted. Resorting to ultrafast absorption techniques and DFT calculations allowed information on the excited state dynamics and the role of the solvent-controlled intramolecular charge transfer (ICT) processes to be obtained. The structure-dependent excited state dynamics in nonpolar solvents, where the ICT is slower than solvent rearrangement, and in polar solvents, where an opposite situation is operative, was thus explained. The push-pull character of the three compounds, particularly the anilino-derivative, suggests their potential application in optoelectronics.

  18. Roasting process of coffee beans as studied by nuclear magnetic resonance: time course of changes in composition.

    PubMed

    Wei, Feifei; Furihata, Kazuo; Koda, Masanori; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2012-02-01

    In this paper, we report a (1)H and (13)C nuclear magnetic resonance (NMR)-based comprehensive analysis of coffee bean extracts of different degrees of roast. The roasting process of coffee bean extracts was chemically characterized using detailed signal assignment information coupled with multivariate data analysis. A total of 30 NMR-visible components of coffee bean extracts were monitored simultaneously as a function of the roasting duration. During roasting, components such as sucrose and chlorogenic acids were degraded and components such as quinic acids, N-methylpyridinium, and water-soluble polysaccharides were formed. Caffeine and myo-inositol were relatively thermally stable. Multivariate data analysis indicated that some components such as sucrose, chlorogenic acids, quinic acids, and polysaccharides could serve as chemical markers during coffee bean roasting. The present composition-based quality analysis provides an excellent holistic method and suggests useful chemical markers to control and characterize the coffee-roasting process.

  19. Selective extraction of copper, mercury, silver and palladium ionsfrom water using hydrophobic ionic liquids.

    SciTech Connect

    Papaiconomou, Nicolas; Lee, Jong-Min; Salminen, Justin; VonStosch, Moritz; Prausnitz, John M.

    2007-06-25

    Extraction of dilute metal ions from water was performed near room temperature with a variety of ionic liquids. Distribution coefficients are reported for fourteen metal ions extracted with ionic liquids containing cations 1-octyl-4-methylpyridinium [4MOPYR]{sup +}, 1-methyl-1-octylpyrrolidinium [MOPYRRO]{sup +} or 1-methyl-1-octylpiperidinium [MOPIP]{sup +}, and anions tetrafluoroborate [BF{sub 4}]{sup +}, trifluoromethyl sulfonate [TfO]{sup +} or nonafluorobutyl sulfonate [NfO]{sup +}. Ionic liquids containing octylpyridinium cations are very good for extracting mercury ions. However, other metal ions were not significantly extracted by any of these ionic liquids. Extractions were also performed with four new task-specific ionic liquids. Such liquids containing a disulfide functional group are efficient and selective for mercury and copper, whereas those containing a nitrile functional group are efficient and selective for silver and palladium.

  20. Physicochemical study of solution behavior of ionic liquid prevalent in diverse solvent systems at different temperatures

    NASA Astrophysics Data System (ADS)

    Datta, Biswajit; Roy, Mahendra Nath

    2016-11-01

    Electrolytic conductivity, density, viscosity and FTIR study of an ionic liquid, 1-butyl-4-methylpyridinium hexafluorophosphate ([bmpy]PF6) have been measured in diverse industrially significant solvents viz. acetonitrile, tetrahydrofuran and 1,3 dioxolane at various temperatures. In acetonitrile, the ion-pair formation of the IL was analyzed by Fuoss conductance equation. In Tetrahydrofuran and 1,3 Dioxolane systems, triple-ion formation analyzed by the Fuoss-Kraus theory. Ion-solvent interactions have been inferred in terms of limiting apparent molal volumes and viscosity B-coefficients. The results obtained from the experimental study, have been conferred in terms of ion-dipole interactions, structural aspect, configurational theory and solvatochromic effect.

  1. FABRICATION OF A RETINAL PROSTHETIC TEST DEVICE USING ELECTRODEPOSITED SILICON OVER POLYPYRROLE PATTERNED WITH SU-8 PHOTORESIST

    PubMed Central

    Miller, Eric; Ellis, Daniel; Charles, Duran; McKenzie, Jason

    2016-01-01

    A materials fabrication study of a photodiode array for possible application of retina prosthesis was undertaken. A test device was fabricated using a glassy carbon electrode patterned with SU-8 photoresist. In the openings, p-type polypyrrole was first electrodeposited using 1-butyl-1-methylpyridinium bis(trifluoromethylsulfonyl)imide ionic liquid. The polypyrrole was self-doped with imide ion at ~1.5 mole %, was verified as p-type, and had a resistivity of ~20 Ωcm. N-type Silicon was then electrodeposited over this layer using silicon tetrachloride / phosphorus trichloride in acetonitrile and passivated in a second electrodeposition using trimethylchlorosilane. Electron microscopy revealed the successful electrodeposition of silicon over patterned polypyrrole. Rudimentary photodiode behavior was observed. The passivation improved but did not completely protect the electrodeposited silicon from oxidation by air. PMID:27616940

  2. Nonradiative deactivation of excited hemicyanines studied with submolecular spatial resolution by time-resolved surface second harmonic generation at liquid-liquid interfaces.

    PubMed

    Martin-Gassin, Gaelle; Villamaina, Diego; Vauthey, Eric

    2011-03-02

    The excited-state dynamics of aminostilbazolium dyes is known to be dominated by nonradiative deactivation through large-amplitude motion. In order to identify the coordinate(s) responsible for this process, the excited-state lifetimes of two dialkylaminostyryl-methylpyridinium iodides have been measured at liquid-liquid interfaces using time-resolved surface second harmonic generation. We found that the decay time of the excited-states of both compounds was increasing with the viscosity of the apolar phase, consisting of n-alkanes of varying length, but was unaffected by that of the polar phase, made of water/glycerol mixtures. This indicates that the nonradiative deactivation is associated with the twist of the dialkylaniline group, which is located in the apolar part of the molecule.

  3. Studies of selected organic nonlinear optical and light-emitting materials

    NASA Astrophysics Data System (ADS)

    Tan, Shida

    In this dissertation, the nonlinear optical and light emitting properties of a selected class of organic materials have been studied in detail. Novel organic molecular salts, 4-dimethylaminostyryl-N-methylpyridinium methanesulfonate (DASMS) and 4-diethylaminostyryl-N-methylpyridinium p-toluenesulfonate (DEST), were synthesized. A few selected stilbazolium derivatives, 3-methyl-4-methoxy-4'-nitrostilbene (MMONS), 4-dimethylaminostyryl-N-methylpyridinium p-toluenesulfonate (DAST), and DASMS were grown into excellent optical quality single-crystal thin-films, on which detailed polarized UV-Vis spectroscopy and X-ray diffraction studies were carried out. The crystallographic parameters of p-nitro-benzobromide (NBB) are reported for the first time. The values of the tensor elements of second-order susceptibility of MMONS at the fundamental wavelength of 1064 nm were measured to be d33 = 195 +/- 10 pm/V and d24 = 75 +/- 5 pm/V by detailed polarization selective second-harmonic generation measurements. Both type I and type II phase-matched propagation directions were identified in the MMONS single-crystal. The electro-optic effects in MMONS and DASMS single-crystal thin-films were studied using field-induced birefringence method. Measured r-coefficients of MMONS are r33 = 55rho5 pm/V and r23 = 21rho2 pm/V at 1064 nm. The electro-optic coefficients of DASMS single-crystal thin-films were measured over a broad range of wavelengths (from 632.8 nm to 820 nm). The largest r-coefficients of DASMS were observed at 740 nm to be r11 = 552rho60 pm/V and r12 = 184rho20 pm/V. Compact free-space and fiber-coupled DAST electro-optic thin-film devices with both transmission and reflection geometries were demonstrated for the first time. DEST and 4-(4-hydroxystyryl)-N-methylpyridinium p-toluenesulfonate (HSMPT) were shown to have 20% and 30% spectrally narrowed laser-like emission conversion efficiencies without external mirrors despite their small photoluminescence efficiencies. With 55

  4. An Ising iron(ii) chain exhibits a large finite-size energy barrier and "hard" magnetic behaviour.

    PubMed

    Deng, Yi-Fei; Han, Tian; Xue, Wei; Hayashi, Naoaki; Kageyama, Hiroshi; Zheng, Yan-Zhen

    2017-01-31

    One-dimensional spin chains featuring strong axial anisotropic magnetism are promising candidates for isolatable and miniatured information storage materials, the so-called single-chain magnets (SCMs). Here we show a mixed azido/carboxylato bridged metamagnetic iron(ii) chain [Fe(N3)2(4-mpc)]n (4-mpc = N-methylpyridinium-4-carboxylate) with a large energy barrier of 150 K, a large remnant magnetization (1.55Nβ) and coercivity (1.7 T at 2 K) for homo-spin SCMs. Heat capacity and Mössbauer spectroscopy studies corroborate the intrinsic nature of SCM behavior regardless of weak interchain magnetic interactions, which lead to the coexistence of metamagnetism but not long-range magnetic ordering. Moreover, detailed magnetic investigations indicate that the system is not only within the "Ising limit" but also in the "finite-size" regime.

  5. Exploration of complexes of 18-crown-6 with three similarly substituted imidazolium, pyridinium and pyrrolidinium ionic liquids

    NASA Astrophysics Data System (ADS)

    Saha, Subhadeep; Roy, Mahendra Nath

    2017-09-01

    Supramolecular host-guest complexation with excellent comparison among three similarly substituted ionic liquids, namely, 1-butyl-3-methylimidazolium chloride, 1-butyl-4-methylpyridinium chloride and 1-butyl-1-methylpyrrolidinium chloride have been investigated with 18-crown-6 in acetonitrile medium by conductivity in a range of temperature to elucidate the stoichiometry of the complexes. The programmed mathematical study with the help of conductivity data provides association constants for the complexes, by which the thermodynamic properties have been evaluated for improved understanding about complexation. The molecular interactions have been explained and critically discussed with the help of FT-IR and 1H NMR spectroscopic studies, which illustrate H-bond and ion-dipolar attractions primarily exist in complexation.

  6. Mixed ionic liquid as electrolyte for lithium batteries

    NASA Astrophysics Data System (ADS)

    Diaw, M.; Chagnes, A.; Carré, B.; Willmann, P.; Lemordant, D.

    Ionic liquids like 1-butyl-3-methylimidazolium tetrafluoroborate (IMIBF 4) or hexafluorophosphate (IMIPF 6) and 1-butyl-4-methylpyridinium tetrafluoroborate (PyBF 4) were mixed with organic solvents such as butyrolactone (BL) and acetonitrile (ACN). A lithium salt (LiBF 4 or LiPF 6) was added to these mixtures for possible application in the field of energy storage (batteries or supercapacitors). Viscosities, conductivities and electrochemical windows at a Pt electrode of these electrolytes were investigated. All studied electrolytes are stable toward oxidation and exhibit a vitreous phase transition, which has been determined by application of the VTF theory to conductivity measurements. Mixtures containing the BF 4- anion exhibit the lowest viscosity and the highest conductivity. Two mixtures have been optimized in terms of conductivity: BL/IMIBF 4 (60/40, v/v) and ACN/IMIBF 4 (70/30, v/v).

  7. Spectral-luminescent study of the interaction of some styrylcyanine dyes with bovine serum albumin and DNA in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Nizomov, Negmat; Kurtaliev, Eldar N.; Nizamov, Shawkat N.; Khodjayev, Gayrat

    2009-11-01

    Spectral-luminescent characteristics of the several new styrylcyanine dyes, synthesized on the base of F dye ((E)-4-(4-(dimethylamino)styryl)-1-methylpyridinium iodide), were studied in aqueous solutions in the presence and absence of bovine serum albumin and deoxyribonucleic acid. It was shown, that with the rise of concentration of bovine serum albumin and deoxyribonucleic acid in aqueous solution, the bathochromic shift of electronic absorption spectra band and sharp intensity increase of fluorescence band intensity are observed for studied dyes, while the shape of absorption and fluorescence bands remains intact. Biophysical parameters (the binding constant and quantity of the binding sites) of interaction of studied dyes with BSA and DNA were determined. It is shown, that homodimer styrylcyanine dyes with a pentyl - or longer linking chain have larger binding affinity to specified biomolecules than dyes with shorter link-chain.

  8. Thiophene-Fused Nickel Dithiolenes: A Synthetic Scaffold for Highly Delocalized π-Electron Systems.

    PubMed

    Amb, Chad M; Heth, Christopher L; Evenson, Sean J; Pokhodnya, Konstantin I; Rasmussen, Seth C

    2016-11-07

    A series of thiophene-fused nickel dithiolene complexes have been prepared via synthetic methods which allow the addition of peripheral aryl groups to the fused thiophene of the dithiolene ligand, thus providing access to a range of structural and electronic modifications to the dithiolene core. X-ray structural studies of the anionic complexes show that the peripheral aryl rings lie in near-perfect coplanarity to the dithiolene core and can form π-stacked columns with N-methylpyridinium cations. Density functional theory calculations show significant delocalization of the frontier orbital electron density into the peripheral aryl rings. The complexes exhibit tunable, intense near-IR (NIR) absorption in the range of 1076-1160 nm with molar absorptivity as high as 25100 M(-1) cm(-1) in solution. The electronic tunability as well as the desirable solid-state packing arrangements of these systems suggests significant potential as NIR-absorbing materials for optoelectronic applications.

  9. Functional characteristics of the renal tubular secretion of amprolium, a quaternary organic base.

    PubMed

    Beyer, K H; Gelarden, R T

    1975-11-01

    Amprolium [1-(4-amino-2-propyl-5-pyrimidinemethyl)-2-methyl-pyridinium chloride hydrochloridel is a basic (quaternary) organic compound. At very low plasma concentration, it is cleared by the kidney at a rate approximating renal plasma flow in the dog. Its renal clearance is not depressed by organic acids (p-aminohippurate or probenecid) but is reduced by the quaternary base, mepiperphenidol. Acetate and pantothenate may influence the clearance of amprolium but, if this is the case, the effect is less than for p-aminohippurate. Its clearance is depressed as urinary pH is increased. The clearance of amprolium was not altered over a substantial range in urine flow at either high or low urinary pH.

  10. FABRICATION OF A RETINAL PROSTHETIC TEST DEVICE USING ELECTRODEPOSITED SILICON OVER POLYPYRROLE PATTERNED WITH SU-8 PHOTORESIST.

    PubMed

    Miller, Eric; Ellis, Daniel; Charles, Duran; McKenzie, Jason

    2015-01-01

    A materials fabrication study of a photodiode array for possible application of retina prosthesis was undertaken. A test device was fabricated using a glassy carbon electrode patterned with SU-8 photoresist. In the openings, p-type polypyrrole was first electrodeposited using 1-butyl-1-methylpyridinium bis(trifluoromethylsulfonyl)imide ionic liquid. The polypyrrole was self-doped with imide ion at ~1.5 mole %, was verified as p-type, and had a resistivity of ~20 Ωcm. N-type Silicon was then electrodeposited over this layer using silicon tetrachloride / phosphorus trichloride in acetonitrile and passivated in a second electrodeposition using trimethylchlorosilane. Electron microscopy revealed the successful electrodeposition of silicon over patterned polypyrrole. Rudimentary photodiode behavior was observed. The passivation improved but did not completely protect the electrodeposited silicon from oxidation by air.

  11. Superoxide dismutase activity of the naturally occurring human serum albumin-copper complex without hydroxyl radical formation.

    PubMed

    Kato, Ryunosuke; Akiyama, Matofusa; Kawakami, Hiroyoshi; Komatsu, Teruyuki

    2014-01-01

    The superoxide radical anion (O2(.-)) is biologically toxic and contributes to the pathogenesis of various diseases. Here we describe the superoxide dismutase (SOD) activity of human serum albumin (HSA) complexed with a single Cu(II) ion at the N-terminal end (HSA-Cu complex). The structure of this naturally occurring copper-coordinated blood serum protein has been characterized by several physicochemical measurements. The O2(.-) dismutation ability of the HSA-Cu (1:1) complex is almost the same as that of the well-known SOD mimics, such as Mn(III) -tetrakis(N-methylpyridinium)porphyrin. Interestingly, the HSA-Cu complex does not induce a subsequent Fenton reaction to produce the hydroxyl radical (OH(.)), which is one of the most harmful reactive oxygen species.

  12. Luminescent lanthanide metal-organic frameworks for chemical sensing and toxic anion detection.

    PubMed

    Wu, Rui-Zhi; Yang, Xing; Zhang, Liang-Wei; Zhou, Pan-Pan

    2017-08-01

    Prototype lanthanide metal-organic frameworks (LnMOFs), Ln(BTC) (Ln = Eu and Tb; BTC = benzene-1,3,5-tricarboxylate), have been considered as luminescent sensors for detecting toxic anions, while their neutral pore structures have limited the entrance and encapsulation of anions to produce highly anion-responsive photoluminescence (PL). To facilitate anions to enter the pore space of Ln(BTC), a one-pot synthesis method was proposed in which BTC was partially replaced with its structural analogue L·BF4 (H3L·BF4 = 2,4,6-tricarboxy-1-methylpyridinium tetrafluoroborate) which consists of an anion affinity site of cationic methylpyridinium. Compared to the original Ln(BTC), the co-doped cationic framework Eu0.05Tb0.95-BTC0.9L0.1 is highly sensitive for detecting different toxic anions by tuning the energy absorption of organic chromophores, the energy transfer efficiency to Ln(3+) ions and the energy allocation between different Ln(3+) ions in the PL spectra. We demonstrated that the Eu0.05Tb0.95-BTC0.9L0.1 PL sensor has the capability of decoding various toxic anions with a clearly differentiable and unique emission intensity ratio of (5)D4 → (7)F5 (Tb(3+), 545 nm) to (5)D0 → (7)F2 (Eu(3+), 618 nm) transitions (ITb/IEu). Compared to Ln(BTC), the co-doped Eu0.05Tb0.95-BTC0.9L0.1 presents self-calibrating, high distinguishable and stable PL signals for detecting toxic anions.

  13. Assay at low ppm level of dimethyl sulfate in starting materials for API synthesis using derivatization in ionic liquid media and LC-MS.

    PubMed

    Grinberg, Nelu; Albu, Florin; Fandrick, Keith; Iorgulescu, Elena; Medvedovici, Andrei

    2013-03-05

    Dimethyl sulfate (DMS) is frequently used in pharmaceutical manufacturing processes as an alkylating agent. Trace levels of DMS in drug substances should be carefully monitored since the compound can become an impurity which is genotoxic in nature. Derivatization of DMS with dibenzazepine leads to formation of the N-methyl derivative, which can be retained on a reversed phase column and subsequently separated from other potential impurities. Such derivatization occurs relatively slowly. However, it can be substantially speed up if ionic liquids are used as reaction media. In this paper we report the use of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (IL1) and 1-butyl-4-methylpyridinium tetrafluoroborate (IL2) as reaction media for the derivatization of DMS with dibenzazepine. It was determined that the stoichiometry between the substrate and DMS may be 1:1 or 2:1, in relation with the nature of the reaction media. An (+)ESI-MS/MS approach was used for quantitation of the derivatized product. Alternatively, DMS derivatization may be carried out with pyridine in acetonitrile (ACN). The N-methylpyridinium derivative was separated by hydrophilic interaction liquid chromatography (HILIC) and detected through (+)ESI-MS (in the SIM mode). In both cases, a limit of quantitation (LOQ) of 0.05 μg/ml DMS was achievable, with a linearity range up to 10 μg/ml. Both analytical alternatives were applied to assay DMS in 4-(2-methoxyethyl)phenol, which is used as a starting material in the synthesis of metoprolol. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. Superhydrophilic Antireflective Periodic Mesoporous Organosilica Coating on Flexible Polyimide Substrate with Strong Abrasion-Resistance.

    PubMed

    Wang, Jing; Zhang, Cong; Yang, Chunming; Zhang, Ce; Wang, Mengchao; Zhang, Jing; Xu, Yao

    2017-02-15

    Superhydrophilic antireflective periodic mesoporous organosilica (PMO) coating was prepared on flexible polyimide substrate via solvent-evaporation-induced self-assembly (SEISA) method, in which tetraethoxysilane (TEOS) and a special bridged silsesquioxane were used as reactants. The bridged silsesquioxane, EG-BSQ, was synthesized through the stoichiometric reaction between 3-glycidoxyporpyltrimethoxysilane (GPTMS) and ethylene diamine (EDA). Under the influence of surfactant, TEOS and EG-BSQ co-condensed and enclosed the ordered mesporous in the coating. The results of grazing-incidence small-angle X-ray scattering (GISAXS) and the transmission electron microscope (TEM) indicated that the mesopores belonged to a Fmmm orthorhombic symmetry structure. With increasing EG-BSQ concentration, the mesoporous structure in the PMO coating becomes more and more disordered because silica mesopore walls shrunk or collapsed during calcination and consequently the refractive index of PMO coating became larger. The antireflective (AR) PMO coating showed an optical transmittance of 99.54% on polyimide (PI) much higher than the 88.68% of bare PI. The water contact angle of PMO coating was less than 9.0°, which indicated the AR PMO coating was superhydrophilic. Moreover, the PMO coating showed an excellent mechanical property, the transmittance of the PMO coating displayed a very low loss of 0.1% after abrasion of 25 cycles by CS-10F wearaser.

  15. Synthesis and characterization of complex polymer architectures

    NASA Astrophysics Data System (ADS)

    Farmer, Brandon Scott

    Anionic polymerization based upon high vacuum technique has been used to synthesize different star polymers using varying linking techniques. In particular chlorosilanes, divinylbenzene, and polyhedral oligomeric silsesquioxane (POSS) chlorosilane derivatives were used in the synthesis of star polymers. These polymers, along with polymers synthesized by others, have been characterized by a range of methods in this work. A series of polyisoprene (PI) stars were synthesized from dimethylaminopropyllithium (DMAPLi) and subsequently hydrogenated to form poly (ethylene-co-propylene) (PEP) these were characterized by size exclusion chromatography (SEC) coupled with online two angle laser light scattering (TALLS). These polymers were synthesized in an attempt to make a new series of viscosity index improvers as an oil additive. The polymers were characterized by differential scanning calorimetry and thermal gravimetric analysis. A novel process for producing eight arm star polymers was explored using a Polyhedral Oligomeric Silsesquioxane (POSS) modified with chlorosilanes as the linking agent. The arms of these stars were prepared polybutadiene prepared anionically. A study of the effect of living end-groups was also explored by endcapping the living polybutadiene with a polystrylanion and the linking efficiency was monitored. These polymers were also characterized by SEC coupled with TALLS.

  16. Ceramic microparticles and capsules via microfluidic processing of a preceramic polymer

    PubMed Central

    Ye, Congwang; Chen, Anthony; Colombo, Paolo; Martinez, Carlos

    2010-01-01

    We have developed a robust technique to fabricate monodispersed solid and porous ceramic particles and capsules from single and double emulsion drops composed of silsesquioxane preceramic polymer. A microcapillary microfluidic device was used to generate the monodispersed drops. In this device, two round capillaries are aligned facing each other inside a square capillary. Three fluids are needed to generate the double emulsions. The inner fluid, which flows through the input capillary, and the middle fluid, which flows through the void space between the square and inner fluid capillaries, form a coaxial co-flow in a direction that is opposite to the flow of the outer fluid. As the three fluids are forced through the exit capillary, the inner and middle fluids break into monodispersed double emulsion drops in a single-step process, at rates of up to 2000 drops s−1. Once the drops are generated, the silsesquioxane is cross-linked in solution and the cross-linked particles are dried and pyrolysed in an inert atmosphere to form oxycarbide glass particles. Particles with diameters ranging from 30 to 180 µm, shell thicknesses ranging from 10 to 50 µm and shell pore diameters ranging from 1 to 10 µm were easily prepared by changing fluid flow rates, device dimensions and fluid composition. The produced particles and capsules can be used in their polymeric state or pyrolysed to ceramic. This technique can be extended to other preceramic polymers and can be used to generate unique core–shell multimaterial particles. PMID:20484226

  17. Assignment of the vibrational spectra of the parent polysilsesquioxane (POSS): Octahydridosilasequioxane, H8Si8O12

    NASA Astrophysics Data System (ADS)

    Parker, Stewart F.

    2017-01-01

    Polysilsesquioxanes (POSS) are molecules with the empirical formula (RSiO1.5)n where R is a hydrogen atom or hydroxyl or an organic moiety such as an alkyl, alkene, acrylate or epoxide. The silicon atoms occupy the corners of a cube and oxygen atoms are located on the edges, the versatility of silsesquioxanes arises from the vacant fourth position of silicon. The choice of substituent enables a wide variety of properties to be engineered in a straightforward manner. The parent POSS is octasilsesquioxane, H8Si8O12, with R = H and n = 8. The present work employs periodic density functional theory calculations in conjunction with all the available vibrational (infrared, Raman and inelastic neutron scattering) spectra to generate a complete assignment of all the modes of the parent POSS octasilsesquioxane and some of its isotopomers for both the free, (Oh), molecule and the solid state material (C3i site symmetry) including the forbidden and very weak modes. The latter are of interest because in less symmetrical silsesquioxanes, these modes will be activated.

  18. Computational and experimental determinations of the UV adsorption of polyvinylsilsesquioxane-silica and titanium dioxide hybrids.

    PubMed

    Wang, Haiyan; Lin, Derong; Wang, Di; Hu, Lijiang; Huang, Yudong; Liu, Li; Loy, Douglas A

    2014-01-01

    Sunscreens that absorb UV light without photodegradation could reduce skin cancer. Polyvinyl silsesquioxanes are known to have greater thermal and photochemical stability than organic compounds, such as those in sunscreens. This paper evaluates the UV transparency of vinyl silsesquioxanes (VS) and its hybrids with SiO2(VSTE) and TiO2(VSTT) experimentally and computationally. Based on films of VS prepared by sol-gel polymerization, using benzoyl peroxide as an initiator, vinyltrimethoxysilane (VMS) formulated oligomer through thermal curing. Similarly, VSTE films were prepared from VMS and 5-25 wt-% tetraethoxysilane (TEOS) and VSTT films were prepared from VMS and 5-25 wt-% titanium tetrabutoxide (TTB). Experimental average transparencies of the modified films were found to be about 9-14% between 280-320 nm, 67-73% between 320-350nm, and 86-89% between 350-400nm. Computation of the band gap was absorption edges for the hybrids in excellent agreement with experimental data. VS, VSTE and VSTT showed good absorption in UV-C and UV-B range, but absorbed virtually no UV-A. Addition of SiO2 or TiO2 does not improve UV-B absorption, but on the opposite increases transparency of thin films to UV. This increase was validated with molecular simulations. Results show computational design can predict better sunscreens and reduce the effort of creating sunscreens that are capable of absorbing more UV-B and UV-A.

  19. Synchrotron X-ray scattering studies of nanostructure-formation at interfaces

    NASA Astrophysics Data System (ADS)

    Sanyal, Milan K.

    2013-02-01

    We shall discuss results of a series of synchrotron x-ray scattering studies to understand the ordering of nanostructured materials formed at interfaces. In particular we shall discuss formation of germanium quantum-dots at the MBE grown silicon-germanium super-lattice structure and reversible crystallization of monolayer of Polyhedral Oligomeric SilSesquioxane (POSS) on water surface. The consistent analysis of the x-ray reflectivity and diffraction data collected in the Indian Beamline at Photon Factory Synchrotron, KEK, Japan have allowed determination of electron density and strain profile as a function of depth. The electron density profile obtained from the reflectivity and elemental profile obtained from SIMS measurements were effectively used to calculate diffraction data that provided strain and compositional profiles. The behaviour of amphiphilic Silsesquioxane POSS molecules under in-plane pressure in a Langmuir trough was studied at the ChemMatCARS, Sector 15, Advanced Photon Source, USA. We observe clear evidence of reversible crystallization of the POSS monolayers at the air-water interface - at higher pressure sharp diffraction spots are observed and as the pressure is withdrawn typical monolayer scattering comes back. Results of AFM studies of the lifted films in these two extreme phases were found to be consistent with the x-ray data.

  20. Maleimides in recent sediments - Using chlorophyll degradation products for palaeoenvironmental reconstructions

    NASA Astrophysics Data System (ADS)

    Naeher, Sebastian; Schaeffer, Philippe; Adam, Pierre; Schubert, Carsten J.

    2013-10-01

    Maleimides (transformation products of chlorophylls and bacteriochlorophylls) were studied in recent sediments from the Swiss lake Rotsee and the Romanian Black Sea Shelf to investigate chlorophyll degradation, the role of oxygen in maleimide formation, and to identify their sources. Naturally occurring maleimides (i.e. "free" maleimides) and maleimides obtained after chromic acid oxidation of sediment extracts (i.e. "bound" maleimides) were analysed. 2-Methyl-maleimide (Me,H maleimide), 2,3-dimethyl-maleimide (Me,Me maleimide), 2-methyl-3-vinyl-maleimide (Me,vinyl maleimide), 2-methyl-3-ethyl-maleimide (Me,Et maleimide) and traces of 2-methyl-3-iso-butyl-maleimide (Me,i-Bu maleimide) occurred naturally in the sediment with a large predominance of the Me,Et homologue. Tetrapyrrolic pigments related to chlorophylls were the main source of maleimides, although variable contributions of other sources such as cytochromes and/or phycobilins cannot be completely ruled out. The predominant Me,Et maleimide and Me,vinyl maleimide most likely originate mainly from chlorophyll a related pigments. The same holds for Me,H maleimide, which might be formed following degradation of ring E from the tetrapyrrolic nucleus. Alternatively, Me,H maleimide and Me,Me maleimides might be formed by a recently discovered transformation pathway involving the oxidation of vinylic chlorophyll substituents and the formation of an aldehyde intermediate. 2-Methyl-3-n-propyl-maleimide (Me,n-Pr maleimide) and Me,i-Bu maleimide arising from bacteriochlorophyll related pigments traced the presence of phototrophic sulfur bacteria (Chlorobi), indicating photic zone euxinic and anoxic conditions in Rotsee during the last 150 years and throughout the Black Sea history, including the limnic phase of the Black Sea (Unit 3). Some other minor maleimides with specific alkylation pattern also originate from bacteriochlorophylls, while the source of others could not be identified. Free maleimides were mainly

  1. Oxidation reactions of 2-thiouracil: a theoretical and pulse radiolysis study.

    PubMed

    Prasanthkumar, K P; Suresh, C H; Aravindakumar, C T

    2012-11-08

    The reaction of hydroxyl radical ((•)OH) with the nucleic acid base analogue 2-thiouracil (1) has been studied by pulse radiolysis experiments and DFT. The generic intermediate radicals feasible for the (•)OH reactions with 1, namely, one electron oxidation product (1(•+)), (•)OH-adducts (3(•), 4(•), and 5(•)), and H-abstracted radicals (6(•) and 7(•)), were characterized by interpreting their electronic and structural properties along with calculated energetics and UV-vis spectra. Pulse radiolysis experiments showed that the transient formed in the reaction of (•)OH with 1 in water at pH 6.5 has λ(max) at 430 nm. A bimolecular rate constant, k(2) of 9.6 × 10(9) M(-1) s(-1), is determined for this reaction via competition kinetics with 2-propanol. The experiments suggested that the transient species could be a dimer radical cation 2(•+), formed by the reaction of 1 with the radical cation 1(•+). For this reaction, an equilibrium constant of 4.7 × 10(3) M(-1) was determined. The transient formed in the reaction of 1 with pulse radiolytically produced Br(2)(•-) at pH 6.5 as well as Cl(2)(•-) at pH 1 has also produced λ(max) at 430 nm and suggested the formation of 2(•+). The calculated UV-vis spectra of the transient species (1(•+), 3(•), 4(•), 5(•), 6(•), and 7(•)) showed no resemblance to the experimental spectra, while that of 2(•+) (λ(max) = 420 nm) agreed well with the experimental value and thus confirmed the formation of 2(•+). The 420 nm peak was due to σ → σ* electronic excitation centered on a 2-center-3-electron (2c-3e) sulfur-sulfur bond [-S∴S-]. 2(•+) is the first reported example of a dimer radical cation in a pyrimidine heterocyclic system. Further, 5-C and 6-C substituted (substituents are -F, -Cl, -NH(2), -N(CH(3))(2), -OCH(3), -CF(3), -CH(3), -CH(2)CH(3), n-propyl, phenyl, and benzyl) and 5,6-disubstituted 2-thiouracil systems have been characterized by DFT and found that the reaction (1 + 1

  2. Synthesis and characterization of silicon-based polymers for use as organic/inorganic hybrids and silicon carbide precursors

    NASA Astrophysics Data System (ADS)

    Sellinger, Alan

    Organic/inorganic hybrids from silsesquioxanes. This Dissertation describes the synthesis and characterization of methacrylate, epoxy and liquid crystalline (LC)-containing organic/inorganic hybrid materials based on silsesquioxanes. While the methacrylate and epoxy groups provide polymerizable moieties to the hybrids, the LC component is anticipated to provide toughness, and oxidative stability as well as minimize shrinkage during curing. The inorganic silsesquioxane portion, ((RSiOsb{1.5})sb8, cubes), which closely resembles specific crystalline forms of silica and zeolites, may be covalently linked to a variety of organic functional groups. As a result, single-phase organic/inorganic hybrids are formed that when polymerized mimic silica-reinforced composites. The resultant hybrids are liquids at room temperature, and hence allow for single-phase composite processing, ideal for abrasion-resistant coatings and filling molds, as in dental restorative applications. The reactions are based on inexpensive starting materials, have high yields (>80%), and form soluble products containing up to 65% masked silica. The hybrids were characterized using NMR spectroscopy (sp1H,\\ sp{13}C,\\ sp{29}Si), FTIR, size exclusion chromatography (SEC), and thermal analysis (TGA, DSC). A modified polymethylsilane as a precursor of silicon carbide. It is generally known that polymer precursor routes to silicon carbide (SiC) are very important in the processing of SiC fibers and high performance SiC parts with specific shapes. It is further known that commercial SiC precursor polymers are often not resistant to oxidation, and are based on monomers rich in carbon. As a result of this, their pyrolysis yields SiC rich in oxygen and carbon, a feature which drastically reduces the final materials' ultimate properties (high temperature resistance, tensile strength, modulus). To remedy this, we describe in this work the synthesis and characterization of a modified polymethylsilane (mPMS) which

  3. Development of new polysilsesquioxane spherical particles as stabilized active ingredients for sunscreens

    NASA Astrophysics Data System (ADS)

    Tolbert, Stephanie Helene

    Healthy skin is a sign of positive self-worth, attractiveness and vitality. Compromises to this are frequently caused by extended periods of recreation in the sun and in turn exposure to the harmful effects of UV radiation. To maintain strength and integrity, protection of the skin is paramount. This can be achieved by implementing skin-care products which contain sunscreen active ingredients that provide UV protection. Unfortunately, photo-degradation, toxicity, and photo-allergies limit the effectiveness of present day sunscreen ingredients. Currently, this is moderated by physically embedding within inert silica particles, but leaching of the active ingredient can occur, thereby negating protective efforts. Alternatively, this research details the preparation and investigation of bridged silsesquioxane analogues of commercial ingredients which can be chemically grafted to the silica matrix. Studies with bridged salicylate particles detail facile preparation, minimized leaching, and enhanced UV stability over physically encapsulated and pendant salicylate counterparts. In terms of UVB protective ability, the highest maintenance of sun protection factor (SPF) after extended UV exposure was achieved with bridged incorporation, and has been attributed to corollary UV stability. Additionally, bridged salicylate particles can be classified as broad-spectrum, and rate from moderate to good in terms of UVA protective ability. Particles incorporated with a bridged curcuminoid silsesquioxane were also prepared and displayed comparable results. As such, an attractive method for sunscreen isolation and stabilization has been developed to eliminate the problems associated with current sunscreens, all while maintaining the established UV absorbance profiles of the parent compound. To appreciate the technology utilized in this research, a thorough understanding of sol-gel science as it pertains to hybrid organic/silica particles, including methods of organic fragment

  4. Solvation in pure liquids: what can be learned from the use of pairs of indicators?

    PubMed

    Silva, Priscilla L; Pires, Paulo A R; Trassi, Marco A S; El Seoud, Omar A

    2008-11-27

    The solvation of six solvatochromic probes in a large number of solvents (33-68) was examined at 25 degrees C. The probes employed were the following: 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (RB); 4-[(E)2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePM; 1-methylquinolinium-8-olate, QB; 2-bromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr, 2,6-dichloro-4-(2,4,6-triphenyl pyridinium-1-yl) phenolate (WB); and 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), respectively. Of these, MePMBr is a novel compound. They can be grouped in three pairs, each with similar pK(a) in water but with different molecular properties, for example, lipophilicity and dipole moment. These pairs are formed by RB and MePM; QB and MePMBr; WB and MePMBr(2), respectively. Theoretical calculations were carried out in order to calculate their physicochemical properties including bond lengths, dihedral angles, dipole moments, and wavelength of absorption of the intramolecular charge-transfer band in four solvents, water, methanol, acetone, and DMSO, respectively. The data calculated were in excellent agreement with available experimental data, for example, bond length and dihedral angles. This gives credence to the use of the calculated properties in explaining the solvatochromic behaviors observed. The dependence of an empirical solvent polarity scale E(T)(probe) in kcal/mol on the physicochemical properties of the solvent (acidity, basicity, and dipolarity/polarizability) and those of the probes (pK(a), and dipole moment) was analyzed by using known multiparameter solvation equations. For each pair of probes, values of E(T)(probe) (for example, E(T)(MePM) versus E(T)(RB)) were found to be linearly correlated with correlation coefficients, r, between 0.9548 and 0.9860. For the mercyanine series, the values of E(T)(probe) also correlated linearly, with (r) of 0.9772 (MePMBr versus MePM) and 0.9919 (MePMBr(2) versus MePM). The response

  5. Solvatochromism in binary mixtures: first report on a solvation free energy relationship between solvent exchange equilibrium constants and the properties of the medium.

    PubMed

    Silva, Priscilla L; Trassi, Marco A S; Martins, Clarissa T; El Seoud, Omar A

    2009-07-16

    We have employed UV-vis spectroscopy in order to investigate details of the solvation of six solvatochromicindicators, hereafter designated as "probes", namely, 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate(RB); 4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePM; 1-methylquinolinium-8-olate, QB;2-bromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr, 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (WB); and 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate,MePMBr2, respectively. These can be divided into three pairs, each includes two probes of similar p kappa(a) in water and different lipophilicity. Solvation has been studied in binary mixtures, BMs, of water, W, with 12protic organic solvents, S, including mono- and bifunctional alcohols (2-alkoxyethanoles, unsaturated and chlorinated alcohols). Each medium was treated as a mixture of S, W, and a complex solvent, S-W, formed by hydrogen bonding. Values of lambda max (of the probe intramolecular charge transfer) were converted into empirical polarity scales, ET(probe) in kcal/mol, whose values were correlated with the effective mole fraction of waterin the medium, chi W(effective). This correlation furnished three equilibrium constants for the exchange of solvents int he probe solvation shell; phi W/S (W substitutes S); phi S-W/W (S-W substitutes W), and phi S-W/S (S-W substitutes S), respectively. The values of these constants depend on the physicochemical properties of the probe and the medium. We tested, for the first time, the applicability of a new solvation free energy relationship: phi =constant + a alpha(BM) + b beta(BM) + s(pi* (BM) + d delta) + p log P (BM), where a, b, s, and p are regression coefficients; RBM,alpha (BM), beta(BM) and pi (BM) are solvatochromic parameters of the BM, delta is a correction term for pi*, and log P is an empirical scale of lipophilicity. Correlations were carried out with two-, three-, and four-medium descriptors

  6. Low dielectric and low surface free energy flexible linear aliphatic alkoxy core bridged bisphenol cyanate ester based POSS nanocomposites

    NASA Astrophysics Data System (ADS)

    Alagar, Muthukaruppan; Devaraju, S.; Prabunathan, P.; Selvi, M.

    2013-10-01

    The aim of the present work is to develop a new type of flexible linear aliphatic alkoxy core bridged bisphenol cyanate ester (AECE) based POSS nanocomposites for low k applications. The POSS-AECE nanocomposites were developed by incorporating varying weight percentages (0, 5 and 10 wt %) of octakis (dimethylsiloxypropylglycidylether) silsesquioxane (OG-POSS) into cyanate esters. Data from thermal and dielectric studies imply that the POSS reinforced nanocomposite exhibits higher thermal stability and low dielectric value of k=2.4 (10 wt% POSS-AECE4) compared than those of neat AECE. From the contact angle measurement, it is inferred that, the increase in the percentage incorporation of POSS in to AECE, the values of water contact angle was enhanced. Further, the value of surface free energy was lower when compared to that of neat AECE. The molecular level dispersion of POSS into AECE was ascertained from SEM and TEM analyses.

  7. Polyimide-organosilicate hybrids with improved thermal and optical properties.

    PubMed

    Jung, Youngsuk; Byun, Sunjung; Park, Sungjun; Lee, Hyunmi

    2014-05-14

    Through hydrolysis and polycondensation of amino-silane with alkyl bridged silane, a new type of polysilsesquioxane (PSSQ) was obtained. Here we use amine functionalized silane and bis(silyl)ethane to synthesize alkyl chain linked PSSQ. Compared to conventional polyhedral oligomeric silsesquioxane (POSS), this new silane compound has both enhanced thermal stability and improved compatibility with poly(amic acid). Gelation of this silane compound with poly(amic acid) provides polyimide-organosilicate composite materials. We show that films made from solutions of the composites exhibit higher optical transparency and superior dimensional stability during thermal treatment than films of pure polyimide or of polyimide composites with conventional POSS. Bridging of POSS and chemical bonding between POSS and polyimide chains significantly enhance the physical properties. These results provide useful information for designing molecular architecture for the fabrication of high-performance plastic substrates in the future display devices.

  8. Elastomeric polyurea nanocomposites

    NASA Astrophysics Data System (ADS)

    Casalini, R.; Roland, C. M.

    2012-07-01

    The effect of multiwall carbon nanotubes (MWCNT), nano-layered silicate (nanoclay), and trisilanolphenyl-functionalized polyhedral oligomeric silsesquioxane (POSS) on the rheology and mechanical properties of an oligomeric polydiamine and the polyurea formed by its reaction with isocyanate were measured. The MWCNT and nanoclay increase the viscosity of the polydiamine and form a flocculated filler network at very low concentrations (< 1%). This network imparts a strong strain-dependence to the dynamic modulus. These effects are absent with POSS, which primarily affects the polyurea chemistry. The tensile modulus of the cured polyurea is higher for all three additives, and using POSS significantly tougher material can be obtained, provided adjustments to the stoichiometry are made.

  9. PP/POSS Nanocomposites: Characterization and Properties of Melt Spun Fibers

    NASA Astrophysics Data System (ADS)

    Lee, Byoung-Jo; Roy, Sayantan; Jana, Sadhan

    2009-03-01

    It is known that molecules of polyhedral oligomeric silsesquioxane (POSS) can self-assemble into spherical, fibrillar, or lamellar nanoparticles by bottom-up self assembly process during mixing with host polymers. This study capitalizes on such nanoparticle formation to increase the melt strength and tensile properties of polyolefin blown films and spun fibers. A novel method was developed whereby a sorbitol-type nucleating agent was used as dispersion aids for POSS. The nucleating agent also served as templates for self-assembly of POSS molecules into nanoparticles of 25-200 nm in diameter. A typical polypropylene formulation containing 0.3 wt% nucleating agent and 5-10 wt% POSS was spun into fibers with close to 70% reduction in diameter and 40-45% increase in modulus and 70-75% increase in yield strength compared to unfilled PP. An optimum concentration of POSS was identified.

  10. Development of active biofilms of quinoa (Chenopodium quinoa W.) starch containing gold nanoparticles and evaluation of antimicrobial activity.

    PubMed

    Pagno, Carlos H; Costa, Tania M H; de Menezes, Eliana W; Benvenutti, Edilson V; Hertz, Plinho F; Matte, Carla R; Tosati, Juliano V; Monteiro, Alcilene R; Rios, Alessandro O; Flôres, Simone H

    2015-04-15

    Active biofilms of quinoa (Chenopodium quinoa, W.) starch were prepared by incorporating gold nanoparticles stabilised by an ionic silsesquioxane that contains the 1,4-diazoniabicyclo[2.2.2]octane chloride group. The biofilms were characterised and their antimicrobial activity was evaluated against Escherichiacoli and Staphylococcusaureus. The presence of gold nanoparticles produces an improvement in the mechanical, optical and morphological properties, maintaining the thermal and barrier properties unchanged when compared to the standard biofilm. The active biofilms exhibited strong antibacterial activity against food-borne pathogens with inhibition percentages of 99% against E. coli and 98% against S. aureus. These quinoa starch biofilms containing gold nanoparticles are very promising to be used as active food packaging for the maintenance of food safety and extension of the shelf life of packaged foods.

  11. Synthesis and application of hydride silica composites for rapid and facile removal of aqueous mercury.

    PubMed

    Katok, Kseniia V; Whitby, Raymond L D; Fayon, Franck; Bonnamy, Sylvie; Mikhalovsky, Sergey V; Cundy, Andrew B

    2013-12-16

    The adsorption of ionic mercury(II) from aqueous solution on functionalized hydride silicon materials was investigated. The adsorbents were prepared by modification of mesoporous silica C-120 with triethoxysilane or by converting alkoxysilane into siloxanes by reaction with acetic acid. Mercury adsorption isotherms at 208C are reported, and maximum mercury loadings were determined by Langmuir fitting. Adsorbents exhibited efficient and rapid removal of ionic mercury from aqueous solution, with a maximum mercury loading of approximately 0.22 and 0.43 mmol of Hg g1 of silica C-120 and polyhedraloligomeric silsesquioxane (POSS) xerogel, respectively. Adsorption efficiency remained almost constant from pH 2.7 to 7. These inexpensive adsorbents exhibiting rapid assembly, low pH sensitivity, and high reactivity and capacity, are potential candidates as effective materials for mercury decontamination in natural waters and industrial effluents.

  12. Soft-substrate rigid-feature (SSRF) mold for nanoimprint lithography

    NASA Astrophysics Data System (ADS)

    Menachem, Liran; Schvartzman, Mark

    2016-09-01

    In this work, we introduce a novel concept of hybrid nano-imprint mold based on a soft substrate with rigid relief features. Our approach combines the advantages of soft and rigid molding approaches, and at the same time overcomes their drawbacks. Specifically, this mold provides a unique combination of: (1) High pattern fidelity and small feature size as offered by hard molds and (2) low sensitivity to defects and ability to pattern curved substrates as offered by soft molds. The SSRF mold was fabricated by electron-beam lithography of Hydrogen Silsesquioxane (HSQ) on a sacrificial substrate, followed by transferring the obtained HSQ features to elastomeric PDMS substrate. The pattern replication was demonstrated on nano imprint of UV-curable resist.

  13. Understanding the mechanism of base development of HSQ

    SciTech Connect

    Kim, Jihoon; Chao, Weilun; Griedel, Brian; Liang, Xiaogan; Lewis, Mark; Hilken, Dawn; Olynick, Deirdre

    2009-06-16

    We study the dissolution mechanism of HSQ (hydrogen silsesquioxane) in base solutions with the addition of chloride salts to elucidate the development mechanism. Reaction mechanisms are proposed based on the dissolution mechanism of quartz. Development kinetics points to two dose-dependent development mechanisms. Considering ion sizes, both hydrated and non-hydrated, and ion exchange, we propose that a combination of a surface dominated reaction at higher doses and a matrix dominated reaction at lower doses accounts for the high development contrast with a NaOH base/NaCl salt mixture. The interplay between the hydrated and non-hydrated ion size leads to higher contrast developers, such as tetramethyl ammonium hydroxide (TMAH) with NaCl.

  14. Effect of adding nanometre-sized heterogeneities on the structural dynamics and the excess wing of a molecular glass former

    NASA Astrophysics Data System (ADS)

    Gupta, S.; Fischer, J. K. H.; Lunkenheimer, P.; Loidl, A.; Novak, E.; Jalarvo, N.; Ohl, M.

    2016-10-01

    We present the relaxation dynamics of glass-forming glycerol mixed with 1.1 nm sized polyhedral oligomeric silsesquioxane (POSS) molecules using dielectric spectroscopy (DS) and two different neutron scattering (NS) techniques. Both, the reorientational dynamics as measured by DS and the density fluctuations detected by NS reveal a broadening of the α relaxation when POSS molecules are added. Moreover, we find a significant slowing down of the α-relaxation time. These effects are in accord with the heterogeneity scenario considered for the dynamics of glasses and supercooled liquids. The addition of POSS also affects the excess wing in glycerol arising from a secondary relaxation process, which seems to exhibit a dramatic increase in relative strength compared to the α relaxation.

  15. Structural Analysis of Polymer Composites Using Spectral Domain Optical Coherence Tomography.

    PubMed

    Shirazi, Muhammad Faizan; Jeon, Mansik; Kim, Jeehyun

    2017-05-18

    The structural analysis of nylon/graphene oxide (NY/GO) and polyetherblockamide/ trisilinolphenyl-polyhederal oligomeric silsesquioxane (PEBA/t-POSS) composites were performed using high-resolution spectral domain optical coherence tomography (SD-OCT). This optical technology revealed both cross-sectional, as well as sub-layer depth information of sample. The non-destructive real-time imaging demonstrated the nature of defects in the composites. The thickness and location of each defect point in the composites were measured using A-scan analysis on the SD-OCT images. The cross-sectional and volumetric images clearly demonstrate the effectiveness of SD-OCT for composite research, as well as the for industrial quality assurance of polymer materials.

  16. New insight into the structure of dispersed titania by combining normal-mode analysis with experiment

    NASA Astrophysics Data System (ADS)

    Nitsche, David; Hess, Christian

    2014-11-01

    Normal-mode analysis has been combined with experiment to gain new insight into the vibrational structure of dispersed titania. For the calculations, double- and tri-grafted hydroxylated titania species have been adapted to a model silica support based on polyhedral oligomeric silsesquioxane (POSS). The choice of hydroxylated models was validated by IR detection of the Osbnd H stretching band of dispersed titania (0.7 Ti/nm2). UV resonance Raman experiments have identified three titania-related vibrational features within the spectral region 900-1100 cm-1 due to Tisbnd Osbnd Si interphase, Tisbnd Osbnd Si in-phase and out-of-phase stretching vibrations. This behaviour is fully consistent with the results obtained by the normal-mode analysis.

  17. Polymeric routes to silicon carbide and silicon oxycarbide CMC

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Heimann, Paul J.; Gyekenyesi, John Z.; Masnovi, John; Bu, Xin YA

    1991-01-01

    An overview of two approaches to the formation of ceramic composite matrices from polymeric precursors is presented. Copolymerization of alkyl- and alkenylsilanes (RSiH3) represents a new precursor system for the production of Beta-SiC on pyrolysis, with copolymer composition controlling polymer structure, char yield, and ceramic stoichiometry and morphology. Polysilsesquioxanes which are synthesized readily and can be handled in air serve as precursors to Si-C-O ceramics. Copolymers of phenyl and methyl silsesquioxanes display rheological properties favorable for composite fabrication; these can be tailored by control of pH, water/methoxy ratio and copolymer composition. Composites obtained from these utilize a carbon coated, eight harness satin weave Nicalon cloth reinforcement. The material exhibits nonlinear stress-strain behavior in tension.

  18. Hollow mesoporous organosilica nanoparticles: a generic intelligent framework-hybridization approach for biomedicine.

    PubMed

    Chen, Yu; Meng, Qingshuo; Wu, Meiying; Wang, Shige; Xu, Pengfei; Chen, Hangrong; Li, Yaping; Zhang, Lingxia; Wang, Lianzhou; Shi, Jianlin

    2014-11-19

    Chemical construction of molecularly organic-inorganic hybrid hollow mesoporous organosilica nanoparticles (HMONs) with silsesquioxane framework is expected to substantially improve their therapeutic performance and enhance the biological effects beneficial for biomedicine. In this work, we report on a simple, controllable, and versatile chemical homology principle to synthesize multiple-hybridized HMONs with varied functional organic groups homogeneously incorporated into the framework (up to quintuple hybridizations). As a paradigm, the hybridization of physiologically active thioether groups with triple distinctive disulfide bonds can endow HMONs with unique intrinsic reducing/acidic- and external high intensity focused ultrasound (HIFU)-responsive drug-releasing performances, improved biological effects (e.g., lowered hemolytic effect and improved histocompatibility), and enhanced ultrasonography behavior. The doxorubicin-loaded HMONs with concurrent thioether and phenylene hybridization exhibit drastically enhanced therapeutic efficiency against cancer growth and metastasis, as demonstrated both in vitro and in vivo.

  19. Wavelength control of random polymer fiber laser based on adaptive disorder.

    PubMed

    Hu, Zhijia; Gao, Pengfei; Xie, Kang; Liang, Yunyun; Jiang, Haiming

    2014-12-15

    We demonstrate the realization of two different kinds of random polymer optical fiber lasers to control the random lasing wavelength by changing the disorder of polymer optical fibers (POFs). One is a long-range disorder POF based on copolymer refractive-index inhomogeneity, and the other is a short-range disorder POF based on polyhedral oligomeric silsesquioxanes scattering. By end pumped both disorder POFs, the coherent random lasing for both is observed. Meanwhile, the random lasing wavelength of the short-range disorder POF because of a small scattering mean-free path has been found to be blue shifted with respect to the long-range disorder POF, which will give a way to control the random lasing wavelength.

  20. High-efficiency graphene nanomesh magnets realized by controlling mono-hydrogenation of pore edges

    SciTech Connect

    Kato, T.; Kamijyo, J.; Kobayashi, T.; Yagi, Y.; Haruyama, J.; Nakamura, T.

    2014-06-23

    We demonstrate a drastic improvement in the efficiency of rare-element-free graphene nanomesh (GNM) magnets with saturation magnetization values as large as ∼10{sup −4 }emu/mm{sup 2}, which are 10–100 times greater than those in previous GNM magnets hydrogenated by only annealing under a hydrogen molecule (H{sub 2}) atmosphere, even at room temperature. This improvement is realized by a significant increase in the area of the mono-H-terminated pore edges by using hydrogen silsesquioxane resist treatment with electron beam irradiation, which can produce mono-H by detaching H-silicon (Si) bonds. This result must open the door for industrial applications of graphene magnets to rare-element-free magnetic and spintronic systems.

  1. Effect of nano SiO2 particles on the morphology and mechanical properties of POSS nanocomposite dental resins

    NASA Astrophysics Data System (ADS)

    Liu, Yizhi; Sun, Yi; Zeng, Fanlin; Xie, Weili; Liu, Yang; Geng, Lin

    2014-12-01

    Nanocomposite dental resins composed of polyhedral oligomeric silsesquioxane nanocomposite matrix and 0, 0.5,1, 1.5 and 2 wt% nano SiO2 as filler were prepared by light curing method. The nanocomposite resins were characterized by performing compressive, three-point flexure, nanoindentation and nanoscratch testings as well as optical microscopy and scanning electron microscope analysis. The effects of different nano SiO2 contents were studied on compressive strength, flexural strength, hardness and resistance of composite resin. From the mechanical results, it was found that nano SiO2 effectively enhanced the mechanical properties of the composite resins at low content. With the increase of the nano SiO2 content, the mechanical properties decreased. It was attributed to the content of nano SiO2 and dispersion of nanoparticles in matrix.

  2. Effect of adding nanometre-sized heterogeneities on the structural dynamics and the excess wing of a molecular glass former

    PubMed Central

    Gupta, S.; Fischer, J. K. H.; Lunkenheimer, P.; Loidl, A.; Novak, E.; Jalarvo, N.; Ohl, M.

    2016-01-01

    We present the relaxation dynamics of glass-forming glycerol mixed with 1.1 nm sized polyhedral oligomeric silsesquioxane (POSS) molecules using dielectric spectroscopy (DS) and two different neutron scattering (NS) techniques. Both, the reorientational dynamics as measured by DS and the density fluctuations detected by NS reveal a broadening of the α relaxation when POSS molecules are added. Moreover, we find a significant slowing down of the α-relaxation time. These effects are in accord with the heterogeneity scenario considered for the dynamics of glasses and supercooled liquids. The addition of POSS also affects the excess wing in glycerol arising from a secondary relaxation process, which seems to exhibit a dramatic increase in relative strength compared to the α relaxation. PMID:27725747

  3. A transmission line method for evaluation of vertical InAs nanowire contacts

    SciTech Connect

    Berg, M. Svensson, J. Lind, E. Wernersson, L.-E.

    2015-12-07

    In this paper, we present a method for metal contact characterization to vertical semiconductor nanowires using the transmission line method (TLM) on a cylindrical geometry. InAs nanowire resistors are fabricated on Si substrates using a hydrogen silsesquioxane (HSQ) spacer between the bottom and top contact. The thickness of the HSQ is defined by the dose of an electron beam lithography step, and by varying the separation thickness for a group of resistors, a TLM series is fabricated. Using this method, the resistivity and specific contact resistance are determined for InAs nanowires with different doping and annealing conditions. The contacts are shown to improve with annealing at temperatures up to 300 °C for 1 min, with specific contact resistance values reaching down to below 1 Ω µm{sup 2}.

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

    PubMed Central

    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

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

    PubMed

    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

    2015-07-31

    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.

  6. Low dielectric and low surface free energy flexible linear aliphatic alkoxy core bridged bisphenol cyanate ester based POSS nanocomposites

    PubMed Central

    Devaraju, S.; Prabunathan, P.; Selvi, M.; Alagar, M.

    2013-01-01

    The aim of the present work is to develop a new type of flexible linear aliphatic alkoxy core bridged bisphenol cyanate ester (AECE) based POSS nanocomposites for low k applications. The POSS-AECE nanocomposites were developed by incorporating varying weight percentages (0, 5, and 10 wt %) of octakis (dimethylsiloxypropylglycidylether) silsesquioxane (OG-POSS) into cyanate esters. Data from thermal and dielectric studies imply that the POSS reinforced nanocomposite exhibits higher thermal stability and low dielectric value of k = 2.4 (10 wt% POSS-AECE4) compared than those of neat AECE. From the contact angle measurement, it is inferred that, the increase in the percentage incorporation of POSS in to AECE, the values of water contact angle was enhanced. Further, the value of surface free energy was lower when compared to that of neat AECE. The molecular level dispersion of POSS into AECE was ascertained from SEM and TEM analyses. PMID:24790947

  7. Atomic oxygen effects on POSS polyimides in low earth orbit.

    PubMed

    Minton, Timothy K; Wright, Michael E; Tomczak, Sandra J; Marquez, Sara A; Shen, Linhan; Brunsvold, Amy L; Cooper, Russell; Zhang, Jianming; Vij, Vandana; Guenthner, Andrew J; Petteys, Brian J

    2012-02-01

    Kapton polyimde is extensively used in solar arrays, spacecraft thermal blankets, and space inflatable structures. Upon exposure to atomic oxygen in low Earth orbit (LEO), Kapton is severely eroded. An effective approach to prevent this erosion is to incorporate polyhedral oligomeric silsesquioxane (POSS) into the polyimide matrix by copolymerizing POSS monomers with the polyimide precursor. The copolymerization of POSS provides Si and O in the polymer matrix on the nano level. During exposure of POSS polyimide to atomic oxygen, organic material is degraded, and a silica passivation layer is formed. This silica layer protects the underlying polymer from further degradation. Laboratory and space-flight experiments have shown that POSS polyimides are highly resistant to atomic-oxygen attack, with erosion yields that may be as little as 1% those of Kapton. The results of all the studies indicate that POSS polyimide would be a space-survivable replacement for Kapton on spacecraft that operate in the LEO environment.

  8. Fabrication of single-crystal silicon nanotubes with sub-10 nm walls using cryogenic inductively coupled plasma reactive ion etching.

    PubMed

    Li, Zhiqin; Chen, Yiqin; Zhu, Xupeng; Zheng, Mengjie; Dong, Fengliang; Chen, Peipei; Xu, Lihua; Chu, Weiguo; Duan, Huigao

    2016-09-09

    Single-crystal silicon nanostructures have attracted much attention in recent years due in part to their unique optical properties. In this work, we demonstrate direct fabrication of single-crystal silicon nanotubes with sub-10 nm walls which show low reflectivity. The fabrication was based on a cryogenic inductively coupled plasma reactive ion etching process using high-resolution hydrogen silsesquioxane nanostructures as the hard mask. Two main etching parameters including substrate low-frequency power and SF6/O2 flow rate ratio were investigated to determine the etching mechanism in the process. With optimized etching parameters, high-aspect-ratio silicon nanotubes with smooth and vertical sub-10 nm walls were fabricated. Compared to commonly-used antireflection silicon nanopillars with the same feature size, the densely packed silicon nanotubes possessed a lower reflectivity, implying possible potential applications of silicon nanotubes in photovoltaics.

  9. Toward Controlled Hierarchical Heterogeneities in Giant Molecules with Precisely Arranged Nano Building Blocks

    PubMed Central

    2016-01-01

    Herein we introduce a unique synthetic methodology to prepare a library of giant molecules with multiple, precisely arranged nano building blocks, and illustrate the influence of minute structural differences on their self-assembly behaviors. The T8 polyhedral oligomeric silsesquioxane (POSS) nanoparticles are orthogonally functionalized and sequentially attached onto the end of a hydrophobic polymer chain in either linear or branched configuration. The heterogeneity of primary chemical structure in terms of composition, surface functionality, sequence, and topology can be precisely controlled and is reflected in the self-assembled supramolecular structures of these giant molecules in the condensed state. This strategy offers promising opportunities to manipulate the hierarchical heterogeneities of giant molecules via precise and modular assemblies of various nano building blocks. PMID:27163025

  10. Organic Thin-Film Transistor from a Pentacene Photoprecursor

    NASA Astrophysics Data System (ADS)

    Masumoto, Akane; Yamashita, Yuko; Go, Shintetsu; Kikuchi, Toshihiro; Yamada, Hiroko; Okujima, Tetsuo; Ono, Noboru; Uno, Hidemitsu

    2009-05-01

    Organic thin-film transistors were successfully fabricated by the spin-coating method using a photo-precursor of pentacene, 6,13-dihydro-6,13-ethanopentacene-15,16-dione. After spin coating the soluble precursor, irradiation with visible light gave a pentacene film. A good mobility of 0.34 cm2 V-1 s-1 and a high on/off ratio of 2.0×106 were achieved by treatment of the insulator surface with methyl silsesquioxane and by deposition of pentacene from the precursor with visible light irradiation (>300 nm) and mild heat treatment (110-120 °C). In this case, small grains of pentacene crystals existed in the loosely ordered pentacene mesophase, in which pentacene molecules aligned vertically. Not only the grains of pentacene crystals but also the loosely packed pentacene phase played an important role in the field-effect transistor (FET) performance.

  11. A transmission line method for evaluation of vertical InAs nanowire contacts

    NASA Astrophysics Data System (ADS)

    Berg, M.; Svensson, J.; Lind, E.; Wernersson, L.-E.

    2015-12-01

    In this paper, we present a method for metal contact characterization to vertical semiconductor nanowires using the transmission line method (TLM) on a cylindrical geometry. InAs nanowire resistors are fabricated on Si substrates using a hydrogen silsesquioxane (HSQ) spacer between the bottom and top contact. The thickness of the HSQ is defined by the dose of an electron beam lithography step, and by varying the separation thickness for a group of resistors, a TLM series is fabricated. Using this method, the resistivity and specific contact resistance are determined for InAs nanowires with different doping and annealing conditions. The contacts are shown to improve with annealing at temperatures up to 300 °C for 1 min, with specific contact resistance values reaching down to below 1 Ω µm2.

  12. Fluorinated Polyhedral Oligosilsesquioxane Surfaces and Superhydrophobicity

    NASA Astrophysics Data System (ADS)

    Iacono, Scott T.; Peloquin, Andrew J.; Smith, Dennis W.; Mabry, Joseph M.

    Fluorinated compounds are a logical choice for hydrophobic applications owing to their generally low surface energy. Polyhedral molecules may also improve hydrophobicity by increasing material surface roughness. There have been many recent attempts to synthesize and characterize various types of fluorinated polyhedra. These reports include the fluorination or fluoroalkylation of C60 [1,2]. Unfortunately, C60F48 (fluorinated buckminsterfullerene) cannot be used as a hydrophobic material, since it is metastable and is hydrolyzed by water [3]. However, the perfluorocarborane species, perfluoro-deca-β-methyl-para-carborane, shows remarkable hydrolytic and oxidative stability [4]. Fluorinated carbon nanotubes and nanofibers have also been produced [5]. Many of these fluorinated polyhedral compounds may be useful in hydrophobic applications, but they are generally hazardous to prepare, require air and moisture sensitive manipulations, and have limited economies of scale. For these reasons, alternative fluorinated polyhedra, such as Polyhedral Oligomeric SilSesquioxanes (POS) are highly desired (Figure 6.1).

  13. Tangible nanocomposites with diverse properties for heart valve application

    NASA Astrophysics Data System (ADS)

    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.

  14. Synthesis of functionalized silica nanostructure: Unexpected conversion of cyanopropyl group in chloropropyl one during HCl-catalysed hydrolysis of the corresponding triethoxysilane

    NASA Astrophysics Data System (ADS)

    Dumitriu, Ana-Maria-Corina; Balan, Mihaela; Bargan, Alexandra; Shova, Sergiu; Varganici, Cristian-Dragos; Cazacu, Maria

    2016-04-01

    During acid hydrolysis of 3-cyanopropyltriethoxysilane (CyTES) in a molar ratio HCl:CyTES - 4.6:1 in methanol, with the intention to prepare the properly polyhedral oligomeric silsesquioxane (POSSQ) or carboxyl derivative, the conversion of organic functional group occurred by replacing the CN group with Cl forming octakis(chloropropyl)octasilsesquioxane (Cl-POSSQ). The structure was determined through X-ray single crystal diffraction, spectral (FTIR and NMR) techniques and elemental analysis. The stepwise conversion of the CN group during the 3-cyanopropyltriethoxysilane hydrolysis was monitored through IR and 13C NMR spectroscopy. Thermal behavior was studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Moisture sorption capacity was evaluated by water vapor sorption in dynamic regime (DVS). The biological activity was in vitro tested against three fungi and two bacteria.

  15. Design of a sub phthalocyanine-based hybrid donor of photovoltaic materials and its theoretical investigation

    NASA Astrophysics Data System (ADS)

    Zheng, Shaohui; Tian, Yongping; Chen, Xue; Xiao, Mengyue

    2017-08-01

    Chloro boron-subphthalocyanine (sub PC) is one of promising organic solar materials. Diverse sub PC-based derivatives have been synthesized and proposed. In the present work, we theoretically suggest new inorganic-organic hybrid materials, i.e. sub PC derivatives with the ortho and Meta peripheral substitution by highly symmetric octahedral silsesquioxane (T8). The results of electronic structure of ortho and Meta sub PC-T8 molecules prove that the substitutions of T8 SQ in sub PC have little influences on frontier orbitals. The simulated electronic spectrums of ortho and Meta sub PC-T8 molecules are similar to sub PC alone, but with noticeable stronger absorption oscillator strength than sub PC. Our calculation predicts that the new designed T8-sub PC molecules have great potential to be new promising donor materials and have some merits compared to sub PC molecule.

  16. Topology assisted self-organization of colloidal nanoparticles: application to 2D large-scale nanomastering.

    PubMed

    Kadiri, Hind; Kostcheev, Serguei; Turover, Daniel; Salas-Montiel, Rafael; Nomenyo, Komla; Gokarna, Anisha; Lerondel, Gilles

    2014-01-01

    Our aim was to elaborate a novel method for fully controllable large-scale nanopatterning. We investigated the influence of the surface topology, i.e., a pre-pattern of hydrogen silsesquioxane (HSQ) posts, on the self-organization of polystyrene beads (PS) dispersed over a large surface. Depending on the post size and spacing, long-range ordering of self-organized polystyrene beads is observed wherein guide posts were used leading to single crystal structure. Topology assisted self-organization has proved to be one of the solutions to obtain large-scale ordering. Besides post size and spacing, the colloidal concentration and the nature of solvent were found to have a significant effect on the self-organization of the PS beads. Scanning electron microscope and associated Fourier transform analysis were used to characterize the morphology of the ordered surfaces. Finally, the production of silicon molds is demonstrated by using the beads as a template for dry etching.

  17. Evaporation-induced self-structuring of organised silica nanohybrid films through cooperative physical and chemical interactions.

    PubMed

    Cojocariu, Ana M; Cattoën, Xavier; Le Parc, Rozenn; Maurin, David; Blanc, Christophe; Dieudonné, Philippe; Bantignies, Jean-Louis; Wong Chi Man, Michel; Bartlett, John R

    2016-03-21

    In this work, we develop the concept of evaporation-induced self-structuring as a novel approach for producing organised films by exploiting cooperative physical and chemical interactions under far-from-equilibrium conditions (spin-coating), using sol-gel precursors with multiple functional groups. Thin films of self-structured silsesquioxane nanohybrids have been deposited by spin coating through the sol-gel hydrolysis and condensation of a bridged organosilane bearing self-assembling urea groups. The resulting nanostructure, investigated by FTIR, AFM and SEM, is shown to be highly dependent on the catalyst used (nucleophilic or acidic), and can be further modulated by varying the spinning rate. FTIR studies revealed the presence of highly organised structures under acidic catalysis due to strong hydrogen bonding between urea groups and hydrophobic interactions between long alkylene chains. The preferential orientation of the urea cross-links parallel to the substrate is shown using polarized FTIR experiments.

  18. Hierarchical Self-Assembled Structures from POSS-Containing Block Copolymers Synthesized by Living Anionic Polymerization

    SciTech Connect

    Hirai, Tomoyasu; Leolukman, Melvina; Jin, Sangwoo; Goseki, Raita; Ishida, Yoshihito; Kakimoto, Masa-aki; Hayakawa, Teruaki; Ree, Moonhor; Gopalan, Padma

    2010-03-16

    Two kinds of polyhedral oligomeric silsesquioxane (POSS)-containing block copolymers (BCPs), namely PS-b-PMAPOSS and PMMA-b-PMAPOSS, were synthesized by living anionic polymerization. A wide range of molecular weights were obtained with a very narrow polydispersity index of less than 1.09. The bulk samples prepared by slow evaporation from a polymer solution in chloroform exhibit well-defined microphase-separated structures with long-range order. Thermal annealing induced hierarchical structures consisting of a smaller length scale ordered crystalline POSS domains within the larger microphase-separated structures. We report detailed structural characterization of these hierarchical structures in bulk and thin films by transmission electron microscopy and grazing incidence wide-angle X-ray scattering (GIWAXS). On the basis of this structural analysis, we propose a model for the formation of an orthorhombic lattice structure through the aggregation of POSS segments which formed a helix-like structure.

  19. Chemically Functionalized Conjugated Oligoelectrolyte Nanoparticles for Enhancement of Current Generation in Microbial Fuel Cells.

    PubMed

    Zhao, Cui-e; Chen, Jia; Ding, Yuanzhao; Wang, Victor Bochuan; Bao, Biqing; Kjelleberg, Staffan; Cao, Bin; Loo, Say Chye Joachim; Wang, Lianhui; Huang, Wei; Zhang, Qichun

    2015-07-08

    Water-soluble conjugated oligoelectrolyte nanoparticles (COE NPs), consisting of a cage-like polyhedral oligomeric silsesquioxanes (POSS) core equipped at each end with pendant groups (oligo(p-phenylenevinylene) electrolyte, OPVE), have been designed and demonstrated as an efficient strategy in increasing the current generation in Escherichia coli microbial fuel cells (MFCs). The as-prepared COE NPs take advantage of the structure of POSS and the optical properties of the pendant groups, OPVE. Confocal laser scanning microscopy showed strong photoluminescence of the stained cells, indicating spontaneous accumulation of COE NPs within cell membranes. Moreover, the electrochemical performance of the COE NPs is superior to that of an established membrane intercommunicating COE, DSSN+ in increasing current generation, suggesting that these COE NPs thus hold great potential to boost the performance of MFCs.

  20. Hypoxic condition-selective upconversion via triplet-triplet annihilation based on POSS-core dendrimer complexes.

    PubMed

    Tanaka, Kazuo; Okada, Hiroshi; Ohashi, Wataru; Jeon, Jong-Hwan; Inafuku, Kenichi; Chujo, Yoshiki

    2013-05-15

    The influence on the efficiencies of the triplet-triplet annihilation (TTA)-supported upconversion by oxygen under biomimetic conditions was investigated. From the solution containing the dendrimer complexes based on polyhedral oligomeric silsesquioxane (POSS)-core dendrimer with the Pt complex of octaethylporphyrin (PtOEP) and anthracene in PBS, the fluorescence emission of anthracene depending on the dissolved oxygen (DO) concentrations via the TTA-supported upconversion was obtained with the excitation light at 540 nm. In particular, we observed strong emission only under hypoxic conditions. In addition, it was found that the emission intensity via TTA-supported upconversion can be reversibly regulated by the DO concentrations in the solution. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Supramolecular self-assembly of linear oligosilsesquioxanes on mica--AFM surface imaging and hydrophilicity studies.

    PubMed

    Kowalewska, Anna; Nowacka, Maria; Tracz, Adam; Makowski, Tomasz

    2015-06-28

    Linear oligomeric [2-(carboxymethylthio)ethylsilsesquioxanes] (LPSQ-COOH) adsorb spontaneously on muscovite mica and form smooth, well-ordered lamellar structures at the liquid-solid interface. Side carboxylic groups, having donor-acceptor character with regard to hydrogen bonds, are engaged both in multipoint molecule-to-substrate interactions and intermolecular cross-linking. The unique arrangement of silsesquioxane macromolecules, with COOH groups situated at the interface with air, produces highly hydrophilic surfaces of good thermal and solvolytic stability. Supramolecular assemblies of LPSQ-COOH were studied using atomic force microscopy (AFM), angle-resolved X-ray photoelectron spectroscopy (ARXPS) and attenuated total reflectance (ATR) FTIR spectroscopy. Comparative height profile analysis combined with ATR-FTIR studies of the spectral regions characteristic of carboxylic groups and C1s core level envelope by XPS confirmed specific interactions between LPSQ-COOH and mica.

  2. Substituent effects on the sol-gel chemistry of organotrialkoxysilanes

    SciTech Connect

    LOY, DOUGLAS A.; BAUGHER, BRIGITTA M.; BAUGHER, COLLEEN R.; SCHNEIDER, DUANE A.; RAHIMIAN, KAMYAR

    2000-05-09

    Silsesquioxanes have been the subject of intensive study in the past and are becoming important again as a vehicle for introducing organic functionalities into hybrid organic-inorganic materials through sol-gel processing. Depending on the application, the target hybrid material may be required to be a highly cross-linked, insoluble gel or a soluble polymer that can be cast as a thin film or coating. The former has applications such as catalyst supports and separations media; the latter is an economically important method for surface modification or compatiblization for applying adhesives or introducing fillers. Polysilsesquioxanes are readily prepared through the hydrolysis and condensation of organotrialkoxysilanes, though organotriaminosilane and organotrihalosilane monomers can also be used. This paper explores the kinetics of the preparation route.

  3. Epoxy Resin Composite Based on Functional Hybrid Fillers

    PubMed Central

    Oleksy, Mariusz; Szwarc-Rzepka, Karolina; Heneczkowski, Maciej; Oliwa, Rafał; Jesionowski, Teofil

    2014-01-01

    A study was carried out involving the filling of epoxy resin (EP) with bentonites and silica modified with polyhedral oligomeric silsesquioxane (POSS). The method of homogenization and the type of filler affect the functional and canceling properties of the composites was determined. The filler content ranged from 1.5% to 4.5% by mass. The basic mechanical properties of the hybrid composites were found to improve, and, in particular, there was an increase in tensile strength by 44%, and in Charpy impact strength by 93%. The developed hybrid composites had characteristics typical of polymer nanocomposites modified by clays, with a fine plate morphology of brittle fractures observed by SEM, absence of a plate separation peak in Wide Angles X-ray Scattering (WAXS) curves, and an exfoliated structure observed by TEM. PMID:28788177

  4. Space Environmental Effects on Coated Tether Materials

    NASA Technical Reports Server (NTRS)

    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.

  5. CONDENSED MATTER: STRUCTURE, MECHANICAL AND THERMAL PROPERTIES: Fabrication of 11-nm-Wide Silica-Like Lines Using X-Ray Diffraction Exposure

    NASA Astrophysics Data System (ADS)

    Zhu, Xiao-Li; Xie, Chang-Qing; Zhang, Man-Hong; Liu, Ming; Chen, Bao-Qin; Pan, Feng

    2009-08-01

    Fine silica-like lines with 11 nm width are successfully fabricated using x-ray Fresnel diffraction exposure. X-rays pass a mask of 175-nm-wide lines and 125-nm-wide spaces and form sharp peaks on a wafer coated with a layer of hydrogen silsesquioxane resist (HSQ). By precisely controlling the mask-wafer gap at 10 μm using the laser interferogram method, the fine structures are defined on HSQ. Experimental images are reproduced by a simulation using the one-dimensional beam propagation method. This lithographic technique presents a novel and convenient way to fabricate fine silica-like structures and devices in nano-optical and nanoelectronic applications.

  6. Electrical properties of high density arrays of silicon nanowire field effect transistors

    NASA Astrophysics Data System (ADS)

    Kim, Hye-Young; Lee, Kangho; Lee, Jae Woo; Kim, Sangwook; Kim, Gyu-Tae; Duesberg, Georg S.

    2013-10-01

    Proximity effect corrected e-beam lithography of hydrogen silsesquioxane on silicon on insulator was used to fabricate multi-channel silicon nanowire field-effect transistors (SiNW FETs). Arrays of 15-channels with a line width of 18 nm and pitch as small as 50 nm, the smallest reported for electrically functional devices, were fabricated. These high density arrays were back-gated by the substrate and allowed for investigation of the effects of scaling on the electrical performance of this multi-channel SiNW FET. It was revealed that the drain current and the transconductance (gm) are both reduced with decreasing pitch size. The drain induced barrier lowering and the threshold voltage (Vth) are also decreased, whereas the subthreshold swing (S) is increased. The results are in agreement with our simulations of the electric potential profile of the devices. The study contains valuable information on SiNW FET integration and scaling for future devices.

  7. Pathway toward large two-dimensional hexagonally patterned colloidal nanosheets in solution.

    PubMed

    Ni, Bo; Huang, Mingjun; Chen, Ziran; Chen, Yingchao; Hsu, Chih-Hao; Li, Yiwen; Pochan, Darrin; Zhang, Wen-Bin; Cheng, Stephen Z D; Dong, Xue-Hui

    2015-02-04

    We report the solution self-assembly of an ABC block terpolymer consisting of a polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer tail tethered to a fluorinated polyhedral oligomeric silsesquioxane (FPOSS) cage in 1,4-dioxane/water. With increasing water content, abundant unconventional morphologies, including circular cylinders, two-dimensional hexagonally patterned colloidal nanosheets, and laterally patterned vesicles, are sequentially observed. The formation of toroids is dominated by two competing free energies: the end-cap energy of cylinders and the bending energy to form the circular structures. Incorporating the superhydrophobic FPOSS cages enhances the end-cap energy and promotes toroid formation. Lateral aggregation and fusion of the cylinders results in primitive nanosheets that are stabilized by the thicker rims to partially release the rim-cap energy. Rearrangement of the parallel-aligned FPOSS cylindrical cores generates hexagonally patterned nanosheets. Further increasing the water content induces the formation of vesicles with nanopatterned walls.

  8. Electric field enhanced hydrogen storage on polarizable materials substrates.

    PubMed

    Zhou, J; Wang, Q; Sun, Q; Jena, P; Chen, X S

    2010-02-16

    Using density functional theory, we show that an applied electric field can substantially improve the hydrogen storage properties of polarizable substrates. This new concept is demonstrated by adsorbing a layer of hydrogen molecules on a number of nanomaterials. When one layer of H(2) molecules is adsorbed on a BN sheet, the binding energy per H(2) molecule increases from 0.03 eV/H(2) in the field-free case to 0.14 eV/H(2) in the presence of an electric field of 0.045 a.u. The corresponding gravimetric density of 7.5 wt% is consistent with the 6 wt% system target set by Department of Energy for 2010. The strength of the electric field can be reduced if the substrate is more polarizable. For example, a hydrogen adsorption energy of 0.14 eV/H(2) can be achieved by applying an electric field of 0.03 a.u. on an AlN substrate, 0.006 a.u. on a silsesquioxane molecule, and 0.007 a.u. on a silsesquioxane sheet. Thus, application of an electric field to a polarizable substrate provides a novel way to store hydrogen; once the applied electric field is removed, the stored H(2) molecules can be easily released, thus making storage reversible with fast kinetics. In addition, we show that materials with rich low-coordinated nonmetal anions are highly polarizable and can serve as a guide in the design of new hydrogen storage materials.

  9. Polyelectrolyte Stars and Cylindrical Brushes Made by ATRP: New Building Blocks in Nanotechnology

    NASA Astrophysics Data System (ADS)

    Plamper, Felix; Xu, Youyong; Yuan, Jiayin; Ballauff, Matthias; Müller, Axel H. E.

    Star polymers and cylindrical polymer brushes (CPBs), i.e. polymers possessing side groups densely grafted from a linear main chain, have attracted considerable experimental and theoretical interest over the past decade, owing to their peculiar solution and bulk properties. We have used the grafting-from approach via ATRP to synthesize well-defined star polymers and core—shell CPBs with homopolymer and block copolymer side chains. The diblock copolymer side chains may include combinations of soft-hard, hydrophilic-hydrophobic and crystalline-amorphous block segments. In particular, we have been interested in polyelectrolyte blocks; then the polymers resemble intramolecular spherical and cylindrical micelles, respectively. Star polymers of poly(acrylic acid) (PAA) and poly(N,N-dimethylaminoethyl methacrylate) (DMAEMA) were made using sugar- or silsesquioxane-based ATRP initiators. Their LCST and UCST phase behaviour depends on pH, counterion charge, temperature, and light. PDMAEMA CPBs react in a similar way, and on addition of trivalent counterions they even form helical structures. We have also synthesized hybrid nanowires of semiconducting CdS and CdSe or nanomagnets of γ-Fe2O3 inside the PAA core of CPBs. Here, we present novel water-soluble and biocompatible silica nanowires based on CPBs. They have a core consisting of a silsesquioxane network of crosslinked poly(3-acryloylpropyl trimethoxysilane) (PAPTS) and a shell of poly(oligoe-thyleneglycol methacrylate) (POEGMA). Sequential ATRP of APTS and OEGMA initiated by a polyinitiator backbone (DP = 3,200) was carried out in benzene. Due to the cylindrical shape of the brushes the functional TMS moieties were arranged into a 1D manner and then crosslinked via alkaline condensation, rendering the rigid core—shell hybrid CPBs. Finally, uniform silica nanowires were achieved by the simultaneous removal of the hybrid CPB template via pyrolysis. The length as well as the diameter of silica nanowires are well-defined.

  10. Electric field enhanced hydrogen storage on polarizable materials substrates

    PubMed Central

    Zhou, J.; Wang, Q.; Sun, Q.; Jena, P.; Chen, X. S.

    2010-01-01

    Using density functional theory, we show that an applied electric field can substantially improve the hydrogen storage properties of polarizable substrates. This new concept is demonstrated by adsorbing a layer of hydrogen molecules on a number of nanomaterials. When one layer of H2 molecules is adsorbed on a BN sheet, the binding energy per H2 molecule increases from 0.03 eV/H2 in the field-free case to 0.14 eV/H2 in the presence of an electric field of 0.045 a.u. The corresponding gravimetric density of 7.5 wt% is consistent with the 6 wt% system target set by Department of Energy for 2010. The strength of the electric field can be reduced if the substrate is more polarizable. For example, a hydrogen adsorption energy of 0.14 eV/H2 can be achieved by applying an electric field of 0.03 a.u. on an AlN substrate, 0.006 a.u. on a silsesquioxane molecule, and 0.007 a.u. on a silsesquioxane sheet. Thus, application of an electric field to a polarizable substrate provides a novel way to store hydrogen; once the applied electric field is removed, the stored H2 molecules can be easily released, thus making storage reversible with fast kinetics. In addition, we show that materials with rich low-coordinated nonmetal anions are highly polarizable and can serve as a guide in the design of new hydrogen storage materials. PMID:20133647

  11. Protein profiles of Escherichia coli and Staphylococcus warneri are altered by photosensitization with cationic porphyrins.

    PubMed

    Alves, Eliana; Esteves, Ana Cristina; Correia, António; Cunha, Ângela; Faustino, Maria A F; Neves, Maria G P M S; Almeida, Adelaide

    2015-06-01

    Oxidative stress induced by photodynamic treatment of microbial cells causes irreversible damages to vital cellular components such as proteins. Photodynamic inactivation (PDI) of bacteria, a promising therapeutic approach for the treatment of superficial and localized skin and oral infections, can be achieved by exciting a photosensitizing agent with visible light in an oxygenated environment. Although some studies have addressed the oxidative alterations of PDI in bacterial proteins, the present study is the first to compare the electrophoretic profiles of proteins of Gram-positive and Gram-negative bacteria, having two structurally different porphyrins, with different kinetics of photoinactivation. The cationic porphyrins 5,10,15-tris(1-methylpyridinium-4-yl)-20-(pentafluorophenyl)porphyrin tri-iodide (Tri-Py(+)-Me-PF) and 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin tetra-iodide (Tetra-Py(+)-Me) were used to photosensitize Escherichia coli and Staphylococcus warneri upon white light irradiation at an irradiance of 4.0 mW cm(-2). After different photosensitization periods, proteins were extracted from bacteria and analyzed using one-dimensional SDS-PAGE. Apparent molecular weights and band intensities were determined after an irradiation period corresponding to a reduction of 4 log10 in cell viability. After photodynamic treatment, there was a general loss of bacterial proteins, assigned to large-scale protein degradation. Protein loss was more pronounced after PDI with Tri-Py(+)-Me-PF in both bacteria. There was also an increase in the concentration of some proteins as well as an increase in the molecular weight of other proteins. We show that proteins of E. coli and S. warneri are important targets of PDI. Although there is an attempt of cellular response to the PDI-induced damage by overexpression of a limited number of proteins, the damage is lethal. Our results show that changes occurring in the protein pattern during photodynamic treatment are

  12. Major versus minor groove DNA binding of a bisarginylporphyrin hybrid molecule: A molecular mechanics investigation

    NASA Astrophysics Data System (ADS)

    Gresh, Nohad; Perrée-fauvet, Martine

    1999-03-01

    On the basis of theoretical computations, we have recently synthesised [Perrée-Fauvet, M. and Gresh, N., Tetrahedron Lett., 36 (1995) 4227] a bisarginyl conjugate of a tricationic porphyrin (BAP), designed to target, in the major groove of DNA, the d(GGC GCC)2 sequence which is part of the primary binding site of the HIV-1 retrovirus site [Wain-Hobson, S. et al., Cell, 40 (1985) 9]. In the theoretical model, the chromophore intercalates at the central d(CpG)2 step and each of the arginyl arms targets O6/N7belonging to guanine bases flanking the intercalation site. Recent IR and UV-visible spectroscopic studies have confirmed the essential features of these theoretical predictions [Mohammadi, S. et al., Biochemistry, 37 (1998) 6165]. In the present study, we compare the energies of competing intercalation modes of BAP to several double-stranded oligonucleotides, according to whether one, two or three N- methylpyridinium rings project into the major groove. Correspondingly, three minor groove binding modes were considered, the arginyl arms now targeting N3, O2 sites belonging to the purine or pyrimidine bases flanking the intercalation site. This investigation has shown that: (i) in both the major and minor grooves, the best-bound complexes have the three N-methylpyridinium rings in the groove opposite to that of the phenyl group bearing the arginyl arms; (ii) major groove binding is preferred over minor groove binding by a significant energy (29 kcal/mol); and (iii) the best-bound sequence in the major groove is d(GGC GCC)2 with two successive guanines upstream from the intercalation. On the other hand, due to the flexibility of the arginyl arms, other GC-rich sequences have close binding energies, two of them being less stable than it by less than 8 kcal/mol. These results serve as the basis for the design of derivatives of BAP with enhanced sequence selectivities in the major groove.

  13. Transport interactions of different organic cations during their excretion by the intact rat kidney.

    PubMed

    Pietruck, F; Ullrich, K J

    1995-06-01

    Organic cations, in addition to being filtrated, are secreted or reabsorbed in the proximal renal tubule whereby they have to pass the contraluminal and the luminal cell membrane. Interactions with the transport of other organic cations can occur at either cell side, leading to inhibition or stimulation of net secretion or net reabsorption. A qualitative evaluation of such processes is possible by using the in vivo bolus injection of an organic cation as test substance. Measuring its urinary excretion profile in relation to that of inulin, under control conditions and after application of interfering organic cations, in combination with simultaneous registration of its tissue concentration, allows the demonstration of interaction and also the tentative identification of the cell side at which interference has taken place. As test substance the fluorescent organic cation 4-(4-dimethylaminostyryl)-N-methylpyridinium (4-Di-1-ASP+; denotes permanent positively-charged organic cations was used, having a protein binding of 47% under the given experimental conditions. As interfering organic cations amiloride, benzylamiloride, choline+, cimetidine, and 2-methyl-4-(heptafluorobutoxy)-N-methylpyridinium+ were injected. It was found that: (1) 4-Di-1-ASP+ is filtered and net reabsorbed under control conditions (fractional excretion 0.54 +/- 0.1). All net secreted interfering substances, except bidirectional transported choline+, injected simultaneously with 4-Di-1-ASP+, showed an interference with renal excretion of net reabsorbed 4-Di-1-ASP+, by (2) instantaneously increasing its reabsorption, resulting in a 28 to 33% decrease in urinary excretion, and (3) augmenting its tissue concentration by 19 to 58%. (4) A prolonged effect of the interfering substrates could be observed after a third injection of 4-Di-1-ASP+ (without inhibitor) showing an increased tissue concentration of 4-Di-1-ASP+ of 36 to 46%. The complex interfering pattern of the applied organic cations can be

  14. Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

    SciTech Connect

    Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon; Ocola, Leonidas E.; Nealey, Paul F.

    2016-03-08

    Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which are anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.

  15. The role of peroxyl radicals in polyester degradation--a mass spectrometric product and kinetic study using the distonic radical ion approach.

    PubMed

    Gervasoni, B D; Khairallah, G N; O'Hair, R A J; Wille, U

    2015-04-14

    Mass spectrometric techniques were used to obtain detailed insight into the reactions of peroxyl radicals with model systems of (damaged) polyesters. Using a distonic radical ion approach, it was shown that N-methylpyridinium peroxyl radical cations, Pyr(+)OO˙, do not react with non-activated C-H bonds typically present in polyesters that resist degradation. Structural damage in the polymer, for example small amounts of alkene moieties formed during the manufacturing process, is required to enable reaction with Pyr(+)OO˙, which proceeds with high preference through addition to the π system rather than via allylic hydrogen atom abstraction (kadd/kHAT > 20 for internal alkenes). This is due to the very fast and strongly exothermic subsequent fragmentation of the peroxyl-alkene radical adduct to epoxides and highly reactive Pyr(+)O˙, which both could promote further degradation of the polymer through non-radical and radical pathways. This work provides essential experimental support that the basic autoxidation mechanism is a too simplistic model to rationalize radical mediated degradation of polymers under ambient conditions.

  16. The influence of antidotal treatment of low-level tabun exposure on cognitive functions in rats using a water maze.

    PubMed

    Kassa, J; Kunesova, G

    2006-01-01

    In this study, the influence of antidotal treatment of tabun poisoning on cognitive function, in the case of low-level tabun exposure, was studied. The impairment of cognitive function was evaluated by the measurement of spatial learning and memory in rats poisoned with a sublethal dose of tabun and treated with atropine alone or in combination with newly developed oximes {K027 [1-(4-hydroxyiminomethyl- pyridinium)-3-(4-carbamoylpyridinium) propane dibromide] and K048 [1-(4-hydroxyimino- methylpyridinium)-3-(4-carbamoylpyridinium) butane dibromide]} or currently available oxime (trimedoxime), using the Morris water maze. While atropine alone caused an impairment of studied cognitive functions, the addition of an oxime to atropine contributes to the improvement of cognitive performance of treated tabun-poisoned rats regardless of the type of oxime. The differences in the ameliorative effects of oximes on atropine-induced mnemonic deficits were not significant. Therefore, each low-level nerve agent exposure should be treated by complex antidotal treatment consisting of anticholinergic drug and oxime.

  17. Effect of coffee combining green coffee bean constituents with typical roasting products on the Nrf2/ARE pathway in vitro and in vivo.

    PubMed

    Volz, Nadine; Boettler, Ute; Winkler, Swantje; Teller, Nicole; Schwarz, Christoph; Bakuradze, Tamara; Eisenbrand, Gerhard; Haupt, Larissa; Griffiths, Lyn R; Stiebitz, Herbert; Bytof, Gerhard; Lantz, Ingo; Lang, Roman; Hofmann, Thomas; Somoza, Veronika; Marko, Doris

    2012-09-26

    This study investigated Nrf2-activating properties of a coffee blend combining raw coffee bean constituents with 5-O-caffeoylquinic acid (CGA) as a lead component with typical roasting products such as N-methylpyridinium (NMP). In cell culture (HT29) the respective coffee extract (CN-CE) increased nuclear Nrf2 translocation and enhanced the transcription of ARE-dependent genes as exemplified for NAD(P)H:quinone oxidoreductase and glutathione-S-transferase (GST)A1, reflected in the protein level by an increase in GST enzyme activity. In a pilot human intervention study (29 healthy volunteers), daily consumption of 750 mL of CN-coffee for 4 weeks increased Nrf2 transcription in peripheral blood lymphocytes on average. However, the transcriptional response pattern of Nrf2/ARE-dependent genes showed substantial interindividual variations. The presence of SNPs in the Nrf2-promoter, reported recently, as well as the detection of GSTT1*0 (null) genotypes in the study collective strengthens the hypothesis that coffee acts as a modulator of Nrf2-dependent gene response in humans, but genetic polymorphisms play an important role in the individual response pattern.

  18. Photodynamic inactivation of bacterial and yeast biofilms with a cationic porphyrin.

    PubMed

    Beirão, Sandra; Fernandes, Sara; Coelho, Joel; Faustino, Maria A F; Tomé, João P C; Neves, Maria G P M S; Tomé, Augusto C; Almeida, Adelaide; Cunha, Angela

    2014-01-01

    The efficiency of 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin tetra-iodide (Tetra-Py(+)-Me) in the photodynamic inactivation of single-species biofilms of Staphylococcus aureus, Pseudomonas aeruginosa and Candida albicans and mixed biofilms of S. aureus and C. albicans was evaluated. The effect on the extracellular matrix of P. aeruginosa was also assessed. Irradiation with white light up to an energy dose of 64.8 J cm(-2) in the presence of 20 μm of Tetra-Py(+)-Me caused significant inactivation in all single-species biofilms (3-6 log reductions), although the susceptibility was attenuated in relation to planktonic cells. In mixed biofilms, the inactivation of S. aureus was as efficient as in single-species biofilms but the susceptibility of C. albicans decreased. In P. aeruginosa biofilms, a reduction of 81% in the polysaccharide content of the matrix was observed after treatment with a 20 μm PS concentration and a total light dose of 64.8 J cm(-2). The results show that the Tetra-Py(+)-Me causes significant inactivation of the microorganisms, either in biofilms or in the planktonic form, and demonstrate that polysaccharides of the biofilm matrix may be a primary target of photodynamic damage.

  19. Pharmacological characterization of a fluorescent uptake assay for the noradrenaline transporter.

    PubMed

    Haunsø, Anders; Buchanan, Dawn

    2007-04-01

    The noradrenaline transporter (NET) is a Na(+)/Cl(-) dependent monoamine transporter that mediates rapid clearance of noradrenaline from the synaptic cleft, thereby terminating neuronal signaling. NET is an important target for drug development and is known to be modulated by many psychoactive compounds, including psychostimulants and antidepressants. Here, the authors describe the development and pharmacological characterization of a nonhomogeneous fluorescent NET uptake assay using the compound 4-(4-dimethylaminostyryl)-N-methylpyridinium (ASP(+)). Data presented show that the pharmacology of both the classic radiolabeled (3)H-noradrenaline- and ASP(+)-based uptake assays are comparable, with an excellent correlation between potency obtained for known modulators of NET (r = 0.95, p < 0.0001). Furthermore, the fluorescent uptake assay is highly reproducible and has sufficiently large Z' values to be amenable for high-throughput screening (HTS). The advantage of this assay is compatibility with both 96- and 384-well formats and lack of radioactivity usage. Thus, the authors conclude that the assay is an inexpensive, viable approach for the identification and pharmacological profiling of small-molecule modulators of the monoamine transporter NET and may be amenable for HTS.

  20. Substitution Effects and Linear Free Energy Relationships During Reduction of 4- Benzoyl-n-(4-substituted Benzyl)pyridinium Cations

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas; Zhang, Guo-Hui; Rawashdeh, Abdel-Monem M.; Sotiriou-Leventis, Chariklia; Gray, Hugh R. (Technical Monitor)

    2003-01-01

    In analogy to 4-(para-substituted benzoyl)-N-methylpyridinium cations (1-X's), the title species (2-X's, -X = -OCH3, -CH3, -H, -Br, -COCH3, -NO2) undergo two reversible, well-separated (E(sub 1/2) greater than or equal to 650 mV) one-electron reductions. The effect of substitution on the reduction potentials of 2-X's is much weaker than the effect of the same substituents on 1-X's: the Hammett rho-values are 0.80 and 0.93 for the 1st- and 2nd-e reduction of 2-X's vs. 2.3 and 3.3 for the same reductions of 1-X's, respectively. Importantly, the nitro group of 2-NO2 undergoes reduction before the 2nd-e reduction of the 4-benzoylpyridinium system. These results suggest that the redox potentials of the 4-benzoylpyridinium system can be course-tuned via p-benzoyl substitution and fine-tuned via para-benzyl substitution. Introducing the recently derived substituent constant of the -NO2(sup)- group (sigma para-NO2(sup)- = -0.97) yields an excellent correlation for the 3rd-e reduction of 2- NO2 (corresponding to the reduction of the carbonyl group) with the 2nd-e reduction of the other 2-X's, and confirms the electron donating properties of -NO2(sup)-.

  1. In Vitro Anti-Inflammatory and Cytotoxic Effects of Aqueous Extracts from the Edible Sea Anemones Anemonia sulcata and Actinia equina

    PubMed Central

    Silva, Tânia Costa; de Andrade, Paula Branquinho; Paiva-Martins, Fátima; Valentão, Patrícia; Pereira, David Micael

    2017-01-01

    Marine invertebrates have been attracting the attention of researchers for their application in nutrition, agriculture, and the pharmaceutical industry, among others. Concerning sea anemones (Cnidaria), little is known regarding their metabolic profiles and potential value as a source of pharmacologically-active agents. In this work, the chemical profiles of two species of sea anemones Actinia equina and Anemonia sulcata, were studied by high-performance liquid chromatography with diode-array detection (HPLC-DAD) and its impact upon immune and gastric cells was evaluated. In both species, the methylpyridinium alkaloid homarine was the major compound in aqueous extracts. The extracts were effective in reducing lipopolysaccharide (LPS)-induced levels of nitric oxide (NO) and intracellular reactive oxygen species (ROS) in a macrophage model of inflammation. Both the extracts and the alkaloid homarine were effective in inhibiting phospholipase A2 (PLA2), a pivotal enzyme in the initial steps of the inflammatory cascade. In order to mimic the oral consumption of these extracts; their effect upon human gastric cells was evaluated. While no caspase-9 activation was detected, the fact that the endoplasmic reticulum-resident caspase-4, and also caspase-3, were activated points to a non-classical mechanism of apoptosis in human gastric cells. This work provides new insights on the toxicity and biological potential of sea anemones increasingly present in human nutrition. PMID:28304352

  2. Human proximal tubule epithelial cells cultured on hollow fibers: living membranes that actively transport organic cations.

    PubMed

    Jansen, J; De Napoli, I E; Fedecostante, M; Schophuizen, C M S; Chevtchik, N V; Wilmer, M J; van Asbeck, A H; Croes, H J; Pertijs, J C; Wetzels, J F M; Hilbrands, L B; van den Heuvel, L P; Hoenderop, J G; Stamatialis, D; Masereeuw, R

    2015-11-16

    The bioartificial kidney (BAK) aims at improving dialysis by developing 'living membranes' for cells-aided removal of uremic metabolites. Here, unique human conditionally immortalized proximal tubule epithelial cell (ciPTEC) monolayers were cultured on biofunctionalized MicroPES (polyethersulfone) hollow fiber membranes (HFM) and functionally tested using microfluidics. Tight monolayer formation was demonstrated by abundant zonula occludens-1 (ZO-1) protein expression along the tight junctions of matured ciPTEC on HFM. A clear barrier function of the monolayer was confirmed by limited diffusion of FITC-inulin. The activity of the organic cation transporter 2 (OCT2) in ciPTEC was evaluated in real-time using a perfusion system by confocal microscopy using 4-(4-(dimethylamino)styryl)-N-methylpyridinium iodide (ASP(+)) as a fluorescent substrate. Initial ASP(+) uptake was inhibited by a cationic uremic metabolites mixture and by the histamine H2-receptor antagonist, cimetidine. In conclusion, a 'living membrane' of renal epithelial cells on MicroPES HFM with demonstrated active organic cation transport was successfully established as a first step in BAK engineering.

  3. Lysozyme gelation in mixtures of tetramethylurea with protic solvents: Use of solvatochromic indicators to probe medium microstructure and solute solvent interactions

    NASA Astrophysics Data System (ADS)

    da Silva, Marcelo A.; El Seoud, Omar A.; Arêas, Elizabeth P. G.

    2007-09-01

    This work investigated the relationship between the structure of binary mixtures of tetramethylurea and protic solvents and their capacity to induce lysozyme gelation. In order to get an insight into the mechanism of gel formation, the solvatochromic behavior of zwitterionic probes, employed as simple models for the protein, was investigated. We studied two probes of similar p Ka's, but different hydrophobic character, namely 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate, RB, and 4-[2-(1-methylpyridinium-4-yl) ethenyl] phenolate, MC. The protic solvents used included water, 1-propanol and 2- n-butoxyethanol in the temperature range from 10 to 60 °C, and methanol, from 10 to 40 °C. In all cases, the dependence of the empirical solvent polarity parameter, ET, on mixture composition was non-ideal with negative deviation for TMU-water and positive deviation for TMU-organic solvent. For all binary mixtures, the deviation from linearity decreased as a function of increasing the temperature. In TMU/alcohol, the effect became more pronounced with increasing alcohol hydrophobicity.

  4. Human proximal tubule epithelial cells cultured on hollow fibers: living membranes that actively transport organic cations

    PubMed Central

    Jansen, J.; De Napoli, I. E; Fedecostante, M.; Schophuizen, C. M. S.; Chevtchik, N. V.; Wilmer, M. J.; van Asbeck, A. H.; Croes, H. J.; Pertijs, J. C.; Wetzels, J. F. M.; Hilbrands, L. B.; van den Heuvel, L. P.; Hoenderop, J. G.; Stamatialis, D.; Masereeuw, R.

    2015-01-01

    The bioartificial kidney (BAK) aims at improving dialysis by developing ‘living membranes’ for cells-aided removal of uremic metabolites. Here, unique human conditionally immortalized proximal tubule epithelial cell (ciPTEC) monolayers were cultured on biofunctionalized MicroPES (polyethersulfone) hollow fiber membranes (HFM) and functionally tested using microfluidics. Tight monolayer formation was demonstrated by abundant zonula occludens-1 (ZO-1) protein expression along the tight junctions of matured ciPTEC on HFM. A clear barrier function of the monolayer was confirmed by limited diffusion of FITC-inulin. The activity of the organic cation transporter 2 (OCT2) in ciPTEC was evaluated in real-time using a perfusion system by confocal microscopy using 4-(4-(dimethylamino)styryl)-N-methylpyridinium iodide (ASP+) as a fluorescent substrate. Initial ASP+ uptake was inhibited by a cationic uremic metabolites mixture and by the histamine H2-receptor antagonist, cimetidine. In conclusion, a ‘living membrane’ of renal epithelial cells on MicroPES HFM with demonstrated active organic cation transport was successfully established as a first step in BAK engineering. PMID:26567716

  5. Inorganic-organic hybrid materials based on keggin type polyoxometalates and organic polyammonium cations

    NASA Astrophysics Data System (ADS)

    Vasylyev, Maxym; Popovitz-Biro, Ronit; Shimon, Linda J. W.; Neumann, Ronny

    2003-08-01

    Co-crystallization of a tri-ammonium cation with short and somewhat flexible ‘arms', [N,N,N-tris[2-(dimethylamino)ethyl]-1,3,5-benzenetricarboxamide]3+, with a polyoxometalate trianion, PW12O403-, yielded an insoluble channeled or microporous structure. The polyoxometalate clusters are arranged in a layered and zig-zag fashion along the xy plane. Looking along the x-axis, channels of a dimension of ∼3.5×∼6.5 Å are observed. It was found that C-H⋯O bonds aided in determining the crystal packing by providing directionality to the anion-cation interaction. On the other hand the co-crystallization of a tetraammonium cation with an extended and rigid tetrahedral configuration, 1,3,5,7-tetrakis{4-[(E)-2(N-methylpyridinium-4-yl)vinyl]phenyl adamantane tetraiodide, with a polyoxometalate tetracation, SiW12O404-, yielded a lamellar structure with alternating layers with spacing of 16.6 Å of the inorganic-organic hybrid material.

  6. Effects of ionic liquids on membrane fusion and lipid aggregation of egg-PC liposomes.

    PubMed

    Galletti, Paola; Malferrari, Danilo; Samorì, Chiara; Sartor, Giorgio; Tagliavini, Emilio

    2015-01-01

    In this study we have explored the effects of different groups of ionic liquids (ILs) on membrane fusion. The ILs used contain different head groups: N-methylimidazolium, 3-methylpyridinium and N-methylpyrrolidinium; short alkyl or ether functionalized side chains (with one or two ethoxy functionalities), paired with chloride anion. These ILs have been compared with 1-dodecyl-3-methylimidazolium bromide as example of a highly lipophilic IL. The effect of ILs on membrane fusion was investigated through pyrene steady state fluorescence probing, using the IE factor and excimer/monomer ratio (IE/IM) as parameters. The ratio between the vibronic bands of pyrene (I1/I3 ratio) has been used to monitor the effect of ILs on the aggregation properties of egg-PC liposomes. The effect of different ILs' families was evident; the pyridinium ILs induced a greater extent of fusion than pyrrolidinium and imidazolium ILs having the same side chain. Marginal effect could be attributed to different anions. ILs with short alkyl chains were usually more effective than ether functionalized ones. The aggregation behaviors of ILs having dioxygenated chains have been measured in buffer solution.

  7. Design and Evaluation of Ionic Liquids as Novel CO2 Absorbents

    SciTech Connect

    Edward J. Maginn

    2006-01-12

    Progress from the fourth quarter 2005 activity on the project ''Design and Evaluation of Ionic Liquids as Novel CO{sub 2} Absorbents'' is provided. Major activities in three areas are reported: compound synthesis, property measurement and molecular modeling. Last quarter we reported the first ever experimental measurement of SO{sub 2} solubility in an ionic liquid. We showed that SO{sub 2} was very soluble in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([hmim][Tf{sub 2}N]). This quarter, we have measured SO{sub 2} solubility in two more ionic liquids: 1-hexyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide ([hmpy][Tf{sub 2}N]) and 1-hexyl-3-methylimidazolium lactate ([hmim][lactate]). As with [hmim][Tf{sub 2}N], we find very high solubility of SO{sub 2} in these ionic liquids, but the lactate compounds shows the highest affinity for SO{sub 2} at low pressure. CO{sub 2} solubility was measured in three new compounds: [boronium][Tf{sub 2}N], 1-hexyl-3-methylimidazolium acesulfumate ([hmim][ace]), and 1-hexyl-3-methylimidazolium saccharinate ([hmim][sac]). We find relatively poor solubility of CO{sub 2} in the latter two compounds, and solubility comparable to [hmim][Tf{sub 2}N] in the boronium compound. We also synthesized four new ionic liquids this quarter and continued refinement of our molecular simulation technique for measuring gas solubility.

  8. Diagnosis-Therapy Integrative Systems Based on Magnetic RNA Nanoflowers for Co-drug Delivery and Targeted Therapy.

    PubMed

    Guo, Yingshu; Li, Shuang; Wang, Yujie; Zhang, Shusheng

    2017-02-21

    This study was to develop a codrug delivery system for targeting cancer therapy based on magnetic RNA nanoflowers (RNA NF). Compared with traditional nucleic acid structure, convenient separation can be achieved by introducing magnetic nanoparticle (MNP) into RNA NF. Folic acid (FA) modified MNP/RNA NF (FA/MNP/RNA NF) was used as a targeting nanocarrier with excellent biocompatibility to overcome the nonselectivity of MNP/RNA NF. And then, anticancer drug doxorubicin (DOX) and photosensitizer 5, 10, 15, 20-tetrakis (1-methylpyridinium-4-yl) porphyrin (TMPyP4) binding with RNA NF were used as codrug cargo models. RNA NF was first used for codrug delivery. So, imaging fluorescent tags, target recognition element, and drug molecules were all assembled together on the surface of MNP/RNA NF. The experimental results suggested that the treatment efficacy of codrug delivery platform (FA/MNP/RNA NF/D/T) was better than single-drug delivery platform (FA/MNP/RNA NF/D). Besides, the FA/MNP/RNA NF was used as a probe for cancer cell detection. The limit of detection was 50 HeLa cells. In conclusion, the codrug delivery platform based on FA/MNP/RNA NF was a promising approach for the intracellular quantification of other biomolecules, as well as a diagnosis-therapy integrative system.

  9. Structural effects of ionic liquids on microalgal growth inhibition and microbial degradation.

    PubMed

    Pham, Thi Phuong Thuy; Cho, Chul-Woong; Yun, Yeoung-Sang

    2016-03-01

    In the present study, we investigated structural effects of various ionic liquids (ILs) on microalgal growth inhibition and microbial biodegradability. For this, we tested pyridinium- and pyrrolidinium-based ILs with various alkyl chain lengths and bromide anion, and compared the toxicological effects with log EC50 values of imidazolium-based IL with the same alkyl chains and anion from literature. Comparing determined EC50 values of cationic moieties with the same alkyl chain length, pyridinium-based ILs were found to be slightly more toxic towards the freshwater green alga, Pseudokirchneriella subcapitata, than a series of pyrrolidinium and imidazolium except to 1-octyl-3-methylimidazolium bromide. Concerning the biodegradation study of 12 ILs using the activated sludge microorganisms, the results showed that the pyridinium derivatives except to 1-propyl-3-methylpyridinium cation were degraded. Whereas in case of imidazolium- and pyrrolidinium-based compounds, only n-hexyl and n-octyl substituted cations were fully degraded but no significant biodegradation was observed for the short chains (three and four alkyl chains).

  10. In Vitro Anti-Inflammatory and Cytotoxic Effects of Aqueous Extracts from the Edible Sea Anemones Anemonia sulcata and Actinia equina.

    PubMed

    Silva, Tânia Costa; de Andrade, Paula Branquinho; Paiva-Martins, Fátima; Valentão, Patrícia; Pereira, David Micael

    2017-03-17

    Marine invertebrates have been attracting the attention of researchers for their application in nutrition, agriculture, and the pharmaceutical industry, among others. Concerning sea anemones (Cnidaria), little is known regarding their metabolic profiles and potential value as a source of pharmacologically-active agents. In this work, the chemical profiles of two species of sea anemones Actinia equina and Anemonia sulcata, were studied by high-performance liquid chromatography with diode-array detection (HPLC-DAD) and its impact upon immune and gastric cells was evaluated. In both species, the methylpyridinium alkaloid homarine was the major compound in aqueous extracts. The extracts were effective in reducing lipopolysaccharide (LPS)-induced levels of nitric oxide (NO) and intracellular reactive oxygen species (ROS) in a macrophage model of inflammation. Both the extracts and the alkaloid homarine were effective in inhibiting phospholipase A₂ (PLA₂), a pivotal enzyme in the initial steps of the inflammatory cascade. In order to mimic the oral consumption of these extracts; their effect upon human gastric cells was evaluated. While no caspase-9 activation was detected, the fact that the endoplasmic reticulum-resident caspase-4, and also caspase-3, were activated points to a non-classical mechanism of apoptosis in human gastric cells. This work provides new insights on the toxicity and biological potential of sea anemones increasingly present in human nutrition.

  11. Switching of emission of a styryl dye in cucurbit[7]uril: A comprehensive experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Manna, Anamika; Chakravorti, Sankar

    2015-04-01

    Intriguing colour change and change in fluorescence band of 2-(4-(dimethylamino)styryl)-1-methylpyridinium iodide from nonpolar to polar protic solvent, and also from molecular container cucurbit[7]uril environment to polar protic solvent has been reported here. This interesting colour change of this dye with respect to the medium makes this dye useful as a sensor. Change in spectral characteristics of DASPMI along with change of colour from orange to yellow with increasing polarity of medium is interpreted as due to negative solvatochromatism. Complexations of probe-cucurbit[7]uril (1:1 and 2:1) cause structural change of the probe molecule due to hydrogen bond interaction of cationic part of the dye with Cdbnd O group of cucurbit[7]uril and the colour change of the solution ensued. On addition of sodium chloride to the inclusion complex the dye is released from cucurbit[7]uril interior with colour of the solution reverted back. Theoretical results show that one carbon atom in the styryl part containing the positive charge gets too close to a carbon atom of cucurbit[7]uril to cause a phenomenal increase of dipole moment by 10X.

  12. Polymeric enzyme mimics: catalytic activity of ribose-containing polymers for a phosphate substrate.

    PubMed

    Han, Man Jung; Yoo, Kyung Soo; Kim, Young Heui; Chang, Ji Young

    2003-07-07

    The polymers containing ribose rings: poly(5'-acrylamido-5'-deoxy-1',2'-O-isopropylidene-alpha-D-ribose) (11), poly(5'-acrylamido-5'-deoxy-alpha-D-ribose) (12) and poly(5'-acrylamido-5'-deoxy-1'-O-methyl-D-ribose) (13) were prepared as enzyme mimics. Polymers 12 and 13 with free vic-cis-diol groups catalyzed the hydrolysis of phosphodiester (ethyl p-nitrophenyl phosphate and N-methylpyridinium 4-tert-butylcatechol cyclic phosphate) and phosphomonoester substrates with a rate acceleration of 10 approximately equal to 10(3) compared with the uncatalyzed reaction. They also catalyzed the reverse reactions, i.e., the esterification of phosphomonoester to phosphodiester and the phosphorylation of alcohols with phosphate ions. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles. The catalytic activity was negligible for polymer 11 where vic-cis-diol groups were blocked with isopropylidene groups. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles.

  13. Effects of micelles and vesicles on the oximolysis of p-nitrophenyl diphenyl phosphate: A model system for surfactant-based skin-defensive formulations against organophosphates.

    PubMed

    Gonçalves, Larissa Martins; Kobayakawa, Talita Guedes; Zanette, Dino; Chaimovich, Hernan; Cuccovia, Iolanda Midea

    2009-03-01

    The rates of oximolysis of p-nitrophenyl diphenyl phosphate (PNPDPP) by Acetophenoxime; 10-phenyl-10-hydroxyiminodecanoic acid; 4-(9-carboxynonanyl)-1-(9-carboxy-1-hydroyiminononanyl) benzene; 1-dodecyl-2-[(hydroxyimino)methyl]-pyridinium chloride (IV) and N-methylpyridinium-2-aldoxime chloride were determined in micelles of N-hexadecyl-N,N,N-trimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethylammonium propanesulfonate and dioctadecyldimethylammonium chloride (DODAC) vesicles. The effects of CTAC micelles and DODAC vesicles on the rates of oxymolysis of O,O-Diethyl O-(4-nitrophenyl) phosphate (paraoxon) by oxime IV were also determined. Analysis of micellar and vesicular effects on oximolysis of PNPDPP, using pseudophase or pseudophase with explicit consideration of ion exchange models, required the determination of the aggregate's effects on the pK(a) of oximes and on the rates of PNPDPP hydrolysis. All aggregates increased the rate of oximolysis of PNPDPP and the results were analyzed quantitatively. In particular, DODAC vesicles catalyzed the reaction and increased the rate of oximolysis of PNPDPP by IV several million fold at pH's compatible with pharmaceutical formulations. The rate increase produced by DODAC vesicles on the rate of oximolysis paraoxon by IV demonstrates the pharmaceutical potential of this system, since the substrate is used as an agricultural defensive agent and the surfactant is extensively employed in cosmetic formulations.

  14. APP+, a fluorescent analogue of the neurotoxin MPP+, is a marker of catecholamine neurons in brain tissue, but not a fluorescent false neurotransmitter.

    PubMed

    Karpowicz, Richard J; Dunn, Matthew; Sulzer, David; Sames, Dalibor

    2013-05-15

    We have previously introduced fluorescent false neurotransmitters (FFNs) as optical reporters that enable visualization of individual dopaminergic presynaptic terminals and their activity in the brain. In this context, we examined the fluorescent pyridinium dye 4-(4-dimethylamino)phenyl-1-methylpyridinium (APP+), a fluorescent analogue of the dopaminergic neurotoxin MPP+, in acute mouse brain tissue. APP+ is a substrate for the dopamine transporter (DAT), norepinephrine transporter (NET), and serotonin transporter (SERT), and as such represented a candidate for the development of new FFN probes. Here we report that APP+ labels cell bodies of catecholaminergic neurons in the midbrain in a DAT- and NET-dependent manner, as well as fine dopaminergic axonal processes in the dorsal striatum. APP+ destaining from presynaptic terminals in the dorsal striatum was also examined under the conditions inducing depolarization and exocytotic neurotransmitter release. Application of KCl led to a small but significant degree of destaining (approximately 15% compared to control), which stands in contrast to a nearly complete destaining of the new generation FFN agent, FFN102. Electrical stimulation of brain slices at 10 Hz afforded no significant change in the APP+ signal. These results indicate that the majority of the APP+ signal in axonal processes originates from labeled organelles including mitochondria, whereas only a minor component of the APP+ signal represents the releasable synaptic vesicular pool. These results also show that APP+ may serve as a useful probe for identifying catecholaminergic innervations in the brain, although it is a poor candidate for the development of FFNs.

  15. A dark brown roast coffee blend is less effective at stimulating gastric acid secretion in healthy volunteers compared to a medium roast market blend.

    PubMed

    Rubach, Malte; Lang, Roman; Bytof, Gerhard; Stiebitz, Herbert; Lantz, Ingo; Hofmann, Thomas; Somoza, Veronika

    2014-06-01

    Coffee consumption sometimes is associated with symptoms of stomach discomfort. This work aimed to elucidate whether two coffee beverages, containing similar amounts of caffeine, but differing in their concentrations of (β) N-alkanoyl-5-hydroxytryptamides (C5HTs), chlorogenic acids (CGAs), trigonelline, and N-methylpyridinium (N-MP) have different effects on gastric acid secretion in healthy volunteers. The intragastric pH after administration of bicarbonate with/without 200 mL of a coffee beverage prepared from a market blend or dark roast blend was analyzed in nine healthy volunteers. Coffee beverages were analyzed for their contents of C5HT, N-MP, trigonelline, CGAs, and caffeine using HPLC-DAD and HPLC-MS/MS. Chemical analysis revealed higher concentrations of N-MP for the dark brown blend (87 mg/L) compared to the market blend coffee (29 mg/L), whereas concentrations of C5HT (0.012 versus 0.343 mg/L), CGAs (323 versus 1126 mg/L), and trigonelline (119 versus 343 mg/L) were lower, and caffeine concentrations were similar (607 versus 674 mg/mL). Gastric acid secretion was less effectively stimulated after administration of the dark roast blend coffee compared to the market blend. Future studies are warranted to verify whether a high ratio of N-MP to C5HT and CGAs is beneficial for reducing coffee-associated gastric acid secretion.

  16. Study of surface interactions of ionic liquids with aluminium alloys in corrosion and erosion corrosion processes

    NASA Astrophysics Data System (ADS)

    Bermúdez, María-Dolores; Jiménez, Ana-Eva; Martínez-Nicolás, Ginés

    2007-06-01

    Surface interactions of alkylimidazolium ionic liquids (ILs) with aluminium alloy Al 2011 have been studied by immersion tests in seven neat ILs [1- n-alkyl-3-methylimidazolium X - (X = BF 4; n = 2 (IL1), 6 (IL2), 8 (IL3). X = CF 3SO 3; n = 2 (IL4). X = (4-CH 3C 6H 4SO 3); n = 2 (IL5). X = PF 6; n = 6 (IL6)] and 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide (IL7)]. Immersion tests for Al 2011 have also been carried out in 1 wt.% and 5 wt.% solutions of 1-ethyl,3-methylimidazolium tetrafluoroborate (IL1) in water. No corrosion of Al 2011 by neat ILs is observed. The highest corrosion rate for Al 2011 in water is observed in the presence of a 5 wt.% IL1 due to hydrolysis of the anion with hydrogen evolution and formation of aluminium fluoride. Erosion-corrosion processes have been studied for three aluminium alloys (Al 2011, Al 6061 and Al 7075) in a 90 wt.% IL1 solution in water in the presence of α-alumina particles. The erosion-corrosion rates are around 0.2 mm/year or lower, and increase with increasing copper content to give a corrosion resistance order of Al 6061 > Al 7075 > Al 2011. Results are discussed on the basis of scanning electron microscopy (SEM) observations, energy dispersive spectroscopy (EDS) analysis, X-ray diffraction (XRD) patterns and X-ray photoelectron spectroscopy (XPS) determinations.

  17. Hydrogels containing porphyrin-loaded nanoparticles for topical photodynamic applications.

    PubMed

    González-Delgado, José A; Castro, Pedro M; Machado, Alexandra; Araújo, Francisca; Rodrigues, Francisca; Korsak, Bárbara; Ferreira, Marta; Tomé, João P C; Sarmento, Bruno

    2016-08-20

    5,10,15,20-tetrakis(1-methylpyridinium-4-yl)-porphyrin tetra-iodide (TMPyP), a potent water-soluble photosensitizer (PS) used in antimicrobial applications, was encapsulated into poly(lactic-co-glycolic acid) (PLGA) nanoparticles (TMPyP-PLGA) for topical delivery purposes. Nanoparticles resulted in a mean particle size around 130nm, narrow polydispersity index (PdI), spherical morphology and association efficiency up to 93%. Free TMPyP and TMPyP-PLGA nanoparticles were incorporated into Carbopol(®) hydrogels, resulting in controlled TMPyP release of about 60% and 20% after 4.5h, respectively. Critical properties such as appearance, clarity, viscosity and pH were maintained over time, as hydrogels were stable during 6 months at 4°C, 25°C/60% RH and 40°C/75% RH. For photodynamic applications, the photoproduction of singlet oxygen from these hydrogels was quite efficient being both formulations very photostable after 20min. No TMPyP permeation through pig ear skin was observed after 24h, and histological assays did not show relevant damages in surrounding tissues. All these excellent characteristics make them promising platforms for photodynamic applications through topical clinical use. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Therapeutic manipulation of peroxynitrite attenuates the development of opiate-induced antinociceptive tolerance in mice

    PubMed Central

    Muscoli, Carolina; Cuzzocrea, Salvatore; Ndengele, Michael M.; Mollace, Vincenzo; Porreca, Frank; Fabrizi, Francesca; Esposito, Emanuela; Masini, Emanuela; Matuschak, George M.; Salvemini, Daniela

    2007-01-01

    Severe pain syndromes reduce quality of life in patients with inflammatory and neoplastic diseases, often because chronic opiate therapy results in reduced analgesic effectiveness, or tolerance, leading to escalating doses and distressing side effects. The mechanisms leading to tolerance are poorly understood. Our studies revealed that development of antinociceptive tolerance to repeated doses of morphine in mice was consistently associated with the appearance of several tyrosine-nitrated proteins in the dorsal horn of the spinal cord, including the mitochondrial isoform of superoxide (O2–) dismutase, the glutamate transporter GLT-1, and the enzyme glutamine synthase. Furthermore, antinociceptive tolerance was associated with increased formation of several proinflammatory cytokines, oxidative DNA damage, and activation of the nuclear factor poly(ADP-ribose) polymerase. Inhibition of NO synthesis or removal of O2– blocked these biochemical changes and inhibited the development of tolerance, pointing to peroxynitrite (ONOO–), the product of the interaction between O2– and NO, as a signaling mediator in this setting. Indeed, coadministration of morphine with the ONOO– decomposition catalyst, Fe(III) 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin, blocked protein nitration, attenuated the observed biochemical changes, and prevented the development of tolerance in a dose-dependent manner. Collectively, these data suggest a causal role for ONOO– in pathways culminating in antinociceptive tolerance to opiates. Peroxynitrite (ONOO–) decomposition catalysts may have therapeutic potential as adjuncts to opiates in relieving suffering from chronic pain. PMID:17975673

  19. Consumption of a dark roast coffee decreases the level of spontaneous DNA strand breaks: a randomized controlled trial.

    PubMed

    Bakuradze, T; Lang, R; Hofmann, T; Eisenbrand, G; Schipp, D; Galan, J; Richling, E

    2015-02-01

    Coffee consumption has been reported to decrease oxidative damage in peripheral white blood cells (WBC). However, effects on the level of spontaneous DNA strand breaks, a well established marker of health risk, have not been specifically reported yet. We analyzed the impact of consuming a dark roast coffee blend on the level of spontaneous DNA strand breaks. Healthy men (n = 84) were randomized to consume daily for 4 weeks either 750 ml of fresh coffee brew or 750 ml of water, subsequent to a run in washout phase of 4 weeks. The study coffee was a blend providing high amounts of both caffeoylquinic acids (10.18 ± 0.33 mg/g) and the roast product N-methylpyridinium (1.10 ± 0.05 mg/g). Before and after the coffee/water consumption phase, spontaneous strand breaks were determined by comet assay. At baseline, both groups exhibited a similar level of spontaneous DNA strand breaks. In the intervention phase, spontaneous DNA strand breaks slightly increased in the control (water only) group whereas they significantly decreased in the coffee group, leading to a 27% difference within both arms (p = 0.0002). Food frequency questionnaires indicated no differences in the overall diet between groups, and mean body weight during the intervention phases remained stable. The consumption of the study coffee substantially lowered the level of spontaneous DNA strand breaks in WBC. We conclude that regular coffee consumption contributes to DNA integrity.

  20. Cardiometabolic effects of two coffee blends differing in content for major constituents in overweight adults: a randomized controlled trial.

    PubMed

    Kempf, Kerstin; Kolb, Hubert; Gärtner, Babette; Bytof, Gerhard; Stiebitz, Herbert; Lantz, Ingo; Lang, Roman; Hofmann, Thomas; Martin, Stephan

    2015-08-01

    The hypothesis was tested that coffee types differing in content of major constituents also differ with regard to cardiometabolic effects. Overweight persons (n = 118) were randomized to consume a dark roast [rich in N-methylpyridinium (NMP)] or medium roast (rich in caffeoylquinic acids, trigonelline) coffee blend for 3 months, after a washout period of 4 weeks. Before and after the intervention period, body weight and 15 further general and biochemical parameters were determined. Participants consumed an average of 4-5 cups per day. Mean body weight, body mass index and waist circumference did not change during the coffee consumption phase in either of the study groups. Systolic blood pressure decreased in the dark roast coffee group only (p < 0.05). High-density lipoprotein cholesterol levels increased in the medium roast coffee group only, and triglyceride levels increased in the dark roast coffee group only. Glucoregulation and insulin levels were not affected, although there was a small increase of hemoglobin A1c values in both groups. An increase of adiponectin levels occurred in the medium roast coffee group only and was negatively associated with NMP concentrations. Differences did not remain statistically significant after correction for multiple testing. Medium and dark roast coffee blends exert small but possibly relevant different cardiometabolic effects. Further studies of health outcomes in relation to coffee constituents seem warranted.

  1. Nonaqueous CE using contactless conductivity detection and ionic liquids as BGEs in ACN.

    PubMed

    Borissova, Maria; Gorbatsova, Jelena; Ebber, Arkadi; Kaljurand, Mihkel; Koel, Mihkel; Vaher, Merike

    2007-10-01

    N,N'-Alkylmethylimidazolium cations have been separated in NACE when one of the N,N'-dialkylimidazolium salts (ionic liquids (ILs)) was used as an electrolyte additive to the organic solvent separation medium. The separated species were 1-methyl-, 1-ethyl-, 1-butyl-, 1-octyl-, 1-decyl-3-methylimidazolium and N-butyl-3-methylpyridinium cations and BGE composed of 1-ethyl-3-methylimidazolium ethylsulfate or 1-butyl-3-methylimidazolium trifluoroacetate [BMIm][FAcO] (A6; B2) diluted in ACN. It was demonstrated that contactless conductivity detection (CCD) may be applied to monitoring the separation process in nonaqueous separation media, allowing to use the UV light-absorbing imidazolium-based electrolyte additives. There could be marked three concentration regions of added ILs; at first ionic strength of BGE below 1-2 mM, and then the actual electrophoretic mobility of analytes rises from 0. At concentrations above 1-2 mM, the added IL facilitated separation. In concentration region of 1-20 mM, the actual electrophoretic mobility of analyzed imidazolium cations was increasing with decrease in separation medium ionic strength. At higher concentrations of BGE (above 30 mM), the conductivity of the separation media became too high for this detector. Some organic dyes were also successfully separated and detected by contactless conductivity detector in a 20 mM A6 separation electrolyte in ACN.

  2. Electronic resonance and local field effects on the nonlinear optical activity of H-aggregate-forming stilbazolium amphiphiles

    SciTech Connect

    Xu, Z.; Lu, W.; Bohn, P.W.

    1995-05-04

    Stilbazolium dyes, which form H-aggregates upon condensation at the air-water interface, typically display nonlinear optical (NLO) activity far below what would be predicted on the basis of their large intrinsic molecular hyperpolarizability, {beta}. Three separate hypothesis have been put forward to explain this observation: structural inversion to produce a centrosymmetric head-to-tail structure, local field effects, which act to reduce the effective magnitude of the nonlinear driving field, and changes in electronic structure, which shift the electronic resonance frequencies for the aggregates. Investigation of the linear and nonlinear spectroscopy of the dye 4-(4-dihexadecylaminostyryl)-N-methylpyridinium iodide were performed on a series of samples in which the aggregation state of the structure was changed systematically, but without changing the composition of the film. These experiments show that, for this particular dye, changes in electronic structure upon aggregation comprise the most important factor in determining the reduction in second harmonic generation (SHG) efficiency of the aggregate. 23 refs., 4 figs.

  3. Probing Zeolite Crystal Architecture and Structural Imperfections using Differently Sized Fluorescent Organic Probe Molecules

    PubMed Central

    Hendriks, Frank C.; Schmidt, Joel E.; Rombouts, Jeroen A.; Lammertsma, Koop; Bruijnincx, Pieter C. A.

    2017-01-01

    Abstract A micro‐spectroscopic method has been developed to probe the accessibility of zeolite crystals using a series of fluorescent 4‐(4‐diethylaminostyryl)‐1‐methylpyridinium iodide (DAMPI) probes of increasing molecular size. Staining large zeolite crystals with MFI (ZSM‐5) topology and subsequent mapping of the resulting fluorescence using confocal fluorescence microscopy reveal differences in structural integrity: the 90° intergrowth sections of MFI crystals are prone to develop structural imperfections, which act as entrance routes for the probes into the zeolite crystal. Polarization‐dependent measurements provide evidence for the probe molecule's alignment within the MFI zeolite pore system. The developed method was extended to BEA (Beta) crystals, showing that the previously observed hourglass pattern is a general feature of BEA crystals with this morphology. Furthermore, the probes can accurately identify at which crystal faces of BEA straight or sinusoidal pores open to the surface. The results show this method can spatially resolve the architecture‐dependent internal pore structure of microporous materials, which is difficult to assess using other characterization techniques such as X‐ray diffraction. PMID:28217845

  4. Silica Aerogels Doped with Ru(II) Tris 1,l0-Phenanthro1ine)-Electron Acceptor Dyads: Improving the Dynamic Range, Sensitivity and Response Time of Sol-Gel Based Oxygen Sensors

    NASA Technical Reports Server (NTRS)

    Kevebtusm Bucgikas; Rawashdeh, Abdel M.; Elder, Ian A.; Yang, Jinhua; Dass, Amala; Sotiriou-Leventis, Chariklia

    2005-01-01

    Complexes 1 and 2 were characterized in fluid and frozen solution and as dopants of silica aerogels. The intramolecular quenching efficiency of pendant 4-benzoyl-N-methylpyridinium group (4BzPy) is solvent dependent: emission is quenched completely in acetonitrile but not in alcohols. On the other hand, N-benzyl-N'-methylviologen (BzMeV) quenches the emission in all solvents completely. The differences are traced electrochemically to a stronger solvation effect by the alcohol in the case of 1. In fiozen matrices or absorbed on the surfaces of silica aerogel, both 1 and 2 are photoluminescent. The lack of quenching has been traced to the environmental rigidity. When doped aerogels are cooled to 77K, the emission shifts to the blue and its intensity increases in analogy to what is observed with Ru(II) complexes in media undergoing fluid-to-rigid transition. The photoluminescence of 1 and 2 from the aerogel is quenched by oxygen diffusing through the pores. In the presence of oxygen, aerogels doped with 1 can modulate their emission over a wider dynamic range than aerogels doped with 2, and both are more sensitive than aerogels doped with Ru(II) tris(1,l0- phenanthroline). In contrast to frozen solutions, the luminescent moieties in the bulk of aerogels kept at 77K are still accessible, leading to more sensitive platforms for oxygen sensors than other ambient temperature configurations.

  5. Optical limiting effect in a two-photon absorption dye doped solid matrix

    NASA Astrophysics Data System (ADS)

    He, Guang S.; Bhawalkar, Jayant D.; Zhao, Chan F.; Prasad, Paras N.

    1995-10-01

    We recently reported a new lasing dye, trans-4-[p-(N-ethyl-N-hydroxylethylamino)styryl]-N-methylpyridinium tetraphenylborate (ASPT), which has also been shown to possess a strong two-photon absorption (TPA) and subsequent frequency upconversion fluorescence behavior when excited with near infrared laser radiation. Based on the TPA mechanism, a highly efficient optical limiting performance has been demonstrated in a 2 cm long ASPT-doped epoxy rod pumped with 1.06 μm Q-switched laser pulses at 50-250 MW/cm2 intensity levels. The measured nonlinear absorption coefficient reached 6 cm/GW for the tested sample of dopant concentration d0=4×10-3 M/L. The molecular TPA cross section of ASPT in the epoxy matrix is estimated as σ2=2.5×10-18 cm4/GW or σ2'=4.7×10-46 cm4/photon/s, respectively. Two-photon pumped cavity lasing is also observed in an ASPT-doped polymer rod.

  6. Effect of MPTP on primate chromaffin cells in vitro: relevance for adrenal medullary cell transplantation.

    PubMed

    Notter, M F; Kaniuki, M; Felten, S Y; Hansen, J T; Gash, D M

    1991-01-01

    Primate adrenal medullary cells were exposed to l-methyl-4-phenyl-l,2,3,6-tetrahydropyridine (MPTP) in vitro to examine the effect of this neurotoxic agent on chromaffin cells. Chromaffin cells from monkey and humans were cultured in the presence of 100 ng/ml nerve growth factor for 1 week and then exposed to 150 μM MPTP or its active metabolite methylpyridinium ion (MPP+) for an additional week. Cells which had extended neurites in the presence of NGF showed no morphological effect in response to MPTP or MPP+ at the light microscopic level. However, there was a significant loss in catecholamines as seen by histofluorescence and high performance liquid chromotography (HPLC). Electron microscopy revealed a depletion in dense-core vesicles in chromaffin cells after chronic exposure to MPTP while the mitochondria appeared similar to those observed in control cells. Replacement of MPTP medium with standard medium stimulated restoration of catecholamine histofluorescence after 7 days. An acute 15 min pretreatment of chromaffin cells with MPTP or MPP+ induced secretion of catecholamines over a 1 h pulse, with MPP+ producing the maximum and more rapid secretion as determined by HPLC. These data indicate that MPTP induces a dramatic loss in catecholamines in primate chromaffin cells in vitro after both acute and chronic exposures; however, removal of the toxic agent permits restoration of catecholamines without permanent effect on the integrity of these cells.

  7. Toluidine blue-O is a Nissl bright-field counterstain for lipophilic fluorescent tracers Di-ASP, DiI and DiO.

    PubMed

    Chelvanayagam, D K; Beazley, L D

    1997-03-01

    The stain toluidine blue-O (tol blue), applied to sections of neural tissue, is shown to be compatible with the vivid fluorescent lipophilic neural tracers 4-(4-dihexadecylaminostyryl)-N-methylpyridinium iodide (Di-ASP), 3,3'-dioctadecyloxacarbocyanine perchlorate (DiO) and 1,1'-dioctadecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate (DiI). As with other Nissl stains, toluidine blue-O fluoresces in the red end of the spectrum but such fluorescence quenches upon binding with tissue. Moreover, progressive staining occurs at concentrations low enough to minimise any background fluorescence attributable to non-specific residence of the stain. The bright yellow Di-ASP and vivid green DiO signals are spectrally removed from the red fluorescence of toluidine blue-O. With toluidine blue-O counterstaining, Di-ASP generally offers contrast superior to that with DiI, however, the latter is improved by viewing in a polarised green bright field. Visible Di-ASP emission, although broad, peaks at a more film-sensitive region of the spectrum than that for DiI, thus reducing the photographic exposure required.

  8. Real-time, Spatially Resolved Analysis of Serotonin Transporter Activity And Regulation Using the Fluorescent Substrate, ASP+

    PubMed Central

    Oz, M.; Libby, T.; Kivell, B.; Jaligam, V.; Ramamoorthy, S.; Shippenberg, T.S.

    2010-01-01

    The serotonin transporter (SERT) mediates clearance of serotonin from the synapse, thereby, regulating extracellular serotonin concentrations. Radioligand uptake techniques are typically used to assess SERT function in tissue and heterologous expression systems. The need for sufficient protein in samples, however, requires use of homogenate preparations, potentially masking effects limited to specific cell populations. 4-(4-(dimethylamino)-styryl)-N-methylpyridinium (ASP+) is a fluorescent monoamine transporter substrate that has been used for real-time monitoring of dopamine and norepinephrine transporter function in single cells. The present live cell imaging studies examine the utility of ASP+ for quantifying hSERT function in HEK-293 and neuroblastoma cells. We show rapid membrane binding and intracellular ASP+ accumulation in hSERT expressing cells. Accumulation is saturable; dependent on temperature and the presence of sodium and chloride in the media, and attenuated by serotonin. Acute or prolonged exposure of cells to serotonin re-uptake inhibitors produces a concentration-dependent decrease in accumulation. Similar effects are produced by PKC activation whereas p38MAPK activation increases ASP+ accumulation. These data demonstrate the validity of ASP+ as a probe for monitoring SERT function in living cells. Alterations in SERT binding and uptake can be quantified in the same cell and use of a within cell design permits analysis of time-related alterations in SERT function. PMID:20524964

  9. SDS-PAGE and IR spectroscopy to evaluate modifications in the viral protein profile induced by a cationic porphyrinic photosensitizer.

    PubMed

    Costa, Liliana; Esteves, Ana Cristina; Correia, António; Moreirinha, Catarina; Delgadillo, Ivonne; Cunha, Ângela; Neves, Maria G P S; Faustino, Maria A F; Almeida, Adelaide

    2014-12-01

    Reactive oxygen species can be responsible for microbial photodynamic inactivation due to its toxic effects, which include severe damage to proteins, lipids and nucleic acids. In this study, the photo-oxidative modifications of the proteins of a non-enveloped T4-like bacteriophage, induced by the cationic porphyrin 5,10,15-tris(1-methylpyridinium-4-yl)-20-(pentafluorophenyl)porphyrin tri-iodide were evaluated. Two methods were used: sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) and infrared spectroscopy. SDS-PAGE analysis showed that the phage protein profile was considerably altered after photodynamic treatment. Seven protein bands putatively corresponding to capsid and tail tube proteins were attenuated and two other were enhanced. Infrared spectroscopy confirmed the time-dependent alteration on the phage protein profile detected by SDS-PAGE, indicative of a response to oxidative damage. Infrared analysis showed to be a promising and rapid screening approach for the analysis of the modifications induced on viral proteins by photosensitization. In fact, one single infrared spectrum can highlight the changes induced to all viral molecular structures, overcoming the delays and complex protocols of the conventional methods, in a much simple and cost effective way.

  10. Introduction of Red-Green-Blue Fluorescent Dyes into a Metal-Organic Framework for Tunable White Light Emission.

    PubMed

    Wen, Yuehong; Sheng, Tianlu; Zhu, Xiaoquan; Zhuo, Chao; Su, Shaodong; Li, Haoran; Hu, Shengmin; Zhu, Qi-Long; Wu, Xintao

    2017-10-01

    The unique features of the metal-organic frameworks (MOFs), including ultrahigh porosities and surface areas, tunable pores, endow the MOFs with special utilizations as host matrices. In this work, various neutral and ionic guest dye molecules, such as fluorescent brighteners, coumarin derivatives, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM), and 4-(p-dimethylaminostyryl)-1-methylpyridinium (DSM), are encapsulated in a neutral MOF, yielding novel blue-, green-, and red-phosphors, respectively. Furthermore, this study introduces the red-, green-, and blue-emitting dyes into a MOF together for the first time, producing white-light materials with nearly ideal Commission International ed'Eclairage (CIE) coordinates, high color-rendering index values (up to 92%) and quantum yields (up to 26%), and moderate correlated color temperature values. The white light is tunable by changing the content or type of the three dye guests, or the excitation wavelength. Significantly, the introduction of blue-emitting guests in the methodology makes the available MOF host more extensive, and the final white-light output more tunable and high-quality. Such strategy can be widely adopted to design and prepare white-light-emitting materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. On the interfacial behavior of ionic liquids: surface tensions and contact angles.

    PubMed

    Restolho, José; Mata, José L; Saramago, Benilde

    2009-12-01

    In this work the liquid/vapour and the solid/liquid interfaces of a series of ionic liquids: 1-ethyl-3-methylpyridinium ethyl sulfate, [EMPy][EtSO4], 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIM][EtSO4], 1-ethanol-3-methylimidazolium tetrafluoroborate, [C2OHMIM][BF4], 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4], and 1-octyl-3-methylimidazolium tetrafluoroborate, [OMIM][BF4], were investigated. The surface tension was measured in a wide temperature range, (298-453) K. The contact angles were determined on substrates of different polarities. Both on the polar (glass) and the non-polar substrates ((poly-(tetrafluoroethylene) and poly-(ethylene)), the liquids with maximum and minimum surface tensions lead, respectively, to the highest and the lowest contact angles. The dispersive, gamma(L)(d), and non-dispersive, gamma(L)(nd), components of the liquid surface tension, gamma(L), were calculated from the contact angles on the non-polar substrates using the Fowkes approach. The polarity fraction, gamma(L)(nd)/gamma(L), was compared with the polarity parameter, k, obtained from the fitting of the surface tension vs. temperature data to the Eötvös equation. Good agreement was found for the extreme cases: [OMIM][BF4] exhibits the lowest polarity and [BMIM][BF4], the highest. When compared with the polarity fractions of standard liquids considered as "polar" liquids, the ionic liquids studied may be considered as moderately polar.

  12. The co-occurrence of two pyridine alkaloids, mimosine and trigonelline, in Leucaena leucocephala.

    PubMed

    Ogita, Shinjiro; Kato, Misako; Watanabe, Shin; Ashihara, Hiroshi

    2014-01-01

    Leucaena leucocephala is a nitrogen-fixing tropical leguminous tree that produces two pyridine alkaloids, i. e. mimosine [beta-(3-hydroxy-4-pyridon-1-yl)-L-alanine] and trigonelline (1-methylpyridinium-3-carboxylate). Mimosine has been detected in leaves, flowers, pods, seeds, and roots, and it is one of the principal non-protein amino acids that occurs in all organs. Asparagine was the most abundant amino acid in flowers. The mimosine content varied from 3.3 micromol/g fresh weight (FW) in developing flowers to 171 micromol/g FW in mature seeds. Trigonelline was also detected in leaves, flowers, pods, and seeds, but not roots. The trigonelline content was lower than that of mimosine in all organs. It varied from 0.12 micromol/g FW in developing seeds to 2.6 micromol/g FW in mature seeds. [2-14C]Nicotinic acid supplied to the developing seeds was incorporated into trigonelline but not mimosine. This indicates that the pyridine and dihydroxypyridine structures of these two alkaloids are derived from distinct precursors. The physiological functions of mimosine and trigonelline are discussed briefly.

  13. Optical response of mesoporous synthetic opals to the adsorption of chemical species.

    PubMed

    Yamada, Yuri; Nakamura, Tadashi; Yano, Kazuhisa

    2008-03-18

    We have demonstrated the fabrication of a colloidal crystalline array (synthetic opal) from monodispersed mesoporous silica spheres (MMSS) and the control of its optical response simply by changing the amount of benzene vapor adsorbed into the pores of MMSS. It was revealed that the refractive index of the colloidal crystal of MMSS showed an 11.7% increase by taking advantage of benzene adsorption, and thereby, the structural color changed reversibly. We also conducted the same measurement on silica spheres without mesopores and observed no change in the refractive index or the structural color. This optical response gives rise to the possibility of using MMSS colloidal crystals not only for controlling light reflection but also as sensing devices based on color change due to vapor adsorption. We have also incorporated an organic dye, the porphyrin derivative alpha,beta,chi,delta,-tetrakis(1-methylpyridinium-4-yl)porphyrin rho-toluenesulfonate (TMPyP), into the pores of MMSS. By adopting an electrophoretic deposition process in ethanol, periodic arrays fabricated from TMPyP-MMSS conjugates with absolute zeta-potentials near zero were obtained. The Bragg diffraction peak of the colloidal crystalline array shifted to longer wavelengths due to an increase in the refractive index with increasing amounts of TMPyP adsorbed in the pores. The current work demonstrates the new possibility of creating colloidal crystals from MMSS with mesopores filled with various kinds of adsorbates to control the optical response effectively.

  14. Intrinsic Bioenergetic Properties and Stress Sensitivity of Dopaminergic Synaptosomes

    PubMed Central

    Choi, Sung W.; Gerencser, Akos A.; Lee, Donna W.; Rajagopalan, Subramanian; Nicholls, David G.; Andersen, Julie K.; Brand, Martin D.

    2011-01-01

    Dopaminergic neurons of the substantia nigra pars compacta are defective in Parkinson’s disease, but the specificity of this dysfunction is not understood. One hypothesis is that mitochondrial bioenergetic capacity is intrinsically lower in striatal dopaminergic presynaptic nerve varicosities, making them unusually susceptible to inhibition of electron transport by oxidative damage. To test this hypothesis, we separated isolated synaptosomes bearing dopamine transporters using immunomagnetic beads and compared their respiration with that of the residual nondopaminergic synaptosomes. As predicted, dopaminergic synaptosomes from striatum had lower respiratory rates. However, so did dopaminergic synaptosomes from cortex, indicating a lack of the predicted striatal specificity. We used fluorescent probes to analyze the bioenergetic competence of individual synaptosomes in the two fractions. The respiratory differences became nonsignificant when respiration rates were normalized to the number of respiration-competent synaptosomes, suggesting that differences reflected the quality of the different fractions. To circumvent damage induced by synaptosomal separation, we monitored membrane potentials in whole unseparated single synaptosomes using fluorescent imaging, and then identified the dopaminergic subpopulation using a fluorescent dopamine transporter substrate (ASP+ [4-(4-diethylaminostyryl)-N-methylpyridinium iodide]). The capacity of dopaminergic and nondopaminergic synaptosomes to maintain plasma membrane and mitochondrial membrane potential under several stresses did not differ. In addition, this capacity did not decline in either subpopulation with age, a risk factor for Parkinson’s disease. We conclude that the intrinsic bioenergetic capacities of dopaminergic and nondopaminergic presynaptic synaptosomes from mice do not differ. PMID:21430153

  15. The Alkaline Hydrolysis of Sulfonate Esters: Challenges in Interpreting Experimental and Theoretical Data

    PubMed Central

    2013-01-01

    Sulfonate ester hydrolysis has been the subject of recent debate, with experimental evidence interpreted in terms of both stepwise and concerted mechanisms. In particular, a recent study of the alkaline hydrolysis of a series of benzene arylsulfonates (Babtie et al., Org. Biomol. Chem.10, 2012, 8095) presented a nonlinear Brønsted plot, which was explained in terms of a change from a stepwise mechanism involving a pentavalent intermediate for poorer leaving groups to a fully concerted mechanism for good leaving groups and supported by a theoretical study. In the present work, we have performed a detailed computational study of the hydrolysis of these compounds and find no computational evidence for a thermodynamically stable intermediate for any of these compounds. Additionally, we have extended the experimental data to include pyridine-3-yl benzene sulfonate and its N-oxide and N-methylpyridinium derivatives. Inclusion of these compounds converts the Brønsted plot to a moderately scattered but linear correlation and gives a very good Hammett correlation. These data suggest a concerted pathway for this reaction that proceeds via an early transition state with little bond cleavage to the leaving group, highlighting the care that needs to be taken with the interpretation of experimental and especially theoretical data. PMID:24279349

  16. Investigation of anti-inflammatory and anti-proliferative activities promoted by photoactivated cationic porphyrin.

    PubMed

    Carrenho, Luise Zozula Blind; Moreira, Camila Guimarães; Vandresen, Camila Chevonica; Gomes Junior, Rubens; Gonçalves, Alan Guilherme; Barreira, Sandra Mara Woranovicz; Noseda, Miguel Daniel; Duarte, Maria Eugênia Rabello; Ducatti, Diogo Ricardo Bazan; Dietrich, Michele; Paludo, Kátia; Cabrini, Daniela Almeida; Otuki, Michel Fleith

    2015-09-01

    Photodynamic therapy (PDT) is a technique that uses light and a photosensitizer, converting local molecular oxygen into singlet oxygen, which eliminates a target unhealthy tissue. It has been increasingly used for the treatment of several diseases including skin disorders. Psoriasis is a chronic inflammatory skin disease expressing immune and hyperproliferative features. This study aimed to evaluate the effect of the photosensitizer 5,10-diphenyl-15,20-di(N-methylpyridinium-4-yl)porphyrin (Di-cis-Py+) in in vivo models whereby some psoriasis-like parameters could be investigated. The antiinflammation and antiproliferative activities of Di-cis-Py+ photoactivated was measured by myeloperoxidase (MPO) and N-acetyl-β-d-glucosaminidase (NAG) enzyme activity assay, measurement of IL-6, IL-1β and TNF-α levels, evaluation of proliferating cell nuclear antigen (PCNA) levels by immunohistochemistry and by Western blot. Treatment involving PDT and Di-cis-Py+ resulted in reduction of edema, cellular infiltration, proinflammatory cytokines, as well as reduced hyperproliferation of the epidermis. All the evaluated parameters were promoted by topical application of phlogistic agents and are similar to that observed in lesions of psoriatic skin. The results shows the advantage of topical application, do not cause apparently photosensitivity and have effects comparable to dexamethasone, a first-line drug for the treatment of the disease. Copyright © 2015. Published by Elsevier B.V.

  17. Pesticide Removal from Aqueous Solutions by Adding Salting Out Agents

    PubMed Central

    Moscoso, Fátima; Deive, Francisco J.; Esperança, José M. S. S.; Rodríguez, Ana

    2013-01-01

    Phase segregation in aqueous biphasic systems (ABS) composed of four hydrophilic ionic liquids (ILs): 1-butyl-3-methylimidazolium methylsulfate and 1-ethyl-3-methylimidazolium methylsulfate (CnC1im C1SO4, n = 2 and 4), tributylmethyl phosphonium methylsulfate (P4441 C1SO4) and methylpyridinium methylsulfate (C1Py C1SO4) and two high charge density potassium inorganic salts (K2CO3 and K2HPO4) were determined by the cloud point method at 298.15 K. The influence of the addition of the selected inorganic salts to aqueous mixtures of ILs was discussed in the light of the Hofmeister series and in terms of molar Gibbs free energy of hydration. The effect of the alkyl chain length of the cation on the methylsulfate-based ILs has been investigated. All the solubility data were satisfactorily correlated to several empirical equations. A pesticide (pentachlorophenol, PCP) extraction process based on the inorganic salt providing a greater salting out effect was tackled. The viability of the proposed process was analyzed in terms of partition coefficients and extraction efficiencies. PMID:24145747

  18. Control of cytolocalization and mechanism of cell death by encapsulation of a photosensitizer.

    PubMed

    Deda, Daiana K; Pavani, Christiane; Caritá, Eduardo; Baptista, Maurício S; Toma, Henrique E; Araki, Koiti

    2013-08-01

    The most challenging and wanted development in photodynamic therapy is the control of photosensitizer (PS) cytolocalization and the mechanism of cell death. 5,10,15-triphenyl-20-(3-N-methylpyridinium-yl)porphyrin (3MMe) administered to HeLa cells as DMSO solution accumulates in the cytoplasmic membrane (CM) where it causes severe photodamage and cell necrosis. In contrast, when incorporated in marine atelocollagen/xantham gum polymeric nanocapsules, the PS is shuttled through CM allowing its gradual release and accumulation in mitochondria and lysosomes. Little photodamage was caused to cells in this case, but compelling evidences are presented showing that encapsulation changes the cytolocalization and shifts the cell death mechanism from necrosis to apoptosis. In conclusion, both of those challenges can be overcome by encapsulation of typical PSs such as 3MMe by using the new concept of photodynamic treatment with minimal cell damage by targeting specifically some key organelles. We are confident that these findings are important for the development of more efficient photosensitizers tailored to induce apoptosis while minimizing undesirable side effects such as over-inflammation.

  19. Inhibition of ( sup 3 H)dopamine uptake into rat striatal slices by quaternary N-methylated nicotine metabolites

    SciTech Connect

    Dwoskin, L.P.; Leibee, L.L.; Jewell, A.L.; Fang, Zhaoxia; Crooks, P.A. )

    1992-01-01

    The effects of quaternary N-methylated nicotine derivatives were examined on in vitro uptake of ({sup 3}H)dopamine (({sup 3}H)DA) in rat striatal slices. Striatal slices were incubated with a 10 {mu}M concentration of the following compounds: N-methylnicotinium, N-methylnornicotinium, N-methylcotininium, N,N{prime}-dimethylnicotinium and N{prime}-methylnicotinium salts. The results clearly indicated that significant inhibition of ({sup 3}H)DA uptake occurred with those compounds possessing a N-methylpyridinium group; whereas, compounds that were methylated at the N{prime}-pyrrolidinium position were less effective or exhibited no inhibition of ({sup 3}H)DA uptake. The results suggest that high concentrations of quaternary N-methylated nicotine metabolites which are structurally related to the neurotoxin MPP{sup +}, and which may be formed in the CNS, may protect against Parkinson's Disease and explain the inverse relationship between smoking and Parkinsonism reported in epidemiologic studies.

  20. Hybrid systems based on gold nanostructures and porphyrins as promising photosensitizers for photodynamic therapy.

    PubMed

    Ferreira, Daniele C; Monteiro, Camila S; Chaves, Claudilene R; Sáfar, Gustavo A M; Moreira, Roberto L; Pinheiro, Maurício V B; Martins, Dayse C S; Ladeira, Luiz Orlando; Krambrock, Klaus

    2017-02-01

    Gold nanostructures of two different shapes (spheres and rods) were synthesized to form a colloidal hybrid system with 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin tosylate salt (H2TM4PyP(OTs)4) (POR) for applications in photodynamic therapy (PDT) using light in the visible spectral range. Electron paramagnetic resonance (EPR) experiments in combination with spin trapping were used for the detection of reactive oxygen species (ROS) and evaluation of the efficiency of these novel hybrid systems as photosensitizers. It is shown that the hybrid system consisting of gold nanorods (AuNR) and porphyrin (POR) is by far more efficient than its isolated components. This enhanced efficiency is explained by a synergetic effect between the AuNR and the porphyrin, wherein a rapid energy transfer from the former to the latter produces a large amount of singlet oxygen followed by its conversion into hydroxyl radicals. The mechanism was investigated using different spin traps and different ROS inhibitors. On the other hand, spherical gold nanoparticles (AuNP) do not show this synergetic effect. The synergetic effect for gold nanorods/POR hybrid is attributed to a larger field enhancement close to the gold nanorod surface in addition to the electrostatic attraction between the components of the hybrid system.

  1. The role of tortuosity on ion conduction in block copolymer electrolyte thin films

    NASA Astrophysics Data System (ADS)

    Kambe, Yu; Arges, Christopher G.; Nealey, Paul F.

    This talk discusses the role of grain tortuosity on ion conductivity in block copolymer electrolyte (BCE) thin films. In particular, we studied lamellae forming BCEs with both domains oriented perpendicular to the substrate surface and connected directly from one electrode to another - i.e., tortuosity of one. The BCE is composed of ion-conducting, poly(2-vinyl n-methylpyridinium) blocks and non-ionic polystyrene blocks. Prior to creating the BCE, the pristine block copolymer, poly(styrene- b-2-vinyl pyridine), was directly self-assembled (DSA) on topographical or chemical patterns via graphoepitaxy and chemoepitaxy. A chemical vapor infiltration reaction modified the P2VP block into positively charged, fixed quaternary ammonium groups paired with mobile counteranions. The graphoepitaxy process utilized topographical interdigitated gold nanoelectrodes (100s of nanometers spacing between electrodes) created via e-beam lithography. Alternatively, chemical patterns had gold electrodes incorporated into them with 10s to 100s of microns spacing using conventional optical lithography. The interdigitated gold electrodes enabled in-plane ion conductivity measurements of the DSA BCEs to study the role of grain tortuosity on ion conductivity. U.S. Department of Energy Office of Science: Contract No. DE-AC02-06CH11357.

  2. Design, synthesis and evaluation of redox radiopharmaceuticals: a potential new approach for the development of brain imaging agents

    SciTech Connect

    Srivastava, P.C.; Knapp, F.F. Jr.

    1986-01-01

    The fabrication and complete evaluation are described of a dihydropyridine in equilibrium pyridinium salt type redox system for the delivery of radioiodinated agents to the brain. The pivotal intermediate, N-succinimidyl (1-methylpyridinium iodide)-3-carboxylate was prepared by condensation of nicotinic acid and N-hydroxysuccinimide in the presence of dicyclohexylcarbodimide, followed by quaternization of III with methyl iodide. Tissue distribution studies of /sup 125/I-labeled 4-iodoaniline and the redox agents were performed in rats. (/sup 125/I)Iodoaniline initially showed moderate (0.58% dose/gm) brain uptake with subsequent release of the radioactivity from the brain. (/sup 125/I)Iodoaniline, when coupled to a dihydropyridine carrier showed higher uptake and retention in the brain. The (/sup 125/I)iodophenylethyl analogue showed uptake and retention in the brain to be very similar. Apparently the lipophilic agents cross the blood-brain barrier and are oxidized (quaternized) within the brain. The blood-brain barrier then prevents their release resulting in high uptake and retention in the brain and high brain:blood ratios. 11 refs., 3 figs.

  3. Structural properties and antibacterial effects of hydrophobic and oleophobic sol-gel coatings for cotton fabrics.

    PubMed

    Vilcnik, Aljaz; Jerman, Ivan; Surca Vuk, Angela; Kozelj, Matjaz; Orel, Boris; Tomsic, Brigita; Simoncic, Barbara; Kovac, Janez

    2009-05-19

    In a continuation of previous studies, the wetting properties of the hydrophobic diureapropyltriethoxysilane [bis(aminopropyl)-terminated polydimethylsiloxane (1000)] (PDMSU) sol-gel hybrid, which forms washing-resistant water-repellent finishes on cotton fabrics, were further investigated. The addition of 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) to PDMSU resulted in a highly apolar low-energy surface on aluminum with gammaStotal equal to 14.5 mJ/m2 and a DetlaGiwi value of -82 mJ/m2. Mixed PFOTES-PDMSU finishes applied on cotton fabrics increased the water contact angles (thetaw) from approximately 130 degrees (PDMSU) to 147 degrees, also imparting oleophobicity (thetadiiodomethane=130 degrees, thetan-hexadecane=120 degrees) to the finished cotton fabrics. Washing caused breakage of the coating's integrity as established from SEM, which was attributed to the partial removal of PFOTES from the composite films, also shown by subtractive IR attenuated total reflectance (ATR) and XPS spectral measurements made on washed and unwashed fabrics. The antibacterial properties of the PFOTES-PDMSU-finished fabrics were assessed with the transfer method (EN ISO 20743:2007), revealing that the reduction of Escherichia coli bacteria on unwashed cotton fabrics was nearly 100%. Moreover, for washed (10 times) cotton fabrics a much higher bacterial reduction was noted for the PFOTES-PDMSU finishes (60.6+/-10.8%), surpassing PDMSU (30.4+/-6.1%) and commercial fluoroalkoxysilane (FAS) (21.9+/-5.7%) finishes. The structure of PFOTES-PDMSU gels, xerogels, and the corresponding coatings was investigated by analyzing the 29Si NMR and IR ATR spectra and comparing them with the spectra of PFOTES and octameric (T8) PFOTES based polyhedra. The results revealed the tendency of PFOTES to condense in octameric silsesquioxane polyhedra (T8), coexisting in the PDMSU sol-gel network with cyclic tetramers (T4(OH)4) and open cube-like species (T7(OH)3). The presence of -OH

  4. Dynamic control of the location of nanoparticles in hybrid co-assemblies

    NASA Astrophysics Data System (ADS)

    Su, Zhilong; Li, Xiaokang; Jiang, Xuesong; Lin, Shaoliang; Yin, Jie

    2015-03-01

    We herein demonstrated an approach to control the spatial distribution of components in hybrid microspheres. Hybrid core-shell structured microspheres (CSMs) prepared through co-assembly were used as starting materials, which are comprised of anthracene-ended hyperbranched poly(ether amine) (AN-hPEA) in the shell and crystallized anthracene containing polyhedral oligomer silsesquioxane (AN-POSS). Upon thermal annealing at a temperature higher than the melting point of AN-POSS, the diffusion of AN-POSS from the core to the shell of CSM leads to a transition of morphology from the core-shell structure to core-transition-shell to the more stable homogeneous morphology, which has been revealed by experimental results of TEM and DSC. The mechanism for the morphology transition of CSM induced by the diffusion of AN-POSS was disclosed by a dissipative particle dynamics (DPD) simulation. A mathematical model for the diffusion of POSS in the hybrid microsphere is established according to Fick's law of diffusion and can be used to quantify its distribution in CSM. Thus, the spatial distribution of POSS in the microsphere can be controlled dynamically by tuning the temperature and time of thermal annealing.We herein demonstrated an approach to control the spatial distribution of components in hybrid microspheres. Hybrid core-shell structured microspheres (CSMs) prepared through co-assembly were used as starting materials, which are comprised of anthracene-ended hyperbranched poly(ether amine) (AN-hPEA) in the shell and crystallized anthracene containing polyhedral oligomer silsesquioxane (AN-POSS). Upon thermal annealing at a temperature higher than the melting point of AN-POSS, the diffusion of AN-POSS from the core to the shell of CSM leads to a transition of morphology from the core-shell structure to core-transition-shell to the more stable homogeneous morphology, which has been revealed by experimental results of TEM and DSC. The mechanism for the morphology transition

  5. Vibrational and electronic circular dichroism study of the interactions of cationic porphyrins with (dG-dC)10 and (dA-dT)10.

    PubMed

    Nový, Jakub; Urbanová, Marie

    2007-03-01

    The interactions of two different porphyrins, without axial ligands-5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin-Cu(II) tetrachloride (Cu(II)TMPyP) and with bulky meso substituents-5,10,15,20-tetrakis(N,N,N-trimethylanilinium-4-yl)porphyrin tetrachloride (TMAP), with (dG-dC)10 and (dA-dT)10 were studied by combination of vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectroscopy at different [oligonucleotide]/[porphyrin] ratios, where [oligonucleotide] and [porphyrin] are the concentrations of oligonucleotide per base-pair and porphyrin, respectively. The combination of VCD and ECD spectroscopy enables us to identify the types of interactions, and to specify the sites of interactions: The intercalative binding mode of Cu(II)TMPyP with (dG-dC)(10), which has been well described, was characterized by a new VCD "marker" and it was shown that the interaction of Cu(II)TMPyP with (dA-dT)10 via external binding to the phosphate backbone and major groove binding caused transition from the B to the non-B conformer. TMAP interacted with the major groove of (dG-dC)10, was semi-intercalated into (dA-dT)10, and caused significant variation in the structure of both oligonucleotides at the higher concentration of porphyrin. The spectroscopic techniques used in this study revealed that porphyrin binding with AT sequences caused substantial variation of the DNA structure. It was shown that VCD spectroscopy is an effective tool for the conformational studies of nucleic acid-porphyrin complexes in solution. (c) 2007 Wiley Periodicals, Inc.

  6. An ultrafast spectroscopic and quantum mechanical investigation of multiple emissions in push-pull pyridinium derivatives bearing different electron donors.

    PubMed

    Carlotti, B; Benassi, E; Cesaretti, A; Fortuna, C G; Spalletti, A; Barone, V; Elisei, F

    2015-08-28

    A joint experimental and theoretical approach, involving state-of-the-art femtosecond fluorescence up-conversion measurements and quantum mechanical computations including vibronic effects, was employed to get a deep insight into the excited state dynamics of two cationic dipolar chromophores (Donor-π-Acceptor(+)) where the electron deficient portion is a N-methyl pyridinium and the electron donor a trimethoxyphenyl or a pyrene, respectively. The ultrafast spectroscopic investigation, and the time resolved area normalised emission spectra in particular, revealed a peculiar multiple emissive behaviour and allowed the distinct emitting states to be remarkably distinguished from solvation dynamics, occurring in water in a similar timescale. The two and three emissions experimentally detected for the trimethoxyphenyl and pyrene derivatives, respectively, were associated with specific local emissive minima in the potential energy surface of S1 on the ground of quantum-mechanical calculations. A low polar and planar Locally Excited (LE) state together with a highly polar and Twisted Intramolecular Charge Transfer (TICT) state is identified to be responsible for the dual emission of the trimethoxyphenyl compound. Interestingly, the more complex photobehaviour of the pyrenyl derivative was explained considering the contribution to the fluorescence coming not only from the LE and TICT states but also from a nearly Planar Intramolecular Charge Transfer (PICT) state, with both the TICT and the PICT generated from LE by progressive torsion around the quasi-single bond between the methylpyridinium and the ethene bridge. These findings point to an interconversion between rotamers for the pyrene compound taking place in its excited state against the Non-equilibrated Excited Rotamers (NEER) principle.

  7. Multi-parametric approach to identify coffee components that regulate mechanisms of gastric acid secretion.

    PubMed

    Rubach, Malte; Lang, Roman; Seebach, Elisabeth; Somoza, Mark M; Hofmann, Thomas; Somoza, Veronika

    2012-02-01

    Chlorogenic acid (CA), caffeine (CAFF), pyrogallol (PYR), catechol (CAT), (β)N-alkanoyl-hydroxytryptamides (C5HT) and N-methylpyridinium (N-MP) were evaluated for their influence on mechanisms of gastric acid secretion as single compounds and in biomimetic mixtures. Compounds were tested in coffee representative concentrations. Human gastric cancer cells (HGT-1) were used to study the proton secretory activity by Ussing chamber experiments and FACS analysis. For activation of EGFr, Akt1, ERK1/2, ATF-2 and cAMP levels, we performed pathway screening assays. Time-dependent expression of related genes were determined by real-time PCR. Part of the data was used for neural network modeling to identify the most relevant compounds. N-MP increased the expression of the anti-secretory somatostatin receptor by 114%, whereas C5HT decreased its expression by 52%. N-MP down-regulated the pro-secretory CHRM3 receptor by 36% and the H⁺,K⁺-ATPase by 36%. CAFF stimulated the secretory activity in the functional assays, whereas N-MP and CA decreased proton secretion. After applying a pathway analysis, we were able to discriminate between CAFF, CA, CAT, C5HT, PYR and histamine-activating EGFr signaling and N-MP-associated ERK1/2 signaling. By applying a multi-parametric approach, N-MP was shown to effectively down-regulate mechanisms of gastric acid secretion in human parietal gastric cells. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Activity-guided fractionation to characterize a coffee beverage that effectively down-regulates mechanisms of gastric acid secretion as compared to regular coffee.

    PubMed

    Rubach, Malte; Lang, Roman; Skupin, Carola; Hofmann, Thomas; Somoza, Veronika

    2010-04-14

    In some individuals, the consumption of coffee beverages is related to symptoms of gastric irritation. Hot water steam-treatment of raw coffee beans is hypothesized to reduce the contents of stomach irritating compounds, and products to which this technology is applied are launched as stomach-friendly coffee. However, data on the effect of steam-treated coffee on gastric acid secretion are conflicting and it has not been proven yet as to which coffee components act as pro- or antisecretory stimulants. The work presented here aimed at the characterization of a coffee beverage that effectively down-regulates mechanisms of proton secretion in human gastric cells (HGT-1). At first, a regular coffee beverage was fractionated by using solvents of different polarity: water, ethylacetate, dichloromethane, and pentane. Functional assays on the proton secretory activity (PSA) of these solvent fractions revealed the least pronounced effect for the water fraction, for which quantitative analyses demonstrated the highest distribution of chlorogenic acid (95%), (beta)N-alkanoyl-5-hydroxytryptamides (55%), and N-methylpyridinium (N-MP, >99%) among all fractions. Following experiments demonstrated that HGT-1 cells treated with regular coffee fortified with N-MP at a concentration of about 20 mg/mL N-MP showed a significantly decreased PSA as compared to cells which were exposed to coffee beverages containing higher (32-34 mg/L) or lower (5 mg/L) N-MP concentrations. Results from cellular pathway analyses of transcription (ATF-1 and Akt1) and signaling (cAMP and EGFr) factors and kinases (ERK1/2), and experiments on the gene expression of pro (histamine-HRH2 and acetylcholine-CHRM3)- and anti (somatostatin-SSTR1)-secretory receptors and H(+),K(+)-ATPase verified this antisecretory activity of N-MP in coffee beverages.

  9. Measurement of the intracellular ph in human stomach cells: a novel approach to evaluate the gastric acid secretory potential of coffee beverages.

    PubMed

    Weiss, Carola; Rubach, Malte; Lang, Roman; Seebach, Elisabeth; Blumberg, Simone; Frank, Oliver; Hofmann, Thomas; Somoza, Veronika

    2010-02-10

    As the consumption of coffee beverages sometimes is reported to cause gastric irritation, for which an increased stomach acid secretion is one of the promoting factors, different processing technologies such as steam-treatment have been developed to reduce putative stomach irritating compounds. There is evidence-based data neither on the effect of detailed processing variations nor on individual coffee components affecting the proton secretory activity (PSA). This work aimed at developing a screening model suitable for investigating the effects of commercial coffee beverages and components thereof on human parietal cells. Human gastric cancer cells (HGT-1) were treated with reconstituted freeze-dried coffee beverages prepared from customary coffee products such as regular coffee (RC, n = 4), mild bean coffee (MBC, n = 5), stomach friendly coffee (SFC, n = 4), and SFC decaffeinated (SFCD, n = 3). PSA was analyzed by flow cytometry using the pH-sensitive dye SNARF-AM. Treatment of the cells with MBC did not result in a PSA different from RC treatment (p methylpyridinium, and catechol in SFCD compared to RC. However, none of these compounds seem to act as the sole key bioactive reducing the PSA of SFCD, since their contents in MBC and SFC samples were not different from those in RC samples, although the PSA of these beverages was significantly lower than that of reconstituted freeze-dried RC beverage.

  10. Presence and Function of Dopamine Transporter (DAT) in Stallion Sperm: Dopamine Modulates Sperm Motility and Acrosomal Integrity

    PubMed Central

    Covarrubias, Alejandra A.; Rodríguez-Gil, Joan Enric; Ramírez-Reveco, Alfredo; Concha, Ilona I.

    2014-01-01

    Dopamine is a catecholamine with multiple physiological functions, playing a key role in nervous system; however its participation in reproductive processes and sperm physiology is controversial. High dopamine concentrations have been reported in different portions of the feminine and masculine reproductive tract, although the role fulfilled by this catecholamine in reproductive physiology is as yet unknown. We have previously shown that dopamine type 2 receptor is functional in boar sperm, suggesting that dopamine acts as a physiological modulator of sperm viability, capacitation and motility. In the present study, using immunodetection methods, we revealed the presence of several proteins important for the dopamine uptake and signalling in mammalian sperm, specifically monoamine transporters as dopamine (DAT), serotonin (SERT) and norepinephrine (NET) transporters in equine sperm. We also demonstrated for the first time in equine sperm a functional dopamine transporter using 4-[4-(Dimethylamino)styryl]-N-methylpyridinium iodide (ASP+), as substrate. In addition, we also showed that dopamine (1 mM) treatment in vitro, does not affect sperm viability but decreases total and progressive sperm motility. This effect is reversed by blocking the dopamine transporter with the selective inhibitor vanoxerine (GBR12909) and non-selective inhibitors of dopamine reuptake such as nomifensine and bupropion. The effect of dopamine in sperm physiology was evaluated and we demonstrated that acrosome integrity and thyrosine phosphorylation in equine sperm is significantly reduced at high concentrations of this catecholamine. In summary, our results revealed the presence of monoamine transporter DAT, NET and SERT in equine sperm, and that the dopamine uptake by DAT can regulate sperm function, specifically acrosomal integrity and sperm motility. PMID:25402186

  11. Photocatalytic Reduction of Artificial and Natural Nucleotide Co-factors with a Chlorophyll-Like Tin-Dihydroporphyrin Sensitizer

    PubMed Central

    2013-01-01

    An efficient photocatalytic two-electron reduction and protonation of nicotine amide adenine dinucleotide (NAD+), as well as the synthetic nucleotide co-factor analogue N-benzyl-3-carbamoyl-pyridinium (BNAD+), powered by photons in the long-wavelength region of visible light (λirr > 610 nm), is demonstrated for the first time. This functional artificial photosynthetic counterpart of the complete energy-trapping and solar-to-fuel conversion primary processes occurring in natural photosystem I (PS I) is achieved with a robust water-soluble tin(IV) complex of meso-tetrakis(N-methylpyridinium)-chlorin acting as the light-harvesting sensitizer (threshold wavelength of λthr = 660 nm). In buffered aqueous solution, this chlorophyll-like compound photocatalytically recycles a rhodium hydride complex of the type [Cp*Rh(bpy)H]+, which is able to mediate regioselective hydride transfer processes. Different one- and two-electron donors are tested for the reductive quenching of the irradiated tin complex to initiate the secondary dark reactions leading to nucleotide co-factor reduction. Very promising conversion efficiencies, quantum yields, and excellent photosensitizer stabilities are observed. As an example of a catalytic dark reaction utilizing the reduction equivalents of accumulated NADH, an enzymatic process for the selective transformation of aldehydes with alcohol dehydrogenase (ADH) coupled to the primary photoreactions of the system is also demonstrated. A tentative reaction mechanism for the transfer of two electrons and one proton from the reductively quenched tin chlorin sensitizer to the rhodium co-catalyst, acting as a reversible hydride carrier, is proposed. PMID:24073596

  12. Uremic Toxins Induce ET-1 Release by Human Proximal Tubule Cells, which Regulates Organic Cation Uptake Time-Dependently

    PubMed Central

    Schophuizen, Carolien M. S.; Hoenderop, Joost G. J.; Masereeuw, Rosalinde; van den Heuvel, Lambert P.

    2015-01-01

    In renal failure, the systemic accumulation of uremic waste products is strongly associated with the development of a chronic inflammatory state. Here, the effect of cationic uremic toxins on the release of inflammatory cytokines and endothelin-1 (ET-1) was investigated in conditionally immortalized proximal tubule epithelial cells (ciPTEC). Additionally, we examined the effects of ET-1 on the cellular uptake mediated by organic cation transporters (OCTs). Exposure of ciPTEC to cationic uremic toxins initiated production of the inflammatory cytokines IL-6 (117 ± 3%, p < 0.001), IL-8 (122 ± 3%, p < 0.001), and ET-1 (134 ± 5%, p < 0.001). This was accompanied by a down-regulation of OCT mediated 4-(4-(dimethylamino)styryl)-N-methylpyridinium-iodide (ASP+) uptake in ciPTEC at 30 min (23 ± 4%, p < 0.001), which restored within 60 min of incubation. Exposure to ET-1 for 24 h increased the ASP+ uptake significantly (20 ± 5%, p < 0.001). These effects could be blocked by BQ-788, indicating activation of an ET-B-receptor-mediated signaling pathway. Downstream the receptor, iNOS inhibition by (N(G)‐monomethyl‐l‐arginine) l-NMMA acetate or aminoguanidine, as well as protein kinase C activation, ameliorated the short-term effects. These results indicate that uremia results in the release of cytokines and ET-1 from human proximal tubule cells, in vitro. Furthermore, ET-1 exposure was found to regulate proximal tubular OCT transport activity in a differential, time-dependent, fashion. PMID:26132391

  13. The carnitine transporter SLC22A5 is not a general drug transporter, but it efficiently translocates mildronate.

    PubMed

    Grigat, Silke; Fork, Christian; Bach, Markus; Golz, Stefan; Geerts, Andreas; Schömig, Edgar; Gründemann, Dirk

    2009-02-01

    In addition to its function as carnitine transporter, novel organic cation transporter type 2 (OCTN2; human gene symbol SLC22A5) is widely recognized as a transporter of drugs. This notion is based on several reports of direct measurement of drug accumulation. However, a rigorous, comparative, and comprehensive analysis of transport efficiency of OCTN2 has not been available so far. In the present study, OCTN2 orthologs from human, rat, and chicken were expressed in 293 cells using an inducible expression system. Uptake of trans-4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide (ASP(+)), cephaloridine, ergothioneine, gabapentin, mildronate, pyrilamine, quinidine, spironolactone, tetraethylammonium, verapamil, and vigabatrin was determined by liquid chromatography/mass spectrometry. For reference, uptake of carnitine was measured in parallel. Our results indicate that OCTN2-mediated uptake of drugs was not significantly different from zero or, with tetraethylammonium and ergothioneine, was minute relative to carnitine. The carnitine congener mildronate, by contrast, was transported very efficiently. Thus, OCTN2 is not a general drug transporter but a highly specific carrier for carnitine and closely related molecules. Transport parameters (cellular accumulation, transporter affinity, sodium dependence) were similar for mildronate and carnitine. Efficiency of transport of mildronate was even higher than that of carnitine. Hence, our results establish that OCTN2 is a key target of the cardioprotective agent mildronate because it controls, as integral protein of the plasma membrane, cellular entry of mildronate and enables efficient access to intracellular targets. The highest levels of human OCTN2 mRNA were detected by real-time reverse transcription-polymerase chain reaction in kidney, ileum, breast, small intestine, skeletal muscle, and ovary but also in some heart and central nervous system tissues.

  14. Viscosity Measurements on Ionic Liquids: A Cautionary Tale

    NASA Astrophysics Data System (ADS)

    Diogo, João C. F.; Caetano, Fernando J. P.; Fareleira, João M. N. A.; Wakeham, William A.

    2014-10-01

    The vibrating-wire viscometer has proven to be an exceedingly effective means of determining the viscosity of liquids over a wide range of temperature and pressure. The instrument has a long history but a variety of technological and theoretical developments over a number of years have improved its precision and most recently have enabled absolute measurements of high accuracy. However, the nature of the electrical measurements required for the technique has inhibited its widespread use for electrically conducting liquids so that there have been only a limited number of measurements. In the particular context of ionic liquids, which have themselves attracted considerable attention, this is unfortunate because it has meant that one primary measurement technique has seldom been employed for studies of their viscosity. In the last 2 years systematic efforts have been made to explore the applicability of the vibrating-wire technique by examining a number of liquids of increasing electrical conductivity. These extensions have been successful. However, in the process we have had cause to review previous studies of the viscosity and density of the same liquids at moderate temperatures and pressures and significant evidence has been accumulated to cause concern about the application of a range of viscometric techniques to these particular fluids. Because the situation is reminiscent of that encountered for a new set of environmentally friendly refrigerants at the end of the last decade, in this paper the experimental methods employed with these liquids have been reviewed which leads to recommendations for the handling of these materials that may have consequences beyond viscometric measurements. In the process new viscosity and density data for 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [mim][], 1-ethyl-3-methylimidazolium ethyl sulfate [mim][], and 1-ethyl-3-methylpyridinium ethyl sulfate [mpy][] have been obtained.

  15. Ionogel fibres of bis(trifluoromethanesulfonyl)imide anion-based ionic liquids for the headspace solid-phase microextraction of chlorinated organic pollutants.

    PubMed

    Pena-Pereira, F; Marcinkowski, Ł; Kloskowski, A; Namieśnik, J

    2015-11-07

    Ionogels, a family of hybrid materials in which ionic liquids (ILs) are confined in a sol-gel network, are receiving much attention in a variety of scientific and technological fields. In this work, ionogels derived from three different ILs based on the anion bis(trifluoromethanesulfonyl)imide (TFSI), namely 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide ([C4C1Py][TFSI]), 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([C4C1Pyrr][TFSI]), and 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide ([C4C1Pip][TFSI]) were obtained on the outer surface of optical fibres by sol-gel technology. The obtained hybrid materials were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDX), and subsequently evaluated as sorbent coatings for the headspace solid-phase microextraction (HS-SPME) of volatile chlorinated organic compounds in combination with gas chromatography with barrier ionization discharge detection (GC-BID). The ionogel based on [C4C1Pyrr][TFSI] exhibited the highest extractability for target analytes. The experimental parameters that affect the extraction process were optimized by means of a central composite design. Under optimal conditions, the proposed method yielded excellent enrichment factors (EFs) in the range 3889-20 919 and limits of detection (LODs) between 11 and 151 ng L(-1) for the target compounds. The inter-day repeatability, intra-day reproducibility and fibre-to-fibre reproducibility, were less than 8.5, 9.6 and 16.9%, respectively. Finally, the developed method was applied to the analysis of water samples, showing recovery values in the range 95-106%.

  16. Optical detection/collection of toxic Cd(II) ions using cubic Ia3d aluminosilica mesocage sensors.

    PubMed

    El-Safty, Sherif A; Shenashen, Mohamed A; Khairy, Mohamed

    2012-08-30

    Optical sensors for selective removal and detection of extremely toxic ions such as cadmium (Cd(II)) in aquatic samples were successfully fabricated via simple strategy. Aluminosilica-based network platforms are used as selective mesopore shape and size carriers in order to fabricate optical sensors through the direct functionalization of α, β, γ, and δ-tetrakis(1-methylpyridinium-4-yl)porphine ρ-toluenesulfonate (TMPyP) moieties without any prior surface modification using silane or thiol agents. In turn, the key advantage of a heretical three-dimensional (3D) cubic Ia3d mesocage is the facile access of target ions such as ion transports and the high affinity responses of TMPyP receptor-Cd(II) analyte binding events, which result in the easy generation and transduction of optical signals even at the trace level of the Cd(II) ion. The optical sensor design-based aluminosilica cages enable the sensitive detection and selective removal of Cd(II) ions even at ultra-trace concentrations of 10(-10)mol/dm(3) with rapid response time (in minutes). This rational strategy is crucial to the development of optical mesocollectors (i.e., probe surface-mounted naked-eye ion-sensor strips) with highly selective Cd(II) ion removal from aqueous water. These new classes of optical mesocollectors exhibit long-term stability and reusability of deleterious Cd(II) ions, which makes them efficient for various analytical applications. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Upscaling of a living membrane for bioartificial kidney device.

    PubMed

    Chevtchik, Natalia Vladimirovna; Fedecostante, Michele; Jansen, Jitske; Mihajlovic, Milos; Wilmer, Martijn; Rüth, Marieke; Masereeuw, Rosalinde; Stamatialis, Dimitrios

    2016-11-05

    The limited removal of metabolic waste products in dialyzed kidney patients leads to high morbidity and mortality. One powerful solution for a more complete removal of those metabolites might be offered by a bioartificial kidney device (BAK), which contains a hybrid "living membrane" with functional proximal tubule epithelial cells (PTEC). These cells are supported by an artificial functionalized hollow fiber membrane (HFM) and are able to actively remove the waste products. In our earlier studies, conditionally immortalized human PTEC (ciPTEC) showed to express functional organic cationic transporter 2 (OCT2) when seeded on small size flat or hollow fiber polyethersulfone (PES) membranes. Here, an upscaled "living membrane" is presented. We developed and assessed the functionality of modules containing three commercially available MicroPES HFM supporting ciPTEC. The HFM were optimally coated with L-Dopa and collagen IV to support a uniform and tight monolayer formation of matured ciPTEC under static culturing conditions. Both abundant expression of zonula occludens-1 (ZO-1) protein and limited diffusion of FITC-inulin confirm a clear barrier function of the monolayer. Furthermore, the uptake of 4-(4-(dimethylamino)styryl)-N-methylpyridinium iodide (ASP(+)), a fluorescent OCT2 substrate, was studied in absence and presence of known OCT inhibitors, such as cimetidine and a cationic uremic solutes mixture. The ASP(+) uptake by the living upscaled membrane was decreased by 60% in the presence of either inhibitor, proving the active function of OCT2. In conclusion, this study presents a successful upscaling of a living membrane with active organic cation transport as a support for BAK device. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Evaluation of resistance development and viability recovery by a non-enveloped virus after repeated cycles of aPDT.

    PubMed

    Costa, Liliana; Tomé, João P C; Neves, Maria G P M S; Tomé, Augusto C; Cavaleiro, José A S; Faustino, Maria A F; Cunha, Ângela; Gomes, Newton C M; Almeida, Adelaide

    2011-09-01

    Nowadays, the emergence of drug resistant microorganisms is a public health concern. The antimicrobial photodynamic therapy (aPDT) has an efficient action against a wide range of microorganisms and can be viewed as an alternative approach for treating microbial infections. The aim of this study was to determine if a model target virus (T4-like bacteriophage), in the presence of the tricationic porphyrin 5,10,15-tris(1-methylpyridinium-4-yl)-20-(pentafluorophenyl)porphyrin tri-iodide (Tri-Py(+)-Me-PF), can develop resistance to aPDT and recover its viability after photodynamic treatments. To assess the development of aPDT resistance after repeated treatments, a suspension of T4-like bacteriophage was irradiated with white light (40 Wm(-2)) for 120 min in the presence of 5.0 μM of Tri-Py(+)-Me-PF (99.99% of inactivation) and new phage suspensions were produced from the surviving phages, after each cycle of light exposure. The procedure was repeated ten times. To evaluate the recovery of viral viability after photoinactivation, a suspension of T4-like bacteriophage was irradiated with white light for 120 min in the presence of 5.0 μM of Tri-Py(+)-Me-PF on five consecutive days. In each day, an aliquot of the irradiated suspension was plated and the number of lysis plaques was counted after 24, 48, 72, 96 and 120 h of dark incubation at 37 °C. The profile of bacteriophage photoinactivation did not change after ten consecutive cycles and no recovery of viability was detected after five accumulated cycles of photodynamic treatment. The results suggest that aPDT represents a valuable and promising alternative therapy to treat viral infections, overcoming the problem of microbial resistance. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Slow relaxation of the magnetization in non-linear optical active layered mixed metal oxalate chains.

    PubMed

    Cariati, Elena; Ugo, Renato; Santoro, Giuseppe; Tordin, Elisa; Sorace, Lorenzo; Caneschi, Andrea; Sironi, Angelo; Macchi, Piero; Casati, Nicola

    2010-12-06

    New Co(II) members of the family of multifunctional materials of general formula [DAMS](4)[M(2)Co(C(2)O(4))(6)]·2DAMBA·2H(2)O (M(III) = Rh, Fe, Cr; DAMBA = para-dimethylaminobenzaldehyde and [DAMS(+)] = trans-4-(4-dimethylaminostyryl)-1-methylpyridinium) have been isolated and characterized. Such new hybrid mixed metal oxalates are isostructural with the previously investigated containing Zn(II), Mn(II), and Ni(II). This allows to preserve the exceptional second harmonic generation (SHG) activity, due to both the large molecular quadratic hyperpolarizability of [DAMS(+)] and the efficiency of the crystalline network which organizes [DAMS(+)] into head-to-tail arranged J-type aggregates, and to further tune the magnetic properties. In particular, the magnetic data of the Rh(III) derivative demonstrate that high spin octacoordinated Co(II) centers behave very similarly to the hexacoordinated Co(II) ones, being dominated by a large orbital contribution. The Cr(III) derivative is characterized by ferromagnetic Cr(III)-Co(II) interactions. Most relevantly, the Fe(III) compound is characterized by a moderate antiferromagnetic interaction between Fe(III) and Co(II), resulting in a ferrimagnetic like structure. Its low temperature dynamic magnetic properties were found to follow a thermally activated behavior (τ(0) = 8.6 × 10(-11) s and ΔE = 21.4 K) and make this a candidate for the second oxalate-based single chain magnet (SCM) reported up to date, a property which in this case is coupled to the second order non linear optical (NLO) ones.

  20. Thermo-solvatochromism in binary mixtures of water and ionic liquids: on the relative importance of solvophobic interactions.

    PubMed

    Sato, Bruno M; de Oliveira, Carolina G; Martins, Clarissa T; El Seoud, Omar A

    2010-02-28

    The thermo-solvatochromism of 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), has been studied in mixtures of water, W, with ionic liquids, ILs, in the temperature range of 10 to 60 degrees C, where feasible. The objectives of the study were to test the applicability of a recently introduced solvation model, and to assess the relative importance of solute-solvent solvophobic interactions. The ILs were 1-allyl-3-alkylimidazolium chlorides, where the alkyl groups are methyl, 1-butyl, and 1-hexyl, respectively. The equilibrium constants for the interaction of W and the ILs were calculated from density data; they were found to be linearly dependent on N(C), the number of carbon atoms of the alkyl group; van't Hoff equation (log K versus 1/T) applied satisfactorily. Plots of the empirical solvent polarities, E(T) (MePMBr(2)) in kcal mol(-1), versus the mole fraction of water in the binary mixture, chi(w), showed non-linear, i.e., non-ideal behavior. The dependence of E(T) (MePMBr(2)) on chi(w), has been conveniently quantified in terms of solvation by W, IL, and the "complex" solvent IL-W. The non-ideal behavior is due to preferential solvation by the IL and, more efficiently, by IL-W. The deviation from linearity increases as a function of increasing N(C) of the IL, and is stronger than that observed for solvation of MePMBr(2) by aqueous 1-propanol, a solvent whose lipophilicity is 12.8 to 52.1 times larger than those of the ILs investigated. The dependence on N(C) is attributed to solute-solvent solvophobic interactions, whose relative contribution to solvation are presumably greater than that in mixtures of water and 1-propanol.

  1. Density and Viscosity of Binary Mixtures of Thiocyanate Ionic Liquids + Water as a Function of Temperature.

    PubMed

    Domańska, U; Królikowska, M

    2012-09-01

    Densities and viscosities have been determined for binary mixtures of the ionic liquids (ILs) 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN], or 1-butyl-4-methylpyridinium thiocyanate [BMPy][SCN], or 1-butyl-1-methylpyrrolidinium thiocyanate [BMPYR][SCN], or 1-butyl-1-methylpiperidinium thiocyanate [BMPIP][SCN] with water over wide range of temperatures (298.15-348.15) K and ambient pressure. The thermal properties of [BMPy][SCN], i.e. glass transition temperature and the heat capacity at glass transition, have been measured using a differential scanning microcalorimetry, DSC. The decomposition of [BMPy][SCN] was detected. The density and viscosity correlations for these systems have been made using an empirical second-order polynomial and by the Vogel-Fulcher-Tammann equation, respectively. The concentration dependences have been described by polynomials. The excess molar volumes and deviations in viscosity have been calculated from the experimental values and were correlated by Redlich-Kister polynomial expansions. The variations of these parameters, with compositions of the mixtures and temperature, have been discussed in terms of molecular interactions. A qualitative analysis of the trend of properties with composition and temperature was performed. Further, the excess partial molar volumes, [Formula: see text] and [Formula: see text], were calculated and discussed. The isobaric expansivities (coefficient of thermal expansion), α, and the excess isobaric expansivities, α(E), were determined for four ILs and their mixtures with water. The results indicate that the interactions of thiocyanate ILs with water is not as strong as with alcohols, which is shown by the positive/slightly negative excess molar volumes in these binary systems. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s10953-012-9875-7) contains supplementary material, which is available to authorized users.

  2. Interaction of a tricationic meso-substituted porphyrin with guanine-containing polyribonucleotides of various structures

    NASA Astrophysics Data System (ADS)

    Ryazanova, Olga; Zozulya, Victor; Voloshin, Igor; Glamazda, Alexander; Dubey, Igor; Dubey, Larysa; Karachevtsev, Victor

    2016-09-01

    The interaction of a tricationic water-soluble meso-(N-methylpyridinium)-substituted porphyrin, TMPyP3+, derived from classic TMPyP4, with double-stranded poly(G)  ṡ  poly(C) and four-stranded poly(G) polyribonucleotides has been studied in aqueous buffered solutions, pH 6.9, of low and near-physiological ionic strengths in a wide range of molar phosphate-to-dye ratios (P/D). To clarify the binding modes of TMPyP3+ to biopolymers various spectroscopic techniques, including absorption and polarized fluorescence spectroscopy, Raman spectroscopy, and resonance light scattering, were used. As a result, two competitive binding modes were revealed. In solution of low ionic strength outside binding of the porphyrin to the polynucleotide backbone with self-stacking prevailed at low P/D ratios (P/D  <  3.5). It manifested itself by the substantial quenching of porphyrin fluorescence. Also the formation of large-scale porphyrin aggregates was observed near the stoichiometric binding ratio. The spectral changes observed at P/D  >  30 including emission enhancement were supposed to be caused by the embedding of partially stacked porphyrin J-dimers into the polymer groove. TMPyP3+ binding to poly(G) induced a fluorescence increase 2.5 times as large as that observed for poly(G)  ṡ  poly(C). In solution of near-physiological ionic strength the efficiency of external porphyrin binding was reduced substantially due to the competitive binding of Na+ ions with the polymer backbone. The spectroscopic characteristics of porphyrin bound to polynucleotides at different conditions were compared with those for free porphyrin.

  3. Variable toxicity of ionic liquid-forming chemicals to Lemna minor and the influence of dissolved organic matter.

    PubMed

    Larson, James H; Frost, Paul C; Lamberti, Gary A

    2008-03-01

    Ionic liquids (ILs) are nonvolatile organic salts that remain liquid over a wide range of temperatures. Ionic liquids are promoted as environmentally friendly alternatives to the volatile organic solvents that are currently in widespread industrial usage. Although ILs are unlikely to contribute to air pollution, their potential effects on aquatic ecosystems are largely unknown. Furthermore, information is lacking on how ILs will interact with common features of aquatic environments, such as dissolved organic matter (DOM). We assessed the effect of five IL-forming chemicals on the growth of duckweed, Lemna minor, a common aquatic vascular plant. In general, 1-alkyl-3-methylimidazolium chemicals with longer alkyl chains were more toxic to L. minor than those with short alkyl chain lengths. The concentration that produced a 50% reduction (the EC50) in root growth was 8.56 ppm when a butyl chain was present but was 0.25 ppm (i.e., much more toxic) when an octyl chain was substituted. Butyl-substituted 3-methylpyridinium (root growth EC50 of 7.49 ppm) and 3-methylimidazolium cations had similar toxicity, whereas a tetrabutyl ammonium cation was considerably less toxic (root growth EC50 of 32.71 ppm). When we tested whether DOM reduced the toxicity of these cations, we saw no effect of a low-molecular-weight organic acid or commercial humic matter. In contrast, natural DOM reduced the toxicity of imidazolium, but only at low concentrations. Design and use of ILs and other new chemicals should incorporate not only standard toxicity tests but also information on how such chemicals will interact with other components of aquatic ecosystems.

  4. Description of the behavior of dichloroalkanes-containing solutions with three [bXmpy][BF4] isomers, using the experimental information of thermodynamic properties, 1H NMR spectral and the COSMO-RS-methodology.

    PubMed

    Fernández, Luis; Ortega, Juan; Palomar, José; Toledo, Francisco; Marrero, Elena

    2015-02-26

    This work studies the binaries of 1-butyl-X-methylpyridinium tetrafluoroborate [bXmpy][BF4] (X = 2, 3, and 4) with four 1,ω-dichloroalkanes, ω = 1-4, using the results obtained for the mixing properties h(E) and v(E) at two temperatures. The three isomers of the ionic liquid (IL) are weakly miscible with the 1,ω-dichloroalkanes when ω ≥ 5 and moderately soluble for ω = 4. The v(E)s of all the binaries present contractive effects, v(E) < 0, which are more pronounced with increasing temperature; the variation in v(E) with ω is positive, although this changes after ω = 4 due to problems of immiscibility. The energetic effects of the mixing process are exothermic in the solutions with the shorter dichloroalkanes, ω = 1 and 2, and this effect increases slightly with temperature. However, mildly exothermic effects are found in the binaries with larger halides, where (dh(E)/dT) > 0. The experimental data are correlated with a suitable equation. The study is completed with (1)H NMR measurements of both the pure compounds and some of the solutions, which showed minor diamagnetic shifts with increasing IL compositions, related to the anisotropy of the pyridine ring. The variation in h(E) with ω for a same IL, due to an increase in the contact surfaces, is related to the reduction in polarity which, in turn, depends on the smaller chemical shifts of the pure dihalide compounds. The COSMO-RS method determines the energetic effects of the mixing process and predicts an exothermic contribution for the electrostatic Misfit-interaction which is quantitatively very similar for the three IL isomers. The differences proposed by the model are mainly reflected in the van der Waals interactions, which are exothermic and clearly influenced by the position of the methylene group in the IL. The contribution made by hydrogen bonds is negligible.

  5. Methylene blue inhibits function of the 5-HT transporter

    PubMed Central

    Oz, Murat; Isaev, Dmytro; Lorke, Dietrich E; Hasan, Muhammed; Petroianu, Georg; Shippenberg, Toni S

    2012-01-01

    BACKGROUND AND PURPOSE Methylene blue (MB) is commonly employed as a treatment for methaemoglobinaemia, malaria and vasoplegic shock. An increasing number of studies indicate that MB can cause 5-HT toxicity when administered with a 5-HT reuptake inhibitor. MB is a potent inhibitor of monoamine oxidases, but other targets that may contribute to MB toxicity have not been identified. Given the role of the 5-HT transporter (SERT) in the regulation of extracellular 5-HT concentrations, the present study aimed to characterize the effect of MB on SERT. EXPERIMENTAL APPROACH Live cell imaging, in conjunction with the fluorescent SERT substrate 4-(4-(dimethylamino)-styryl)-N-methylpyridinium (ASP+), [3H]5-HT uptake and whole-cell patch-clamp techniques were employed to examine the effects of MB on SERT function. KEY RESULTS In EM4 cells expressing GFP-tagged human SERT (hSERT), MB concentration-dependently inhibited ASP+ accumulation (IC50: 1.4 ± 0.3 µM). A similar effect was observed in N2A cells. Uptake of [3H]5-HT was decreased by MB pretreatment. Furthermore, patch-clamp studies in hSERT expressing cells indicated that MB significantly inhibited 5-HT-evoked ion currents. Pretreatment with 8-Br-cGMP did not alter the inhibitory effect of MB on hSERT activity, and intracellular Ca2+ levels remained unchanged during MB application. Further experiments revealed that ASP+ binding to cell surface hSERT was reduced after MB treatment. In whole-cell radioligand experiments, exposure to MB (10 µM; 10 min) did not alter surface binding of the SERT ligand [125I]RTI-55. CONCLUSIONS AND IMPLICATIONS MB modulated SERT function and suggested that SERT may be an additional target upon which MB acts to produce 5-HT toxicity. PMID:21542830

  6. New method to visualize neurons with DAT in slices of rat VTA using fluorescent substrate for DAT, ASP+

    PubMed

    Inyushin, Mikhail U; Arencibia-Albite, Francisco; de la Cruz, Angel; Vázquez-Torres, Rafael; Colon, Katiria; Sanabria, Priscila; Jiménez-Rivera, Carlos A

    2013-04-01

    The ventral tegmental area (VTA), and in particular dopamine (DA) neurons in this region of midbrain, has been shown to play an important role in motivation (goal-directed behavior), reward, and drug addiction. Most evidence that implicates VTA DA neurons in these functions are based on widely accepted but indirect electrophysiological characterization, including the hyperpolarization activated non-specific cation current (Ih), spike frequency, and inhibition by D2 receptor agonists. In this study, we used a known neuronal dopamine transporter (DAT) fluorescent substrate [4-(4- (dimethylamino) styryl)-N-methylpyridinium iodide] (ASP+) to visualize DAT-containing cell bodies of DA neurons in VTA region in rat brain slices. Uptake of 100 nM of ASP+ in brain slices of rat VTA region marked 38% of visible neurons, while other neurons from this region and 100% neurons from hippocampus slices were not fluorescent. Using patch-clamp techniques, we have found that pronounced Ih current was present in all fluorescent neurons from VTA area, also spike frequency was similar to the widely accepted values for DA neurons. Furthermore, additional study has shown that there are 84% coincidence of ASP+ fluorescence in neuronal cell bodies and Falck-Hillarp labeling of DA cells. Electrophysiological recordings during ASP+ application have confirmed that low concentrations (100 nM) of ASP+ have no visible effect on neuronal activity during 1-2 hours after staining. Thus, uptake of fluorescent monoamine analog ASP+ by DAT can be an additional criterion for identification of DAT-containing neurons in slices.

  7. Potent and Selective Inhibition of Plasma Membrane Monoamine Transporter by HIV Protease Inhibitors

    PubMed Central

    Duan, Haichuan; Hu, Tao; Foti, Robert S.; Pan, Yongmei; Swaan, Peter W.

    2015-01-01

    Plasma membrane monoamine transporter (PMAT) is a major uptake-2 monoamine transporter that shares extensive substrate and inhibitor overlap with organic cation transporters 1–3 (OCT1–3). Currently, there are no PMAT-specific inhibitors available that can be used in in vitro and in vivo studies to differentiate between PMAT and OCT activities. In this study, we showed that IDT307 (4-(4-(dimethylamino)phenyl)-1-methylpyridinium iodide), a fluorescent analog of 1-methyl-4-phenylpyridinium (MPP+), is a transportable substrate for PMAT and that IDT307-based fluorescence assay can be used to rapidly identify and characterize PMAT inhibitors. Using the fluorescent substrate-based assays, we analyzed the interactions of eight human immunodeficiency virus (HIV) protease inhibitors (PIs) with human PMAT and OCT1–3 in human embryonic kidney 293 (HEK293) cells stably transfected with individual transporters. Our data revealed that PMAT and OCTs exhibit distinct sensitivity and inhibition patterns toward HIV PIs. PMAT is most sensitive to PI inhibition whereas OCT2 and OCT3 are resistant. OCT1 showed an intermediate sensitivity and a distinct inhibition profile from PMAT. Importantly, lopinavir is a potent PMAT inhibitor and exhibited >120 fold selectivity toward PMAT (IC50 = 1.4 ± 0.2 µM) over OCT1 (IC50 = 174 ± 40 µM). Lopinavir has no inhibitory effect on OCT2 or OCT3 at maximal tested concentrations. Lopinavir also exhibited no or much weaker interactions with uptake-1 monoamine transporters. Together, our results reveal that PMAT and OCTs have distinct specificity exemplified by their differential interaction with HIV PIs. Further, we demonstrate that lopinavir can be used as a selective PMAT inhibitor to differentiate PMAT-mediated monoamine and organic cation transport from those mediated by OCT1–3. PMID:26285765

  8. Highly sensitive simultaneous quantification of estrogenic tamoxifen metabolites and steroid hormones by LC-MS/MS.

    PubMed

    Johänning, Janina; Heinkele, Georg; Precht, Jana C; Brauch, Hiltrud; Eichelbaum, Michel; Schwab, Matthias; Schroth, Werner; Mürdter, Thomas E

    2015-09-01

    Tamoxifen is a mainstay in the treatment of estrogen receptor-positive breast cancer and is metabolized to more than 30 different compounds. Little is known about in vivo concentrations of estrogenic metabolites E-metabolite E, Z-metabolite E, and bisphenol and their relevance for tamoxifen efficacy. Therefore, we developed a highly sensitive HPLC-ESI-MS/MS quantification method for tamoxifen metabolites bisphenol, E-metabolite E, and Z-metabolite E as well as for the sex steroid hormones estradiol, estrone, testosterone, androstenedione, and progesterone. Plasma samples were subjected to protein precipitation followed by solid phase extraction. Upon derivatization with 3-[(N-succinimide-1-yl)oxycarbonyl]-1-methylpyridinium iodide, all analytes were separated on a sub-2-μm column with a gradient of acetonitrile in water with 0.1 % of formic acid. Analytes were detected on a triple-quadrupole mass spectrometer with positive electrospray ionization in the multiple reaction monitoring mode. Our method demonstrated high sensitivity, accuracy, and precision. The lower limits of quantification were 12, 8, and 25 pM for bisphenol, E-metabolite E, and Z-metabolite E, respectively, and 4 pM for estradiol and estrogen, 50 pM for testosterone and androstenedione, and 25 pM for progesterone. The method was applied to plasma samples of postmenopausal patients taken at baseline and under tamoxifen therapy. Graphical Abstract Sample preparation and derivatization for highly sensitive quantification of estrogenic tamoxifen metabolites and steroid hormones by HPLC-MS/MS.

  9. Salvinorin A Regulates Dopamine Transporter Function Via A Kappa Opioid Receptor and ERK1/2-Dependent Mechanism

    PubMed Central

    Kivell, Bronwyn; Uzelac, Zeljko; Sundaramurthy, Santhanalakshmi; Rajamanickam, Jeyaganesh; Ewald, Amy; Chefer, Vladimir; Jaligam, Vanaja; Bolan, Elizabeth; Simonson, Bridget; Annamalai, Balasubramaniam; Mannangatti, Padmanabhan; Prisinzano, Thomas; Gomes, Ivone; Devi, Lakshmi A.; Jayanthi, Lankupalle D.; Sitte, Harald H.; Ramamoorthy, Sammanda; Shippenberg, Toni S.

    2014-01-01

    Salvinorin A (SalA), a selective κ-opioid receptor (KOR) agonist, produces dysphoria and pro-depressant like effects. These actions have been attributed to inhibition of striatal dopamine release. The dopamine transporter (DAT) regulates dopamine transmission via uptake of released neurotransmitter. KORs are apposed to DAT in dopamine nerve terminals suggesting an additional target by which SalA modulates dopamine transmission. SalA produced a concentration-dependent, nor-binaltorphimine (BNI)- and pertussis toxin-sensitive increase of ASP+ accumulation in EM4 cells coexpressing myc-KOR and YFP-DAT, using live cell imaging and the fluorescent monoamine transporter substrate, trans 4-(4-(dimethylamino)-styryl)-N-methylpyridinium) (ASP+). Other KOR agonists also increased DAT activity that was abolished by BNI pretreatment. While SalA increased DAT activity, SalA treatment decreased serotonin transporter (SERT) activity and had no effect on norepinephrine transporter (NET) activity. In striatum, SalA increased the Vmax for DAT mediated DA transport and DAT surface expression. SalA up-regulation of DAT function is mediated by KOR activation and the KOR-linked extracellular signal regulated kinase-½ (ERK1/2) pathway. Co-immunoprecipitation and BRET studies revealed that DAT and KOR exist in a complex. In live cells, DAT and KOR exhibited robust FRET signals under basal conditions. SalA exposure caused a rapid and significant increase of the FRET signal. This suggests that the formation of KOR and DAT complexes is promoted in response to KOR activation. Together, these data suggest that enhanced DA transport and decreased DA release resulting in decreased dopamine signaling may contribute to the dysphoric and pro-depressant like effects of SalA and other KOR agonists. PMID:25107591

  10. Salvinorin A regulates dopamine transporter function via a kappa opioid receptor and ERK1/2-dependent mechanism.

    PubMed

    Kivell, Bronwyn; Uzelac, Zeljko; Sundaramurthy, Santhanalakshmi; Rajamanickam, Jeyaganesh; Ewald, Amy; Chefer, Vladimir; Jaligam, Vanaja; Bolan, Elizabeth; Simonson, Bridget; Annamalai, Balasubramaniam; Mannangatti, Padmanabhan; Prisinzano, Thomas E; Gomes, Ivone; Devi, Lakshmi A; Jayanthi, Lankupalle D; Sitte, Harald H; Ramamoorthy, Sammanda; Shippenberg, Toni S

    2014-11-01

    Salvinorin A (SalA), a selective κ-opioid receptor (KOR) agonist, produces dysphoria and pro-depressant like effects. These actions have been attributed to inhibition of striatal dopamine release. The dopamine transporter (DAT) regulates dopamine transmission via uptake of released neurotransmitter. KORs are apposed to DAT in dopamine nerve terminals suggesting an additional target by which SalA modulates dopamine transmission. SalA produced a concentration-dependent, nor-binaltorphimine (BNI)- and pertussis toxin-sensitive increase of ASP(+) accumulation in EM4 cells coexpressing myc-KOR and YFP-DAT, using live cell imaging and the fluorescent monoamine transporter substrate, trans 4-(4-(dimethylamino)-styryl)-N-methylpyridinium) (ASP(+)). Other KOR agonists also increased DAT activity that was abolished by BNI pretreatment. While SalA increased DAT activity, SalA treatment decreased serotonin transporter (SERT) activity and had no effect on norepinephrine transporter (NET) activity. In striatum, SalA increased the Vmax for DAT mediated DA transport and DAT surface expression. SalA up-regulation of DAT function is mediated by KOR activation and the KOR-linked extracellular signal regulated kinase-½ (ERK1/2) pathway. Co-immunoprecipitation and BRET studies revealed that DAT and KOR exist in a complex. In live cells, DAT and KOR exhibited robust FRET signals under basal conditions. SalA exposure caused a rapid and significant increase of the FRET signal. This suggests that the formation of KOR and DAT complexes is promoted in response to KOR activation. Together, these data suggest that enhanced DA transport and decreased DA release resulting in decreased dopamine signalling may contribute to the dysphoric and pro-depressant like effects of SalA and other KOR agonists.

  11. Nanosized sustained-release pyridostigmine bromide microcapsules: process optimization and evaluation of characteristics

    PubMed Central

    Tan, Qunyou; Jiang, Rong; Xu, Meiling; Liu, Guodong; Li, Songlin; Zhang, Jingqing

    2013-01-01

    Background Pyridostigmine bromide (3-[[(dimethylamino)-carbonyl]oxy]-1-methylpyridinium bromide), a reversible inhibitor of cholinesterase, is given orally in tablet form, and a treatment schedule of multiple daily doses is recommended for adult patients. Nanotechnology was used in this study to develop an alternative sustained-release delivery system for pyridostigmine, a synthetic drug with high solubility and poor oral bioavailability, hence a Class III drug according to the Biopharmaceutics Classification System. Novel nanosized pyridostigmine-poly(lactic acid) microcapsules (PPNMCs) were expected to have a longer duration of action than free pyridostigmine and previously reported sustained-release formulations of pyridostigmine. Methods The PPNMCs were prepared using a double emulsion-solvent evaporation method to achieve sustained-release characteristics for pyridostigmine. The preparation process for the PPNMCs was optimized by single-factor experiments. The size distribution, zeta potential, and sustained-release behavior were evaluated in different types of release medium. Results The optimal volume ratio of inner phase to external phase, poly(lactic acid) concentration, polyvinyl alcohol concentration, and amount of pyridostigmine were 1:10, 6%, 3% and 40 mg, respectively. The negatively charged PPNMCs had an average particle size of 937.9 nm. Compared with free pyridostigmine, PPNMCs showed an initial burst release and a subsequent very slow release in vitro. The release profiles for the PPNMCs in four different types of dissolution medium were fitted to the Ritger-Peppas and Weibull models. The similarity between pairs of dissolution profiles for the PPNMCs in different types of medium was statistically significant, and the difference between the release curves for PPNMCs and free pyridostigmine was also statistically significant. Conclusion PPNMCs prepared by the optimized protocol described here were in the nanometer range and had good uniformity

  12. Nanosized sustained-release pyridostigmine bromide microcapsules: process optimization and evaluation of characteristics.

    PubMed

    Tan, Qunyou; Jiang, Rong; Xu, Meiling; Liu, Guodong; Li, Songlin; Zhang, Jingqing

    2013-01-01

    Pyridostigmine bromide (3-[[(dimethylamino)-carbonyl]oxy]-1-methylpyridinium bromide), a reversible inhibitor of cholinesterase, is given orally in tablet form, and a treatment schedule of multiple daily doses is recommended for adult patients. Nanotechnology was used in this study to develop an alternative sustained-release delivery system for pyridostigmine, a synthetic drug with high solubility and poor oral bioavailability, hence a Class III drug according to the Biopharmaceutics Classification System. Novel nanosized pyridostigmine-poly(lactic acid) microcapsules (PPNMCs) were expected to have a longer duration of action than free pyridostigmine and previously reported sustained-release formulations of pyridostigmine. The PPNMCs were prepared using a double emulsion-solvent evaporation method to achieve sustained-release characteristics for pyridostigmine. The preparation process for the PPNMCs was optimized by single-factor experiments. The size distribution, zeta potential, and sustained-release behavior were evaluated in different types of release medium. The optimal volume ratio of inner phase to external phase, poly(lactic acid) concentration, polyvinyl alcohol concentration, and amount of pyridostigmine were 1:10, 6%, 3% and 40 mg, respectively. The negatively charged PPNMCs had an average particle size of 937.9 nm. Compared with free pyridostigmine, PPNMCs showed an initial burst release and a subsequent very slow release in vitro. The release profiles for the PPNMCs in four different types of dissolution medium were fitted to the Ritger-Peppas and Weibull models. The similarity between pairs of dissolution profiles for the PPNMCs in different types of medium was statistically significant, and the difference between the release curves for PPNMCs and free pyridostigmine was also statistically significant. PPNMCs prepared by the optimized protocol described here were in the nanometer range and had good uniformity, with significantly slower pyridostigmine

  13. Effect of ion structure on conductivity in lithium-doped ionic liquid electrolytes: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Liu, Hongjun; Maginn, Edward

    2013-09-01

    Molecular dynamics simulations were performed to examine the role cation and anion structure have on the performance of ionic liquid (IL) electrolytes for lithium conduction over the temperature range of 320-450 K. Two model ionic liquids were studied: 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([bmim][Tf2N]) and 1-butyl-4-methylpyridinium pyrrolide ([bmpyr][pyl]) doped with Li[Tf2N] and Li[pyl], respectively. The results have demonstrated that the Li+ doped IL containing the planar [bmpyr] cation paired with the planar [pyl] anion significantly outperformed the [bmim][Tf2N] IL. The different coordination of Li+ with the [Tf2N]- or [pyl]- anions produces a remarkable change in IL structure with a concomitant effect on the transport of all ions. For the doped [bmim][Tf2N], each Li+ is coordinated by four oxygen atoms from [Tf2N]- anions. Formation of a rigid structure between Li+ and [Tf2N]- induces a decrease in the mobility of all ions. In contrast, for the doped [bmpyr][pyl], each Li+ is coordinated by two nitrogen atoms from [pyl]- anions. The original alternating structure cation|anion|cation in the neat [bmpyr][pyl] is replaced by another alternating structure cation|anion|Li+|anion|cation in the doped [bmpyr][pyl]. Increases of Li+ mole fraction in doped [bmpyr][pyl] affects the dynamics to a much lesser extent compared with [bmim][Tf2N] and leads to reduced diffusivities of cations and anions, but little change in the dynamics of Li+. More importantly, the calculations predict that the Li+ ion conductivity of doped [bmpyr][pyl] is comparable to that observed in organic liquid electrolytes and is about an order of magnitude higher than that of doped [bmim][Tf2N]. Such Li+ conductivity improvement suggests that this and related ILs may be promising candidates for use as electrolytes in lithium ion batteries and capacitors.

  14. Morphological changes of the dermatophyte Trichophyton rubrum after photodynamic treatment: a scanning electron microscopy study.

    PubMed

    Smijs, Threes G M; Mulder, Aat A; Pavel, Stan; Onderwater, Jos J M; Koerten, Henk K; Bouwstra, Joke A

    2008-06-01

    Treatment strategies for superficial mycosis caused by the dermatophyte Trichophyton rubrum consist of the use of topical or oral antifungal preparations. We have recently discovered that T. rubrum is susceptible to photodynamic treatment (PDT), with 5,10,15-tris(4-methylpyridinium)-20-phenyl-[21H,23H]-porphine trichloride (Sylsens B) as a photosensitizer. The susceptibility appeared to depend on the fungal growth stage, with PDT efficacy higher with microconidia when compared to mycelia. The aim of this study was to investigate, with the use of scanning electron microscopy, the morphological changes caused by a lethal PDT dose to T. rubrum when grown on isolated human stratum corneum. Corresponding dark treatment and light treatment without photosensitizer were used as controls. A sub-lethal PDT dose was also included in this investigation The morphologic changes were followed at various time points after the treatment of different fungal growth stages. Normal fungal growth was characterized by a fiber-like appearance of the surface of the hyphae and microconidia with the exception of the hyphal tips in full mycelia and the microconidia shortly after attachment to the stratum corneum. Here, densely packed globular structures were observed. The light dose (108 J/cm2) in the absence of Sylsens B, or the application of the photosensitizer in the absence of light, caused reversible fungal wall deformations and bulge formation. However, after a lethal PDT, a sequence of severe disruptions and deformations of both microconidia and the mycelium were observed leading to extrusion of cell material and emptied fungal elements. In case of a non-lethal PDT, fungal re-growth started on the remnants of the treated mycelium.

  15. Chronic Intermittent Hypoxia Alters Local Respiratory Circuit Function at the Level of the preBötzinger Complex

    PubMed Central

    Garcia, Alfredo J.; Zanella, Sebastien; Dashevskiy, Tatiana; Khan, Shakil A.; Khuu, Maggie A.; Prabhakar, Nanduri R.; Ramirez, Jan-Marino

    2016-01-01

    Chronic intermittent hypoxia (CIH) is a common state experienced in several breathing disorders, including obstructive sleep apnea (OSA) and apneas of prematurity. Unraveling how CIH affects the CNS, and in turn how the CNS contributes to apneas is perhaps the most challenging task. The preBötzinger complex (preBötC) is a pre-motor respiratory network critical for inspiratory rhythm generation. Here, we test the hypothesis that CIH increases irregular output from the isolated preBötC, which can be mitigated by antioxidant treatment. Electrophysiological recordings from brainstem slices revealed that CIH enhanced burst-to-burst irregularity in period and/or amplitude. Irregularities represented a change in individual fidelity among preBötC neurons, and changed transmission from preBötC to the hypoglossal motor nucleus (XIIn), which resulted in increased transmission failure to XIIn. CIH increased the degree of lipid peroxidation in the preBötC and treatment with the antioxidant, 5,10,15,20-Tetrakis (1-methylpyridinium-4-yl)-21H,23H-porphyrin manganese(III) pentachloride (MnTMPyP), reduced CIH-mediated irregularities on the network rhythm and improved transmission of preBötC to the XIIn. These findings suggest that CIH promotes a pro-oxidant state that destabilizes rhythmogenesis originating from the preBötC and changes the local rhythm generating circuit which in turn, can lead to intermittent transmission failure to the XIIn. We propose that these CIH-mediated effects represent a part of the central mechanism that may perpetuate apneas and respiratory instability, which are hallmark traits in several dysautonomic conditions. PMID:26869872

  16. Assessment of alcohol ethoxylate surfactants and fatty alcohols mixtures in river sediments and prospective risk assessment.

    PubMed

    Dyer, Scott D; Sanderson, Hans; Waite, Scott W; Van Compernolle, Remi; Price, Bradford; Nielsen, Allen M; Evans, Alex; Decarvalho, Alvaro J; Hooton, Dennis J; Sherren, Andrew J

    2006-09-01

    A feasible and relatively readily available analytical method was adapted for the assessment of alcohol ethoxylates (AE) and fatty alcohols (FA) in sediments. This study illustrates the simultaneous measurement of 38 of 114 possible alcohol ethoxylate ethoxymers (AE) and fatty alcohols (FA) found in commercially important AE products. We predicted toxicity for all identified fractions, as well as the total mixture toxicity, relative to three exposure scenarios via sewage treatment plants (STP) for these widely used chemicals in consumer products and hence generate a preliminary environmental risk screening for AE and FA in sediments. The method is based on derivatization of solvent or solid-phase extracts with 2-fluoro-N-methylpyridinium p-toluenesulfonate (Pyr+). The derivatized extracts were analyzed with liquid chromatography/mass spectrometry (LC/MS) operating in the positive ion electrospray mode. The extraction efficiency of AE and FA in three different sediments of varying composition was evaluated with spike-recovery studies, ranging from 64% to 80%. The detection limits for individual ethoxymers typically ranged from 1 to 5 ngg(-1)on a dry weight basis. The mean limit of detection (LOD) was 6 ngg(-1)and the median LOD was 3 ngg(-1). AE and FA in sediments were found to be stable for two weeks if preserved with 3% (v/v) formalin and stored at 4-6( composite function)C. Based on equilibrium partitioning, background concentrations of AE and FA were predicted to be below concentrations known to elicit chronically toxic effects. Total worst case mixture toxicities for all AE ethoxymers combined with FA were predicted to result in a risk quotient less than 0.6. Activated sludge treatment (STP) significantly reduced the release of total AE and FA by four-fold, suggesting that the total mixture risk quotient would be < 0.15 for sediment dependent organisms.

  17. Evaluation of organic cation transporter 3 (SLC22A3) inhibition as a potential mechanism of antidepressant action.

    PubMed

    Zhu, Hao-Jie; Appel, David I; Gründemann, Dirk; Richelson, Elliott; Markowitz, John S

    2012-04-01

    Organic cation transporter 3 (OCT3, SLC22A3) is a low-affinity, high-capacity transporter widely expressed in the central nervous system (CNS) and other major organs in both humans and rodents. It is postulated that OCT3 has a role in the overall regulation of neurotransmission and maintenance of homeostasis within the CNS. It is generally believed that all antidepressant drugs in current clinical use exert their primary therapeutic effects through inhibition of one or more of the high-affinity neuronal plasma membrane monoamine transporters, such as the norepinephrine transporter and the serotonin transporter. In the present study, we investigated the inhibitory effects of selected antidepressants on OCT3 activity in OCT3-transfected cells to evaluate whether OCT3 inhibition may at least in part contribute to the pharmacological effects of tested antidepressants. The studies demonstrated that all examined antidepressants inhibited OCT3-mediated uptake of the established OCT3 substrate 4-(4-(dimethylamino)styryl)-N-methylpyridinium iodide (4-Di-1-ASP) in a concentration-dependent manner. The IC(50) values were determined to be 4.7 μM, 7.4 μM, 12.0 μM, 18.6 μM, 11.2 μM, and 21.9 μM for desipramine, sertraline, paroxetine, amitriptyline, imipramine, and fluoxetine, respectively. Additionally, desipramine had an IC(50) value of 0.7 μM for the uptake of NE by OCT3, while the IC(50) value of sertraline was 2.3 μM for 5-HT uptake. Both desipramine and sertraline appeared to inhibit OCT3 activity via a non-competitive mechanism. In vivo studies are warranted to determine whether such effects on OCT3 inhibition are of sufficient magnitude to contribute to the overall therapeutic effects of antidepressants.

  18. Lipopolysaccharide-induced serotonin transporter up-regulation involves PKG-I and p38MAPK activation partially through A3 adenosine receptor.

    PubMed

    Zhao, Rui; Wang, Shoubao; Huang, Zhonglin; Zhang, Li; Yang, Xiuying; Bai, Xiaoyu; Zhou, Dan; Qin, Zhizhen; Du, Guanhua

    2015-12-01

    Serotonin transporter (SERT) is a critical determinant of synaptic serotonin (5-hydroxytryptamine, 5-HT) inactivation which plays a critical role in the pathology of depression and other mood disorders. Lipopolysaccharide (LPS), a potent activator of the inflammatory system, has been reported to cause depression symptoms by the modulation of SERT in vivo and in vitro. This study is aimed to investigate the underlying mechanism of LPS-induced SERT modulation. The 4-(4-(dimethylamino) styryl)-N-methylpyridinium iodide (ASP) assay was used to detect dynamic 5-HT uptake as read out of SERT activities in RBL-2H3 cells, and cytosol Ca(2+) concentrations ([Ca(2+)]i) and nitric oxide (NO) were examined. Using specific cyclic GMP-dependent protein kinase type I (PKG-I), p38 mitogen-activated protein kinases (p38MAPK) and A3 adenosine receptor (A3AR) inhibitors, SERT expression was evaluated by western blot and immunofluorescence analysis. Results showed that 24 h treatment with LPS stimulated 5-HT transport and up-regulate plasma membrane distribution of SERT in RBL-2H3 cells. LPS treatment increased NO and [Ca(2+)]i, and led to significant increases in levels of phosphorylated calcium/calmodulin-dependent protein kinase type II (CaMK-II), inducible NOS (iNOS) and PKG-I as well as active p38 MAPK. Moreover, PKG-I inhibitor KT5823 or p38MAPK inhibitor SB203580 respectively impaired SERT activation and transposition to plasma membrane by LPS. Notably, A3 adenosine receptor inhibitor MRS1191 also hindered SERT stimulation by LPS. In conclusion, LPS-induced 5-HT uptake and transposition to plasma membrane of SERT in RBL-2H3 cells involves CaMK-II/iNOS/PKG-I and p38 MAPK activation, which may be partially mediated by A3 adenosine receptor activation. This finding provides a novel insight into the interrelationship between LPS and depression.

  19. On the investigation of the bilayer functionalities of 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) large unilamellar vesicles using cationic hemicyanines as optical probes: a wavelength-selective fluorescence approach.

    PubMed

    Moyano, Fernando; Silber, Juana J; Correa, N Mariano

    2008-01-01

    The behavior of the cationic hemicyanines trans-4-[4-(dimethylamino)-styryl]-1-methylpyridinium iodide (HC) and 4,(4-(dihexadecylamino)styryl-N-methyl-pyridinium iodide (DIA) were studied in large unilamellar vesicles (LUV) of 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) using absorption, emission, depolarization and time resolved spectroscopies. Also, thorough spectroscopic studies were performed in homogeneous media to investigate the different interactions that the dyes can experience with its microenvironment. These results help us to comprehend the dye performance under different media and, consequently find interesting features of the DOPC membrane properties. The studies in homogeneous media analyzed by the Kamlet and Taft's solvatochromic comparison method demonstrate, for the first time, that the cationic hemycianines undergo specific interactions with the medium through the solvents ability to donate an electron pair as measured by the beta parameter. Thus, the absorption bands shifts bathochromically with beta while, the emission band shifts hypsochromically. In addition, for the relaxed hemicyanines the 00 energy, nu00, is invariant with the solvent properties. The results in LUV of DOPC show that, DIA undergoes a strong association with the vesicle bilayer while HC partitions between the water and the bilayer pseudophases. To monitor directly the microenvironment and dynamics around HC and DIA inside the DOPC bilayer, we use the wavelength-selective fluorescence approach, which is based on the red edge effect in fluorescence spectroscopy, in addition with the nu00 energy of the hemicyanines. The results show that the fluid state of the DOPC bilayer resembles the microenvironment of sodium bis (2-ethylhexyl) sulfosuccinate (AOT) reverse micelles at W=[H2O]/[AOT] below 10 where there is no free water forming the water pool. Moreover, it is demonstrated for the first time, that the region of the bilayer close to the polar head of DOPC is a

  20. Presence and function of dopamine transporter (DAT) in stallion sperm: dopamine modulates sperm motility and acrosomal integrity.

    PubMed

    Urra, Javier A; Villaroel-Espíndola, Franz; Covarrubias, Alejandra A; Rodríguez-Gil, Joan Enric; Ramírez-Reveco, Alfredo; Concha, Ilona I

    2014-01-01

    Dopamine is a catecholamine with multiple physiological functions, playing a key role in nervous system; however its participation in reproductive processes and sperm physiology is controversial. High dopamine concentrations have been reported in different portions of the feminine and masculine reproductive tract, although the role fulfilled by this catecholamine in reproductive physiology is as yet unknown. We have previously shown that dopamine type 2 receptor is functional in boar sperm, suggesting that dopamine acts as a physiological modulator of sperm viability, capacitation and motility. In the present study, using immunodetection methods, we revealed the presence of several proteins important for the dopamine uptake and signalling in mammalian sperm, specifically monoamine transporters as dopamine (DAT), serotonin (SERT) and norepinephrine (NET) transporters in equine sperm. We also demonstrated for the first time in equine sperm a functional dopamine transporter using 4-[4-(Dimethylamino)styryl]-N-methylpyridinium iodide (ASP(+)), as substrate. In addition, we also showed that dopamine (1 mM) treatment in vitro, does not affect sperm viability but decreases total and progressive sperm motility. This effect is reversed by blocking the dopamine transporter with the selective inhibitor vanoxerine (GBR12909) and non-selective inhibitors of dopamine reuptake such as nomifensine and bupropion. The effect of dopamine in sperm physiology was evaluated and we demonstrated that acrosome integrity and thyrosine phosphorylation in equine sperm is significantly reduced at high concentrations of this catecholamine. In summary, our results revealed the presence of monoamine transporter DAT, NET and SERT in equine sperm, and that the dopamine uptake by DAT can regulate sperm function, specifically acrosomal integrity and sperm motility.