Tryptophan photooxidation promoted by new hybrid materials prepared by condensation of naphthalene imides with silicate by the sol-gel process

Three novel hybrid organic/inorganic materials were synthesized from 4-substituted (NO(2), Br, H) 1,8-naphthalene imide-N-propyltriethoxysilane by the sol-gel process. These materials were obtained as a xerogel and partially characterized. The ability to photosensitize the oxidation and degradation of tryptophan indole ring by these materials was studied through photophysical and photochemical techniques. Although the derivatives containing Br and NO(2) as substituent do not cause efficient tryptophan photodamage, the hybrid material obtained from 1,8-naphthalic anhydride is very efficient to promote tryptophan photooxidation. By using laser flash photolysis it was possible to verify the presence of naphthalene imide transient radical species. The presence of oxygen causes an increase of the yield of radical formation. These results suggest that the mechanism of photodegradation of tryptophan occurs by type I, i.e. the transient radical (TrpH(center dot+)) formed by the direct reaction of the triplet state of the naphthalene imide moiety with tryptophan. Thus a inorganic-organic hybrid material that can be used to promote the oxidation of biomolecules was obtained. (C) 2009 Elsevier B.V. All rights reserved.

Identification of lift-off mechanism failure for salt drill-in drilling fluid containing polymer filter cake through adsorption/desorption studies

Drilling fluid`s contact with the productive zone of horizontal or complex wells can reduce well productivity by fluid invasion in the borehole wall. Salted drilling drill-in fluid containing polymers has often been applied in horizontal or complex petroleum wells in the poorly consolidated sandstone reservoirs of the Campos basin, Rio de Janeiro, Brazil. This fluid usually consists of natural polymers such as starch and xanthan gum, which are deposited as a filter cake on the wellbore wall during the drilling. Therefore, the identification of a lift-off mechanism failure, which can be detachment or blistering and pinholing, will enable formulation improvements. increasing the chances of success during filter cake removal in open hole operations. Likewise, knowledge of drill-in drilling fluid adsorption/desorption onto sand can help understand the filter cake-rock adhesion mechanism and consequently filter cake lift-off mechanism failures. The present study aimed to identify the lift-off failure mechanism for this type of fluid filter cake studying adsorption/desorption onto SiO(2) using solutions of natural polymers, lubricants, besides the fluid itself. Ellipsometry was employed to measure this process. The adsorption/desorption studies showed that the adsorbed layer of drilling fluid onto the walls of the rock pores is made up of clusters of polymers, linked by hydrogen bonds, which results in a force of lower cohesion compared to the electrostatic interaction between silica and polymers. Consequently, it was found that the most probable filter cake failure mechanism is rupture (blistering and pinholing), which results in the formation of ducts within the filter cake. (C) 2009 Elsevier B.V. All rights reserved.

Nitric oxide sensing by cytochrome c bonded to a conducting polymer modified glassy carbon electrode

A nitric oxide biosensor based on cytochrome c (an heme protein) covalently immobilized to poly(5-amino-1-naphthol) by using cyanuric chloride as a bridge was developed. The immobilization was studied by cyclic voltammetry and quartz crystal microbalance. The nitric oxide detection as a function of poly(5-amino-1-naphthol) amount was recorded, and the best result was obtained with the electrode prepared by 70 cycles. The sensitivity and detection limit were 0.015 mu A cm(-2)/mu mol L(-1) and 2.85 mu mol L(-1), respectively. (C) 2009 Elsevier B.V. All rights reserved.

On the energy transfer from a polymer host to the rhenium(I) complex in OLEDs

Photoluminescence and electroluminescence of PVK films doped with fac-[ClRe(CO)(3)(bpy)], bpy=2,2`-bipyridine, are investigated. Photoluminescence spectra of spin-coated PVK films (lambda(exc)=290 nm) exhibit a broad band centered at 405 nm. As the concentration of dopant increases, the polymer emission is quenched and a band at 555 nm appears (isosbestic point at 475 nm). In OLEDs with ITO/PEDOT:PSS/PVK/butylPBD/Al architecture doped with fac-[ClRe(CO)(3)(bpy)], the polymer host emission is completely quenched even at the lowest concentration of dopant. The electroluminescence spectra of the devices show that there is an efficient energy transfer from the host to the dopant, which exhibits a very intense emission at 580 nm. (C) 2009 Elsevier B.V. All rights reserved.

PVP superabsorbent nanogels

Monomer free hydrogel nanoparticles (nanogels) were prepared by crosslinking preformed poly(N-vinyl-2-pyrrolidone) (PVP) entrapped in the aqueous pool of hexadecyltrimethylammonium bromide reverse micelles using the Fenton reaction. The PVP nanoparticles were spherical with a dry diameter of 27 nm. The diameter of the swollen particles was ten times higher, i.e., a swelling ratio, Q, above 900, characterizing this preparation as superabsorbent. PVP nanogel swelling was dependent on bound Fe(3+) and varied with pH and ionic strength. Nanogel deswelling by salt followed the anions lyotropic series, i.e., SCN(-) < HSO(3)(-) < NO(3)(-) < I(-) < Cl(-) < CH(3)COO(-) < CF(3)SO(3)(-). The value of Q reached 6,000 in iron-free PVP nanoparticles at low pH, making this nanogel one of the most efficient swelling systems so far described.

Luminescent nanoparticles of MgAl(2)O(4):Eu, Dy prepared by citrate sol-gel method

MgAl(2)O(4):Eu, Dy nanoparticles were prepared by citrate sol-gel method and thermally treated at 600, 700, 800 and 900 degrees C. The trivalent europium ion is partially reduced to the divalent state at 700 and 800 degrees C. Infrared spectra of the phosphors showed bands around 700 and 520 cm(-1) corresponding to the AlO(6) groups. X-ray diffraction patterns present sharp reflections of samples heated from 700 to 900 degrees C indicating the MgAl(2)O(4) spinel phase. Grain size in the range 20-30 nm were observed by measurement of transmission electron microscopy (TEM). The emission spectra of the phosphors show a broadened band at 480 nm assigned to the 4f(G)5d -> 4f(7) ((8)S(7/2)) transition of Eu(2+) ion overlapped to the (4)F(9/2) -> (6)H(15/2) transition of the Dy(3+) ion. Besides, the (4)F(9/2) -> (6)H(13/2) transition (579 nm) of Dy(3+) ion is overlapped with the (5)D(0) -> (7)F(0) (578 nm) and (5)D(0) -> (7)F(1) (595 nm) transitions from the Eu(3+) ion. Excitation spectra of the sample heated at 900 degrees C monitoring the excitation at 615 nm of (5)D(0) -> (7)F(2) transition of Eu(3+) ion exhibit a broad band assigned to the O -> Eu(3+) ligand-to-metal charge-transfer states (LMCT) around 280 nm. The samples present green persistent luminescence after exposure to UV radiation. The chromaticity coordinates were obtained from the luminescence emission spectrum. (C) 2008 Elsevier B.V. All rights reserved.

A selective conductive polymer-based sensor for volatile halogenated organic compounds (VHOC)

A novel poly(p-xylylene), PPX, derivative bearing alkoxyphenyl side groups was electrochemically synthesized in 87% yield. The polymer, poly(4`-hexyloxy-2,5-biphenyleneethylene) (PHBPE), presented a fraction (92%) soluble in common organic solvents. It showed to be thermally resistant up to 185 degrees C. UV-vis analysis revealed an E-gap of 3.5 eV Gas sensors made from thin films of 10-camphorsulfonic acid-doped PHBPE deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five VHOCs: 1,2-dichloroethane, bromochloromethane, trichloromethane, dichloromethane and tetrachloromethane. The conductance decreased after exposure to tetrachloromethane and increased after exposure to all the other VHOCs. Three-dimensional plots of relative response versus time of half response versus time of half recovery showed good discrimination between the five VHOCs tested. (c) 2008 Elsevier B.V. All rights reserved.

Influence of neodymium ions on photocatalytic activity of TiO(2) synthesized by sol-gel and precipitation methods

Titanium dioxide with and without the addition of neodymium ions was prepared using sol-gel and precipitation methods. The resulting catalysts were characterized by thermal analysis, X-ray diffraction and BET specific surface area. Neodymium addition exerted a remarkable influence on the phase transition temperature and the surface properties of the TiO(2) matrix. TiO(2) samples synthesized by precipitation exhibit an exothermic event related from the amorphous to anatase phase transition at 510 degrees C, whereas in Nd-doped TiO(2) this transition occurred at 527 degrees C. A similar effect was observed in samples obtained using sol-gel method. The photocatalytic reactivity of the catalysts was evaluated by photodegradation of Remazol Black B (RB) under ultraviolet irradiation. Nd-doped TiO(2) showed enhanced photodegradation ability compared to undoped TiO(2) samples, independent of the method of synthesis. In samples obtained by sol-gel, RB decoloration was enhanced by 16% for TiO(2) doped with 0.5% neodymium ions. (C) 2010 Elsevier B.V. All rights reserved.

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether, lithium perchlorate, and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) with LiClO(4), PEGdME/LiClO(4), and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, PEGdME/[bmim]PF(6), are compared. Raman spectroscopy suggests stronger interactions in PEGdME/LiClO(4) than PEGdmE/[bmim]PF(6), thus corroborating previous results obtained by molecular dynamics simulations. Quantum Chemistry methods have been used to calculate vibrational frequencies and the equilibrium structure of segments of the polymer chain around the cation. A consistent picture has been obtained from Raman spectroscopy, density functional theory (DFT) calculations, and molecular dynamics simulations for these polymer electrolytes. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and spectroscopic characterization of polymer and oligomers of ortho-phenylenediamine

Poly(ortho-phenylenediamine) and oligomers of ortho-phenylenediamine were chemically synthesized and characterized by UV-vis, (1)H and (13)C NMR, FTIR and resonance Raman spectroscopies. Polymerization of ortho-phenylenediamine in HCl medium with ammonium persulfate only leads the trimer compound, in disagreement with some previous reports. Nevertheless, in acetic acid medium it was possible to prepare a polymer constituted by ladder phenazinic segments with different protonation levels and quinonediimine rings (polyaniline-like). X-ray absorption at N K-edge (N K XANES), X-ray photoelectron (XPS) and Electron paramagnetic resonance (EPR) spectroscopies were used to determine the different kinds of nitrogen presents in this class of polymer. N K XANES spectrum of poly(ortho-phenylenediamine) shows the band of -N=nitrogen of non-protonated phenazinic rings at 398.2 eV. In addition, XPS and N K XANES data confirm the presence of different types of protonated nitrogens in the polymeric poly(ortho-phenylenediamine) chain and the EPR spectrum shows that the polymer has a very weak polaronic signal. (C) 2009 Elsevier Ltd. All rights reserved.

External polyacrylate-coating as alternative material for preparation of photopolymerized sol-gel monolithic column

Photopolymerized sol-gel monolithic columns for use in capillary electrochromatography were prepared in 125 mu m i.d. polyacrylate-coated fused-silica capillaries. The polyacrylate-coating, unlike the polyimide one, is transparent to the radiation used (approximate to 370 nm), and thus, no coating removal is necessary. This is a very important particularity since intrinsic capillary column characteristics, such as flexibility and mechanical resistance, are unchanged. A mixture containing metacryloxypropyltrimethoxysilane (MPTMS) as the polymeric precursor, hydrochloric acid as the catalyst, toluene as the porogen and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819) as the photoinitiator was irradiated at 370 nm for 20 min inside the capillaries to prepare the columns through sol-gel approach. The versatility and viability of the use of polyacrilate as a new capillary external coating were shown through preparation of two columns under different conditions, which were tested in electrochromatography for separation of standard mixture containing thiourea (marker compound), propylbenzene, phenanthrene and pyrene. (C) 2008 Elsevier B.V. All rights reserved.

All solid-state electrochromic devices with gelatin-based electrolyte

6 x 8cm(2) electrochromic devices (ECDs) with the configuration K-glass/EC-layer/electrotype/ion-storage (IS) layer/K-glass, have been assembled using Nb2O5:Mo EC layers, a (CeO2)(0.81)-TiO2 IS-layer and a new gelatin electrolyte containing Li+ ions. The structure of the electrolyte is X-ray amorphous. Its ionic conductivity passed by a maximum of 1.5 x 10(-5) S/CM for a lithium concentration of 0.3g/15ml. The value increases with temperature and follows an Arrhenius law with an activation energy of 49.5 kJ/mol. All solid-state devices show a reversible gray coloration, a long-term stability of more than 25,000 switching cycles (+/- 2.0 V/90 s), a transmission change at 550 nm between 60% (bleached state) and 40% (colored state) corresponding to a change of the optical density (Delta OD = 0. 15) with a coloration efficiency increasing from 10cm(2)/C (initial cycle) to 23cm(2)/C (25,000th cycle). (c) 2007 Elsevier B.V. All rights reserved.

The effects of hydrogen sulfide on the polymer electrolyte membrane fuel cell anode catalyst: H(2)S-Pt/C interaction products

The performance of a polymer electrolyte membrane fuel cell (PEMFC) operating on a simulated hydrocarbon reformate is described. The anode feed stream consisted of 80% H(2),similar to 20% N(2), and 8 ppm hydrogen sulfide (H(2)S). Cell performance losses are calculated by evaluating cell potential reduction due to H(2)S contamination through lifetime tests. It is found that potential, or power, loss under this condition is a result of platinum surface contamination with elemental sulfur. Electrochemical mass spectroscopy (EMS) and electrochemical techniques are employed, in order to show that elemental sulfur is adsorbed onto platinum, and that sulfur dioxide is one of the oxidation products. Moreover, it is demonstrated that a possible approach for mitigating H(2)S poisoning on the PEMFC anode catalyst is to inject low levels of air into the H(2)S-contaminated anode feeding stream. (C) 2011 Elsevier B.V. All rights reserved.

Gelatin-based protonic electrolyte for electrochromic windows

Proton-conducting gel polymer electrolytes based on gelatin plasticized with glycerol and containing acetic acid were investigated, characterized, and applied to electrochromic window. For glycerol contents varying from 7% to 48%, the conductivity of the uniform and predominantly amorphous gel electrolyte was found to follow a Vogel-Tamman-Fulcher behavior with the temperature. Typically, for the electrolyte chosen to make 7 x 2 cm(2) electrochromic smart window with the configuration: glass/fluor-doped tin oxide (FTO)/WO(3)/gelatin electrolyte/CeO(2)-TiO(2)/FTO/glass and containing 28% of glycerol, the conductivities were found to be of the order of 5 x 10(-5) S/cm at room temperature and 3.6 x 10(-4) S/cm at 80 A degrees C. The device was characterized by spectroelectrochemical techniques and was tested up to 10,000 cycles showing a fast coloring/bleaching behavior, where the coloring process was achieved in 10 s and the bleaching in 2 s. The transmission variation at the wavelength of 550 nm was about 15%. The cyclic voltammograms showed a very good reversibility of the cathodic/anodic processes, and the charge density was about 3.5 mC/cm(2). The memory tests showed that the transmittance in the colored state increased by 8% in 90 min after removing the potential.

Thermoset matrix reinforced with sisal fibers: Effect of the cure cycle on the properties of the biobased composite

Thermoset phenolic composites reinforced with sisal fibers were prepared to optimize the cure step. In the present study, processing parameters such as pressure, temperature, and time interval were varied to control the vaporization of the water generated as a byproduct during the crosslinking reaction. These molecules can vaporize forming voids, which in turn affect the final material properties. The set of results on impact strength revealed that the application of higher pressure before the gel point of the phenolic matrix produced composites with better properties. The SEM images showed that the cure cycle corresponding to the application of higher values of molding pressure at the gel point of the phenolic resin led to the reduction of voids in the matrix. In addition, the increase in the molding pressure during the cure step increased the resin interdiffusion. Better filling of the fiber channels decreased the possibility of water molecules diffusing through the internal spaces of the fibers. These molecules then diffused mainly through the bulk of the thermoset matrix, which led to a decrease in the water diffusion coefficient (D) at all three temperatures (25, 55 and 70 degrees C) considered in the experiments. (C) 2009 Elsevier Ltd. All rights reserved.