Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), (1)H and (13)C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, (13)C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.

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.

Thioxanthone Sensitized Photodegradation of Poly(alkyl methacrylate) Films

The thioxanthone-sensitized photodegradation of poly(alkyl methacrylate) films [alkyl = methyl, ethyl, butyl, and hexyl] was studied using near UV-vis light. The photooxidation process continued even after the total consumption of the sensitizer, possibly due to the excitation of the ketyl groups formed during the first stages of the process. The rate of oxidation, as well as the formation of hydroxy, peroxy, and ketyl groups was faster for polymers with larger ester groups. The decrease of the molecular weight of the degradated polymers was also larger for the hexyl substituted polymer. The side-chain size effect was attributed to the larger amount of secondary hydrogens available for abstraction by the triplet state of thioxanthone, present in the larger ester groups. The lower glass transition temperature of the hexyl substituted polymer allows a better diffusion of oxygen to the deeper layers of the films that also contributes to the faster photodegradation rate. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 1283-1288, 2010

Preparation of polymeric micelles for use as carriers of tuberculostatic drugs

Purpose: This paper focuses on the characterization of polymeric micelle-forming tuberculostatic prodrugs and the antimycobacterial activity of these prodrugs.Method: By the condensation of hydroxymethylpyrazinamide, isoniazid and rifampin with free carboxyl groups on the copolymer poly(ethyleneglycol)-poly(aspartic acid), micelle-forming carrier-drug conjugates were obtained. These micelles were characterized by dynamic light scattering, to measure the micelle diameter; by acid-base titration, to determine the percentage of carboxylic groups occupied by the tuberculostatic; by Sudan III solubility tests, to estimate the critical micelle concentration (CMC); and visual control and spectrophotometric measurement, to determine the stability of micelles. These micelles were tested in vitro against several Mycobacterium strains.Results: As expected, the size and distribution of the micelle-forming tuberculostatic prodrugs found to be small (78.2nm, 84.2nm and 98.9 nm) while the level of the drug conjugated was high (65.02-85.7%). Furthermore, the micelles were stable in vitro, exhibiting a low level of CMC and stronger antimycobacterial activity than the original drugs.Conclusion: the results demonstrate that polymeric micelles can be used as efficient carriers for drugs, which alone, exhibit undesired pharmacokinetics, poor solubility, and low stability. The synthesized micelle-forming tuberculostatic prodrugs opens a perspective of alternative prodrugs that prolong action and decrease the toxicity of the tuberculostatic drugs of choice.

Influence of rare earth doping on the structural and catalytic properties of nanostructured tin oxide

Nanoparticles of tin oxide, doped with Ce and Y, were prepared using the polymeric precursor method. The structural variations of the tin oxide nanoparticles were characterized by means of nitrogen physisorption, carbon dioxide chemisorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The synthesized samples, undoped and doped with the rare earths, were used to promote the ethanol steam reforming reaction. The SnO2-based nanoparticles were shown to be active catalysts for the ethanol steam reforming. The surface properties, such as surface area, basicity/base strength distribution, and catalytic activity/selectivity, were influenced by the rare earth doping of SnO2 and also by the annealing temperatures. Doping led to chemical and micro-structural variations at the surface of the SnO2 particles. Changes in the catalytic properties of the samples, such as selectivity toward ethylene, may be ascribed to different dopings and annealing temperatures.

Indium tin oxide films prepared via wet chemical route

In this work, indium tin oxide (ITO) films were prepared using a wet chemical route, the Pechini method. This consists of a polyesterification reaction between an alpha-hydroxicarboxylate complex (indium citrate and tin citrate) with a polyalcohol (ethylene glycol) followed by a post annealing at 500 degrees C. A 10 at.% of doping of Sn4+ ions into an In2O3 matrix was successfully achieved through this method. In order to characterize the structure, the morphology as well as the optical and electrical properties of the produced ITO films, they were analyzed using different experimental techniques. The obtained films are highly transparent, exhibiting transmittance of about 85% at 550 nm. They are crystalline with a preferred orientation of [222]. Microscopy discloses that the films are composed of grains of 30 nm average size and 0.63 nm RMS roughness. The films' measured resistivity, mobility and charge carrier concentration were 5.8 x 10(-3) Omega cm, 2.9 cm(2)/V s and -3.5 x 10(20)/cm(3), respectively. While the low mobility value can be related to the small grain size, the charge carrier concentration value can be explained in terms of the high oxygen concentration level resulting from the thermal treatment process performed in air. The experimental conditions are being refined to improve the electrical characteristics of the films while good optical, chemical, structural and morphological qualities already achieved are maintained. (C) 2007 Elsevier B.V. All rights reserved.

Structure of magnetic poly(oxyethylene)-siloxane nanohybrids doped with Fe-II and Fe-III

Hybrid organic - inorganic nanocomposites doped with Fe-II and Fe-III ions and exhibiting interesting magnetic properties have been obtained by the sol - gel process. The hybrid matrix of these ormosils ( organically modified silicates), classed as di-ureasils and termed U( 2000), is composed of poly( oxyethylene) chains of variable length grafted to siloxane groups by means of urea crosslinkages. Iron perchlorate and iron nitrate were incorporated in the diureasil matrices, leading to compositions within the range 80 greater than or equal to n greater than or equal to 10, n being the molar ratio of ether-type O atoms per cation. The structure of the doped diureasils was investigated by small-angle X-ray scattering (SAXS). For Fe-II-doped samples, SAXS results suggest the existence of a two-level hierarchical structure. The primary level is composed of spatially correlated siloxane clusters embedded in the polymeric matrix and the secondary, coarser level consists of domains where the siloxane clusters are segregated. The structure of Fe-III-doped hybrids is different, revealing the existence of iron oxide based nanoclusters, identified as ferrihydrite by wide-angle X-ray diffraction, dispersed in the hybrid matrix. The magnetic susceptibility of these materials was determined by zero-field-cooling and field-cooling procedures as functions of both temperature and field. The different magnetic features between Fe-II- and Fe-III-doped samples are consistent with the structural differences revealed by SAXS. While Fe-II-doped composites exhibit a paramagnetic Curie-type behaviour, hybrids containing Fe-III ions show thermal and field irreversibilities.

Interface morphology snapshots of vertically segregated thin films of semiconducting polymer/polystyrene blends

We present atomic force microscopic images of the interphase morphology of vertically segregated thin films spin coated from two-component mixtures of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene-vinylene] (MEH-PPV) and polystyrene (PS). We investigate the mechanism leading to the formation of wetting layers and lateral structures during spin coating using different PS molecular weights, solvents and blend compositions. Spinodal decomposition competes with the formation of surface enrichment layers. The spinodal wavelength as a function of PS molecular weight follows a power-law similar to bulk-like spinodal decomposition. Our experimental results indicate that length scales of interface topographical features can be adjusted from the nanometer to micrometer range. The importance of controlled arrangement of semiconducting polymers in thin film geometries for organic optoelectronic device applications is discussed. (c) 2007 Elsevier Ltd. All rights reserved.

Synthesis and some properties of hybrid gels of titanium oxide containing europium (III)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Polyol-mediated synthesis of ultrafine tin oxide nanoparticles for reversible Li-ion storage

A simple, cheap and versatile, polyol-mediated fabrication method has been extended to the synthesis of tin oxide nanoparticles on a large scale. Ultrafine SnO2 nanoparticles with crystallite sizes of less than 5 nm were realized by refluxing SnCl2 . 2H(2)O in ethylene glycol at 195 degrees C for 4 h under vigorous stirring in air. The as-prepared SnO2 nanoparticles exhibited enhanced Li-ion storage capability and cyclability, demonstrating a specific capacity of 400 mAh g(-1) beyond 100 cycles. (c) 2006 Elsevier B.V. All rights reserved.

Dinuclear Azide-Bridged Copper(II) Complex as Building Block for the Assembly of a 2D-Supramolecular Array

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Heterogeneous Fenton reactants: a study of the behavior of iron oxide nanoparticles obtained by the polymeric precursor method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ebselen and cytokine-induced nitric oxide synthase expression in insulin-producing cells

Interleukin-1 (IL-1) may be a mediator of β-cell damage in insulin-dependent diabetes mellitus (IDDM). The IL-1 mechanism of action on insulin-producing cells probably includes activation of the transcription nuclear factor κB (NF-κB), increased transcription of the inducible form of nitric oxide synthase (iNOS) and the subsequent production of nitric oxide (NO). Reactive oxygen intermediates, particularly H2O2, have been proposed as second messengers for NF-κB activation. In the present study, we tested whether ebselen (2-phenyl-1,2-benzisoselenazol-3(2H)-one), a glutathione peroxidase mimicking compound, could counteract the effects of IL-1β, H2O2 and alloxan in rat pancreatic islets and in the rat insulinoma cell line RINm5F (RIN cells). Some of these experiments were also reproduced in human pancreatic islets. Ebselen (20 μM) prevented the increase in nitrite production by rat islets exposed to IL-1β for 6 hr and induced significant protection against the acute inhibitory effects of alloxan or H2O2 exposure, as judged by the preserved glucose oxidation rates. However, ebselen failed to prevent the increase in nitrite production and the decrease in glucose oxidation and insulin release by rat islets exposed to IL-1β for 24 hr. Ebselen prevented the increase in nitrite production by human islets exposed for 14 hr to a combination of cytokines (IL-1β, tumor necrosis factor-α and interferon-γ). In RIN cells, ebselen counteracted both the expression of iNOS mRNA and the increase in nitrite production induced by 6 hr exposure to IL-β but failed to block IL-1β-induced iNOS expression following 24 hr exposure to the cytokine. Moreover, ebselen did not prevent IL-1β-induced NF-κB activation. As a whole, these data indicate that ebselen partially counteracts cytokine-induced NOS activation in pancreatic β-cells, an effect not associated with inhibition of NF-κB activation.

Rheological properties of tin oxide suspensions

The rheological properties of tin oxide slurries were studied experimentally and theoretically. The deflocculants used were ammonium polyacrilate (PAA) and the copolymer poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (PVB-PVA-PVAc), in water and ethanol, respectively. The amount of deflocculant was optimized for different solid contents by means of viscosity measurements. In spite of the high stability of PVB-dispersed slurries, a high solid concentration was not obtained. On the other hand, a slurry with a 56.4 vol.% of solids was attained when PAA was used. A theoretical study of the adsorption of PAA in its dissociated (basic solution) and non-dissociated (acidic solution) forms on SnO 2 (110) is presented. This analysis was made by means of the PM3 method using a large cluster Sn 15O 28 for the surface model. The calculated adsorption energy is larger for the ionized PAA than for the non-ionized form, indicating that alkaline slurries favor PAA adsorption on the SnO 2 surface. © 2002 Elsevier Science Ltd. All rights reserved.

Structural control of photoluminescence of four poly(urethane-urea-co-1,3,5-triazine)s: Synthesis and characterization

A series of segmented poly(urethane-urea)s containing 1,3,5 triazine in the hard block and hexamethylene spacers in the soft block was prepared. The hard to soft segment ratio was varied systematically, to afford a series of polymers in which the chromophore concentration varied from 4.2% to 18.1%. Although triazine emission is located in the UV region, the films with higher content of the chromophore emitted a visible blue light (425 nm) when excited at the very red-edge of the absorption band. The photophysical properties of the materials were strongly dependent on the relative amount of triazine moieties along the main chain. Isolated moieties emit in copolymers with small amount of triazine groups, indicating that even though in solid state, these moieties tend to be apart. Two photophysical consequences were observed when the amount of triazine increases: there is some energy transfer process involving isolated moieties with consequent decrease of the lifetime and an additional red-edge emission attributed to aggregated lumophores. The mono-exponential decay observed for the isolated form is substituted by a bi-exponential decay of the aggregated species. The materials were not strong emitters, but since the N-containing triazine moieties are good electron transport groups, the polymers have potential application as electron transport enhancers in various applications. © 2006 Elsevier B.V. All rights reserved.