59 resultados para BRANCHED POLYMERS

em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"


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Calcium binding and charge distribution on highly branched and linear sulfated L-galactans from ascidians have been studied using a metallochromic indicator and conductimetric titrations. The distance between charged groups of the linear and highly branched galactans does not vary despite their marked differences in sulfate/total sugar molar ratios. These results indicate that the sulfated L-galactose units are concentrated in the central polysaccharide core and not intercalated among non-sulfated units. This inference is consistent with the chemical studies of these galactans. Surprisingly, calcium affinity increases with increasing amounts of non-sulfated sugar branches in the molecule. Thus, calcium binding in these polymers is not a simple function of availability of anion binding sites but a more complex calcium-polysaccharide interaction. (C) 1998 Elsevier B.V. Ltd. All rights reserved.

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Modelling polymers with side chains is always a challenge once the degrees of freedom are very high. In this study, we present a successful methodology to model poly[2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylenevinylene] (MEH-PPV) and poly[3-hexylthiophene] (P3HT) in solutions, taking into account the influence of side chains on the polymer conformation. Molecular dynamics and semi-empirical quantum mechanical methods were used for structure optimisation and evaluation of optical properties. The methodology allows to describe structural and optical characteristics of the polymers in a satisfactory way, as well as to evaluate some usual simplifications adopted for modelling these systems. Effective conjugation lengths of 8-14.6 and 21 monomers were obtained for MEH-PPV and P3HT, respectively, in accordance with experimental findings. In addition, anti/syn conformations of these polymers could be predicted based on intrinsic interactions of the lateral branches. © 2013 Copyright Taylor and Francis Group, LLC.

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

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Organic-inorganic hybrid materials based on the assembly between inorganic 2D host structure and polymer have received considerable attention in the last few years. This emerging class of materials presents several applications according to their structural and functional properties. Particularly, among others, layered double hydroxides (LDHs) provide the opportunity of preparing new organically modified 2D nanocomposites. Pyrrole carboxylic acid derivatives, namely 4-(lH-pyrrol-1-yl)benzoate, 3-(pyrrol-i-yl)-propanoate,7-(pyrrol-1-yl)-heptanoate, and aniline carboxylic acid derivative, namely 3-aminobenzoic acid, have been intercalated in LDHs of intralamellar composition Zn2Al(OH)(6). The LDHs were synthesized by the co-precipitation method at constant pH followed by hydrothermal treatment for 72 h. The materials were characterized by powder X-ray diffraction patterns (PXRD), transmission electron microscopy (TEM) thermogravimetric analysis (TGA), and electron spin resonance (ESR). The basal spacing found by the PXRD technique gives evidence of the formation of bilayers of the intercalated anions. ESR spectra present a typical signal with a superhyperfine structure with 6 + 1 lines (g = 2.005 +/- 0.0004), which is assigned to the interaction between a carboxylate radical from the guest molecules and a nearby aluminium nucleus (I = 5/2) from the host structure. Additionally, the ESR data suggest that the monomers are connected to each other in limited number after thermal treatment. (c) 2007 Elsevier Ltd. All rights reserved.

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Amorphous hydrogenated chlorinated carbon (a-C:H:Cl) films were produced by the plasma polymerization of chloroform-acetylene-argon mixtures in a radiofrequency plasma enhanced chemical vapor deposition system. The main parameter of interest was the proportion of chloroform in the feed, R(C), which was varied from 0 to 80%. Deposition rates of 80 nm min (1) were typical for the chlorinated films. Infrared reflection-absorption spectroscopy revealed the presence of C-Cl groups in all the films produced with chloroform in the feed. X-ray photoelectron spectroscopy confirmed this finding, and revealed a saturation of the chlorine content at similar to 47 at.% for R(C)>= 40%. The refractive index and optical gap, E(04), of the films were roughly in the 1.6 to 1.7, and the 2.8 to 3.7 eV range. These values were calculated from transmission ultraviolet-visible-near infrared spectra. Chlorination leads to an increase in the water surface contact angle from similar to 40 degrees to similar to 77 degrees. (C) 2011 Elsevier B.V. All rights reserved.

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This paper deals with the study of optical, structural and biocompatible properties of PEO-like plasma polymerized films resulting from RF excited diethylene glycol dimethyl ether (CH3O(CH2CH2O)(2)CH3 diglyme) glow discharges. The study was carried out using visible-ultraviolet and FTIR spectroscopies and contact angle measurements. FTIR spectra of plasma polymerized diglyme showed a stronger presence of ethylene glycol groups in film structure for lower RF power levels. The contact angle measurements for water revealed an increasing from 30degrees to 62,5degrees when the RF power was varied from 2 to 45 W, indicating the decreasing of the hydrophilic character of diglyme films with the increasing of RF power. This trend is in agreement with FTIR results. The data from visible-ultraviolet reflectance and transmittance spectra revealed alterations on optical properties of plasma polymerized diglyme films. The film's optical gap varied from 3.8 to 3 eV for RF power running from 5 to 45 W.

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Benzene plasma polymer films were bombarded with Ar ions by plasma immersion ion implantation. The treatments were performed using argon pressure of 3 Pa and 70 W of applied power. The substrate holder was polarized with high voltage negative pulses (25 kV, 3 Hz). Exposure time to the immersion plasma, t, was varied from 0 to 9000 s. Optical gap and chemical composition of the samples were determined by ultraviolet-visible and Rutherford backscattering spectroscopies, respectively. Film wettability was investigated by the contact angle between a water drop and the film surface. Nanoindentation technique was employed in the hardness measurements. It was observed growth in carbon and oxygen concentrations while there was decrease in the concentration of H atoms with increasing t. Furthermore, film hardness and wettability increased and the optical gap decreased with t. Interpretation of these results is proposed in terms of the chain crosslinking and unsaturation. (C) 2002 Elsevier B.V. B.V. All rights reserved.

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Plasma treatments are frequently employed to modify surface properties of materials such as adhesivity, hydrophobicity, oleophobicity etc. Present work deals with surface modification of common commercial polymers such as polyethylene terephthalate (PET) and polyurethane (PU) by an air dielectric barrier discharge (DBD) at atmospheric pressure. The DBD treatment was performed in a plain reactor in wire-duct geometry (non-uniform field reactor), which was driven by a 60 Hz power supply. Material characterization was carried out by water contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The plasma-induced modifications are associated with incorporation of polar oxygen and nitrogen containing groups on the polymer surface. The AFM analysis reveals that the plasma treatment roughens the material surface. Due to these structural and morphological changes the surface of DBD-treated polymers becomes more hydrophilic resulting in enhanced adhesion properties. (C) 2010 Elsevier B.V. All rights reserved.

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Cylinders (3.5 x 5.0 mm) of the reline resins Kooliner (K), New Truliner (N), Tokuso Rebase Fast (T), and Ufi Gel Hard (U) were bonded to cylinders (20 x 20 mm) of the denture base resin Lucitone 550 (L), and samples were divided into two controls and four test groups (n = 8). Shear tests (0.5 mm/min) were performed after polymerization or immersion in water (37 degrees C) for 7 days (controls); two or seven cycles of disinfection by immersion in sodium perborate (50 degrees C/10 min) or microwave irradiation (650 W/6 min). Statistical analyses (alpha = 0.05) revealed that two cycles of microwave and chemical disinfection increased the mean bond strengths of materials T (9.08 to 12.93 MPa) and L (18.89 to 23.02 MPa). For resin L, seven cycles of chemical (15.72 MPa) and microwave (17.82 MPa) disinfection decreased the shear bond strength compared with the respective control (21.74 MPa). Resins U (13.12 MPa), K (8.44 MPa), and N (7.98 MPa) remained unaffected.

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