Mucoadhesive Amphiphilic Methacrylic Copolymer-Functionalized Poly(epsilon-caprolactone) Nanocapsules for Nose-to-Brain Delivery of Olanzapine

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrooptic proprieties of layer-by-layer films of a azobenzene containing copolymer

The methacrylic copolymer functionalized with the azo chromophore 4-[N-ethyl-N-(2-hydroxiethyl)]-amino-2′-chloro-4-nitroazobenzene (MMADR13), in its polyelectrolyte form, can be used to fabricate thin films by the layer-by-layer (LbL) technique just if one alternates this anionic polyelectrolyte with a cationic polyelectrolyte such as poly(allylamine hydrochloride) (PAH). Since PAH does not present any particular optical functionality, the main final film feature will came from the side chain DR13 azo-chromophore group due to its large nonlinear optical properties and photoisomerization capabilities. This work reports the electrooptic activity of MMADR13/DR13 LBL films, which arises from the high hiperpolarizability about the azo side chain group.

Polyethylene/(organo-montmorillonite) composites modified with ethylene/ methacrylic acid copolymer: Morphology and mechanical properties

Several composites based on high-density polyethylene (PE), organically modified montmorillonite (OMMT) and ethylene/methacrylic acid copolymer (EMAA) were prepared by melt compounding. Three Na(+)-montmorillonites (MMT) of different precedence were modified with hexadecyl trimethyl ammonium chloride in order to change their nature from hydrophilic to organophilic. The composites morphology was examined by XRD, SEM and TEM. Mechanical properties were evaluated under static conditions. A slight reinforcement was achieved only when OMMT was added to PE. When EMAA was added to the composites, it negatively interacted with OMMT, diminishing the interlayer distance of OMMT, changing the composite morphology, as if OMMT was not present in composites, and deteriorating their mechanical properties. (C) 2008 Elsevier Ltd. All rights reserved.

Self-Assembly of Stimuli-Responsive Water-Soluble [60]Fullerene End-Capped Ampholytic Block Copolymer

Well-defined, water-soluble, pH and temperature stimuli-responsive [60]fullerene (C₆₀) containing ampholytic block copolymer of poly((methacrylic acid)-block-(2-(dimethylamino)ethyl methacrylate))-block–C₆₀ (P(MAA-b-DMAEMA)-b-C₆₀) was synthesized by the atom transfer radical polymerization (ATRP) technique. The self-assembly behaviour of the C₆₀ containing polyampholyte in aqueous solution was characterized by dynamic light scattering (DLS), and transmission electron microscopy. This amphiphilic mono-C₆₀ end-capped block copolymer shows enhanced solubility in aqueous medium at room and elevated temperatures and at low and high pH but phase-separates at intermediate pH of between 5.4 and 8.8. The self assembly of the copolymer is different from that of P(MAA-b-DMAEMA). Examination of the association behavior using DLS revealed the co-existence of unimers and aggregates at low pH at all temperatures studied, with the association being driven by the balance of hydrophobic and electrostatic interactions. Unimers and aggregates of different microstructures are also observed at high pH and at temperatures below the lower critical solution temperature (LCST) of PDMAEMA. At high pH and at temperatures above the LCST of PDMAEMA, the formation of micelles and aggregates co-existing in solution is driven by the combination of hydrophobic, electrostatic, and charge-transfer interactions.

Charge-balanced copolymer hydrogels:potential as biomedical materials

Polyzwitterionic-containing hydrogel materials been proposed for use in biomaterial applications. Polyzwitterions contain anions and cations in the same monomeric unit, unlike polyampholytes which contain them in different monomeric units. The use of cationic and anionic monomers in stoichiometrically equivalent proportions produces charge-balanced polyampholytes (PA) copolymers. Membranes prepared using either betaine-containing (BT) polyzwitterionic copolymers or PA copolymers can share similar properties, but the range of EWCs offered by membranes incorporating BT and PA monomers is greater than that for conventional neutral hydrogels and methacrylic acid-based systems. Here we compare properties of BT-containing and PA-containing copolymer membranes, relevant to their potential as biomedical materials. Membranes of the copolymers were prepared as previously described. Surface energy was determined using a GBX Digidrop (GBX Scientific Instruments), with diidomethane and water as probes. The absorption of proteins was determined by soaking the membranes in 1mg/ml protein solutions for a predetermined time, and measuring UV absorption of the membranes at certain wavelengths. The BT and PA copolymer membranes displayed similar values for the polar components and dispersive components of total surface free energy. This was perhaps not surprising when the structures of the monomers were considered. The BT and PA copolymer membranes displayed differences in their protein absorption over time, with the PA demonstrating higher uptake of protein than the BT. In addition to the aforementioned greater EWC range, the use of BT and PA copolymer membranes also avoids some of the problems associated with net anionicity. Comparison of the BT copolymer with the “pseudo” zwitterionic PA copolymers shows that controlled molecular architecture is required to gain the benefits of balancing the charges present in the copolymers in a way that will make them beneficial to hydrogel design.

Improved Selective Cholesterol Adsorption By Molecularly Imprinted Poly(methacrylic Acid)/silica (pmaa-sio₂) Hybrid Material Synthesized With Different Molar Ratios.

The present paper describes the synthesis of molecularly imprinted polymer - poly(methacrylic acid)/silica and reports its performance feasibility with desired adsorption capacity and selectivity for cholesterol extraction. Two imprinted hybrid materials were synthesized at different methacrylic acid (MAA)/tetraethoxysilane (TEOS) molar ratios (6:1 and 1:5) and characterized by FT-IR, TGA, SEM and textural data. Cholesterol adsorption on hybrid materials took place preferably in apolar solvent medium, especially in chloroform. From the kinetic data, the equilibrium time was reached quickly, being 12 and 20 min for the polymers synthesized at MAA/TEOS molar ratio of 6:1 and 1:5, respectively. The pseudo-second-order model provided the best fit for cholesterol adsorption on polymers, confirming the chemical nature of the adsorption process, while the dual-site Langmuir-Freundlich equation presented the best fit to the experimental data, suggesting the existence of two kinds of adsorption sites on both polymers. The maximum adsorption capacities obtained for the polymers synthesized at MAA/TEOS molar ratios of 6:1 and 1:5 were found to be 214.8 and 166.4 mg g(-1), respectively. The results from isotherm data also indicated higher adsorption capacity for both imprinted polymers regarding to corresponding non-imprinted polymers. Nevertheless, taking into account the retention parameters and selectivity of cholesterol in the presence of structurally analogue compounds (5-α-cholestane and 7-dehydrocholesterol), it was observed that the polymer synthesized at the MAA/TEOS molar ratio of 6:1 was much more selective for cholesterol than the one prepared at the ratio of 1:5, thus suggesting that selective binding sites ascribed to the carboxyl group from MAA play a central role in the imprinting effect created on MIP.

Aqueous two-phase extraction using thermoseparating copolymer: a new system for phenolic compounds removal from hemicelullosic hydrolysate

BACKGROUND: The hydrolysis of hemicellulosic material can provide liquor with high xylose concentration (which can be used as a fermentation medium) and phenolic compounds (Phs), potentially immunostimulating compounds. However, these hydrolysates must be detoxified in order to remove the Phs that can act as inhibitors in bioconversions. RESULTS: Aqueous two-phase systems composed of thermoseparating copolymers were used for rice straw hydrolysate detoxification. The hydrolysis process was able to promote chemical breakdown of 85% of the total hemicellulose content, 14% of the cellulose, and 2% of the lignin. The hydrolysate obtained contained 19.7 g L-1 of xylose and several phenolic compounds, such as vanillin, vanillic acid, ferullic acid, etc. The phenolics extraction was studied as a function of copolymer molar mass (1100 g mol(-1), 2000 g mol(-1) and 2800 g mol(-1)), their percentages (from 5% to 50%) and Phs initial concentration. Phenolic compounds extraction of around 80% was obtained under the following conditions: 20% (w/w) and 35% (w/w) copolymer 1100 g mol-1, 35% (w/w) copolymer 2000 g mol(-1) and 35% (w/w) copolymer 2800 g mol(-1) at 25 degrees C. CONCLUSIONS: The results demonstrated the viability of this method for the removal of Phs from rice straw hydrolysate, which has potential uses in bioconversion processes. (c) 2007 Society of Chemical Industry.

Three-layer piezoelectrets from fluorinated ethylene-propylene (FEP) copolymer films

A process for preparing three-layer piezoelectrets from fluorinated ethylene-propylene (FEP) copolymer films is introduced. Samples are made from commercial FEP films by means of laser cutting, laser bonding, electrode evaporation, and high-field poling. The observed dielectric-resonance spectra demonstrate the piezoelectricity of the FEP sandwiches. Piezoelectric d (33) coefficients up to a few hundred pC/N are achieved. Charging at elevated temperatures can increase the thermal stability of the piezoelectrets. Isothermal experiments for approximately 15 min demonstrate that samples charged at 140A degrees C keep their piezoelectric activity up to at least 120A degrees C and retain 70% of their initial d (33) even at 130A degrees C. Acoustical measurements show a relatively flat frequency response in the range between 300 Hz and 20 kHz.

Dynamic formation of SEBS copolymer submicrometric structures

Highly ordered A-B-A block copolymer arrangements in the submicrometric scale, resulting from dewetting and solvent evaporation of thin films, have inspired a variety of new applications in the nanometric world. Despite the progress observed in the control of such structures, the intricate scientific phenomena related to regular patterns formation are still not completely elucidated. SEBS is a standard example of a triblock copolymer that forms spontaneously impressive pattern arrangements. From macroscopic thin liquid films of SEBS solution, several physical effects and phenomena act synergistically to achieve well-arranged patterns of stripes and/or droplets. That is, concomitant with dewetting, solvent evaporation, and Marangoni effect, Rayleigh instability and phase separation also play important role in the pattern formation. These two last effects are difficult to be followed experimentally in the nanoscale, which render difficulties to the comprehension of the whole phenomenon. In this paper, we use computational methods for image analysis, which provide quantitative morphometric data of the patterns, specifically comprising stripes fragmentation into droplets. With the help of these computational techniques, we developed an explanation for the final part of the pattern formation, i.e. structural dynamics related to the stripes fragmentation. (C) 2010 Elsevier Ltd. All rights reserved.

Thermal properties of amphiphilic biodegradable triblock copolymer of l,l-lactide and ethylene glycol

Samples of poly(l,l-lactide)-block-poly(ethylene glycol)-block-poly(l,l-lactide) (PLLA-PEG-PLLA) were synthesized from l,l-lactide polymerization using stannous 2-ethylhexanoate, Sn(Oct)(2) as initiator and di-hydroxy-terminated poly(ethylene glycol) (PEG) (M (n) = 4000 g mol(-1)) as co-initiator. The chemical linkage between the PEG segment and the PLA segments was characterized by Fourier transform infrared spectroscopy (FTIR). Thermogravimetry analysis (TG) revealed the copolymers composition and was capable to show the deleterious effect of an excess of Sn(Oct)(2) in the polymer thermal stability, while Differential Scanning Calorimetry (DSC) allowed the observation of the miscibility between the PLLA and PEG segments in the different copolymers.

Free volume and water uptake in a copolymer hydrogel series

A copolymer of X-hydroxyethyl methacrylate (HEMA) with 2-ethoxy ethyl methacrylate (EEMA) was synthesized and the molecular mobility, free volume, and density properties examined as a function of composition. These properties were correlated with the equilibrium water uptake in order to determine which of the properties were most influential in causing high water sorption, as these materials are suitable candidates for hydrogel systems. It was found that the polar HEMA repeat unit results in a rigid, glassy sample at room temperature due to the high degree of hydrogen bonding between chains whereas high EEMA content leads to rubbery samples with subambient glass transition temperatures. The free volume properties on the molecular scale measured by positron annihilation Lifetime spectroscopy (PALS) showed that higher HEMA content led to smaller, fewer holes and a lower free volume fraction than EEMA. Therefore the high water uptake of HEEMA-containing copolymers is largely related to the high polarity of the HEMA unit compared to EEMA, despite the low content of free volume into which the water can initially diffuse. Trends in density with copolymer composition, as measured on a macroscopic level, differs to that seen by PALS and indicates that the two techniques are measuring different scales of packing. (C) 1998 John Wiley & Sons, Inc.

Copolymer hydrogels of 2-hydroxyethyl methacrylate with n-butyl methacrylate and cyclohexyl methacrylate: synthesis, characterization and uptake of water

The bulk free radical copolymerizations of 2-hydroxyethyl methacrylate (HEMA) with n-butyl methacrylate (BMA) or cyclohexyl methacrylate (CHMA) were studied over the composition mole fraction interval of 0-1 for HEMA in the monomer feed. The C-13 NMR (125 MHz) spectra of the copolymers were analysed to determine the copolymer composition and the stereochemical configuration of the copolymers. The terminal model reactivity ratios of HEMA and BMA were found to be r(HEMA) = 1.73 and r(BMA) = 0.65 and for HEMA and CHMA, r(HEMA) = 1.26 and r(CHMA) = 0.31. The BMA and CHMA homopolymers were found to be predominantly syndiotactic with isotacticity parameters of theta(BB) = 0.18 and theta(CC) = 0.19, respectively. The copolymers were also found to be predominantly syndiotactic, indicating a strong tendency for racemic additions of the monomers in the formation of the copolymers. The diffusion of water into cylinders of poly(HEMA-co-BMA) and poly(HEMA-co-CHMA) was studied over a range of copolymer compositions and was found to be Fickian. The diffusion coefficients of water at 37 degrees C were determined from swelling measurements and were found to vary from 1.72 x 10(-11) m(2) s(-1) for polyHEMA to 0.97 x 10(-11) m(2) s(-1) for poly(HEMA-co-BMA) having a mole fraction F-HEMA = 0.80 and to 0.91 x 10(-11) m(2) s(-1) for a poly(HEMA-co-CHMA) also having F-HEMA = 0.80. The mass of water absorbed at equilibrium relative to the mass of dry polymer varied from 58.8 for polyHEMA to 27.2% for poly(HEMA-co-BMA) having F-HEMA = 0.85 and to 21.3% for poly(HEMA-co-CHMA) having F-HEMA = 0.80. (C) 1999 Elsevier Science Ltd. All rights reserved.

Fractured Orbital Wall Reconstruction With an Auricular Cartilage Graft or Absorbable Polyacid Copolymer

Objective: The objective of the study was to compare the functional and aesthetic results of fractured orbital wall reconstruction with an auricular cartilage graft or absorbable polyacid copolymer. Materials and Methods: Twenty patients with blow-out orbital fracture/orbital floor associated or not with the medial wall were assessed by the same craniofacial surgical group. All were evaluated preoperatively and postoperatively by an ophthalmologist for diplopia, enophthalmos, exophthalmos, sensitivity, ophthalmic reflexes, intraocular pressure, and visual field. The patients were subjected to a preoperative facial multislice computed tomographic scan, repeated 6 months after surgery. Eight patients underwent reconstruction with an auricular cartilage graft, and 12 patients, with blade absorbable polyacid copolymer. Subtarsal access was used for all patients. Results: Two patients showed temporary ectropion, 1 in each group. All patients presented satisfactory ocular function, and all tests revealed good orbital delineation, orbital symmetry, periorbital sinus individualization, and reduction of blow-out. Conclusions: The blow-out orbital wall reconstruction can be performed with the use of an auricular cartilage or with a blade absorbable copolymer without differences regarding functional or aesthetic complications and sequelae.