Hydrogen-bonded complexes and blends of poly(acrylic acid) and methylcellulose: nanoparticles and mucoadhesive films for Ocular Delivery of Riboflavin

Poly(acrylic acid) (PAA) and methylcellulose (MC) are able to form hydrogen-bonded interpolymer complexes (IPCs) in aqueous solutions. In this study, the complexation between PAA andMC is explored in dilute aqueous solutions under acidic conditions. The formation of stable nanoparticles is established,whose size and colloidal stability are greatly dependent on solution pH and polymers ratio in the mixture. Poly(acrylic acid) and methylcellulose are also used to prepare polymeric films by casting from aqueous solutions. It is established that uniform films can be prepared by casting from polymer mixture solutions at pH 3.4–4.5. At lower pHs (pH<3.0) the films have inhomogeneous morphology resulting from strong interpolymer complexation and precipitation of polycomplexes, whereas at higher pHs (pH 8.3) the polymers form fully immiscible blends because of the lack of interpolymer hydrogen-bonding. The PAA/MC films cast at pH 4 are shown to be non-irritant to mucosal surfaces. These films provide a platform for ocular formulation of riboflavin, a drug used for corneal crosslinking in the treatment of keratoconus. An in vitro release of riboflavin as well as an in vivo retention of the films on corneal surfaces can be controlled by adjusting PAA/MC ratio in the formulations.

Interparticle Interactions Effects on the Magnetic Order in Surface of Fe(3)O(4) Nanoparticles

We report interparticle interactions effects on the magnetic structure of the surface region in Fe(3)O(4) nanoparticles. For that, we have studied a desirable system composed by Fe(3)O(4) nanoparticles with (d) = 9.3 nm and a narrow size distribution. These particles present an interesting morphology constituted by a crystalline core and a broad (similar to 50% vol.) disordered superficial shell. Two samples were prepared with distinct concentrations of the particles: weakly-interacting particles dispersed in a polymer and strongly-dipolar-interacting particles in a powder sample. M(H, T) measurements clearly show that strong dipolar interparticle interaction modifies the magnetic structure of the structurally disordered superficial shell. Consequently, we have observed drastically distinct thermal behaviours of magnetization and susceptibility comparing weakly- and strongly-interacting samples for the temperature range 2 K < T < 300 K. We have also observed a temperature-field dependence of the hysteresis loops of the dispersed sample that is not observed in the hysteresis loops of the powder one.

Preparation and characterization of the novels terpolymers of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine impregnated with silver nanoparticles

This paper reports the preparation and characterization of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine filled with nanosilver. Theses materials were synthesized by non aqueous polymerization through a chemical reaction using benzoyl peroxide as the initiator. The nanosilver was obtained from chemical reduction using NaBH(4) as reducing agent and sodium citrate as stabilizer. The nanometric dimension of nanosilver was monitored by UV-visible and confirmed through TEM. The morphology was characterized by SEM and the thermal properties were done by TGA and DSC. The antimicrobial action of the polymers impregnated with nanosilver was evaluated using both microorganisms, Staphylococcus aureus and Escherichia coli. The antimicrobial activity of the poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} filled with nanosilver was confirmed by the presence of an inhibition halo of the bacterial growth in seeded culture media, but was not confirmed to the styrene-divinylbenzene-vinylpiridine. The present work suggest that trans - [RuCl(2)(vpy)(4)] complex facilitate the release of silver ion from the media.

PEGylated polyethyleneimine-entrapped gold nanoparticles for enhanced and targeted gene delivery applications

Gene therapy, which involves the transfer of nucleic acid into target cells in patients, has become one of the most important and widely explored strategies to treat a variety of diseases, such as cancer, infectious diseases and genetic disorders. Relative to viral vectors that have high immunogenicity, toxicity and oncogenicity, non-viral vectors have gained a lot of interest in recent years. This is largely due to their ability to mimic viral vector features including the capacity to overcome extra- and intra-cellular barriers and to enhance transfection efficiency. Polyethyleneimine (PEI) has been extensively investigated as a non-viral vector. This cationic polymer, which is able to compact nucleic acid through electrostatic interactions and to transport it across the negatively charged cell membranes, has been shown to effectively transfect nucleic acid into different cell lines. Moreover, entrapment of gold nanoparticles (Au NPs) into such an amine-terminated polymer template has been shown to significantly enhance gene transfection efficiency. In this work, a novel non-viral nucleic acid vector system for enhanced and targeted nucleic acid delivery applications was developed. The system was based on the functionalization of PEI with folic acid (FA; for targeted delivery to cancer cells overexpressing FA receptors on their surface) using polyethylene glycol (PEG) as a linker molecule. This was followed by the preparation of PEI-entrapped Au NPs (Au PENPs; for enhancement of transfection efficiency). In the synthesis process, the primary amines of PEI were first partially modified with fluorescein isothiocyanate (FI) using a molar ratio of 1:7. The formed PEI-FI conjugate was then further modified with either PEG or PEGylated FA using a molar ratio of 1:1. This process was finally followed by entrapment of Au NPs into the modified polymers. The resulting conjugates and Au PENPs were characterized by several techniques, namely Nuclear Magnetic Resonance, Dynamic Light Scattering and Ultraviolet-Visible Spectroscopy, to assess their physicochemical properties. In the cell biology studies, the synthesized conjugates and their respective Au PENPs were shown to be non-toxic towards A2780 human ovarian carcinoma cells. The role of these materials as gene delivery agents was lastly evaluated. In the gene delivery studies, the A2780 cells were successfully transfected with plasmid DNA using the different vector systems. However, FA-modification and Au NPs entrapment were not determinant factors for improved transfection efficiency. In the gene silencing studies, on the other hand, the Au PENPs were shown to effectively deliver small interfering RNA, thereby reducing the expression of the B-cell lymphoma 2 protein. Based on these results, we can say that the systems synthesized in this work show potential for enhanced and targeted gene therapy applications.

Evaluation of the Genotoxicity of Chitosan Nanoparticles for Use in Food Packaging Films

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

Incorporation of Ag nanoparticles into membrane mimetic systems composed by phospholipid layer-by-layer (LbL) films to achieve surface-enhanced Raman scattering as a tool in drug interaction studies

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

Study of the interaction between cardiolipin bilayers and methylene blue in polymer-based Layer-by-Layer and Langmuir films applied as membrane mimetic systems

An increase of the reports involving mimetic systems has been observed. Briefly, these systems use biological phospholipids to exploit specific interactions between membrane-models and drugs. Here, the Layer-by-Layer (LbL) and Langmuir techniques were used to investigate the interaction between cardiolipin (CLP-negative phospholipid) and a cationic-like drug methylene blue (MB). Supported by a cationic polyelectrolyte (PAH), LbL films containing PAH/(CLP + MB) and PAH/(CLP + MB + AgNP) were grown up to 14 bilayers. The optical microscopy analysis revealed a decrease of the CLP vesicle sizes in the presence of MB as a possible consequence of the MB action onto the mechanical properties of the CLP membrane. From FTIR spectra, changes mainly related to peak position and band intensity and shape were observed in the spectra from PAH/CLP when in the presence of MB. The latter supports that the interactions between the phosphate and amine charged groups from CLP and PAH, respectively, established during the LbL film fabrication, besides the CLP hydrocarbon environment, are influenced by the presence of MB. Using the micro-Raman technique, a chemical mapping was build based on MB spectrum by resonance Raman scattering (RRS) and surface-enhanced resonance Raman scattering (SERRS). The later phenomenon was activated by Ag nanoparticles (AgNPs) trapped within the LbL film allowing collecting spectra for a single bilayer of PAH/(CLP + MB + AgNP). A rough estimation showed a SERRS amplification of 10(3) in comparison to RRS spectra. As a complementary approach, Langmuir films of CLP in the presence of co-spread MB were investigated through surface pressure vs mean molecular area (pi-A) isotherms. The results showed that for concentrations of MB below 100 mol%, the drug is expelled to water subphase for high values of surface pressure (condensed phase). For concentration at 100% and higher, the MB keeps bound to CLP floating monolayer. (C) 2010 Elsevier B.V. All rights reserved.

Praziquantel-loaded PLGA nanoparticles: preparation and characterization

Nanoparticles containing praziquantel made of Poly (D,L-lactide-co-glycolide) were designed by an emulsion-solvent evaporation method. Two organic solvents were separately utilized as disperse phase: methylene chloride and ethyl acetate. The size of the particles prepared with the former solvent was bigger than the particles prepared with the latter. The entrapment efficiency was bigger when methylene chloride was used, 79.82% in comparison with 29.27% by using ethyl acetate. DSC and infrared studies showed that no strong chemical interaction between drug and polymer occurred. Release kinetics of praziquantel, used as a model drug, was governed not only by actual drug loading but also by particles size. The higher the drug content and the smaller the particle size resulted in faster drug release.

Development on polymeric precursor routes to produce superconducting nanoparticles

The well-known polymeric precursor route is a simple and low-cost sol-gel method based on the preparation of an aqueous precursor solution of metals followed by the addition of a water-soluble polymer. This method consists of a polyesterification process between a metal chelate complex by using a hydroxycarboxylic acid and a polyhydroxy alcohol. In this work, citric acid (CA), tartaric acid (TA) and ethylenediaminetetraacetic acid (EDTA) are used as the hydroxycarboxylic acid and ethylene glycol (EG) is used as the polyhydroxy alcohol. The effects of the precursor pH solution, time and temperature of polymerization step as well as the combination of different chelating agents in order to obtain nanoscopic YBa2Cu3Oy samples were traced. (c) 2007 Elsevier B.V. All rights reserved.

Silver Distribution and Release from an Antimicrobial Denture Base Resin Containing Silver Colloidal Nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Biodegradable Nanoparticles Containing Benzopsoralens: An Attractive Strategy for Modifying Vascular Function in Pathological Skin Disorders

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermoanalytical study of praziquantel-loaded PLGA nanoparticles

Polymeric nanoparticles have received great attention as potential controlled drug delivery systems. Biodegradable polymers has been extensively used in the development of these drug carriers, and the polyesters such as polylactic acid, polyglycolic acid and their copolymers as poly-lactide-co- glycolide are the most used, considering its biocompatibility and biodegradability. Thermal analysis techniques have been used for pharmaceutical substances for more than 30 years and are routine methods for screening drug-excipient interactions. The aim of this work is to use thermal analysis to characterize PLGA nanoparticles containing a hydrophobic drug, praziquantel. The results show that the drug is in an amorphous state or in disordered crystalline phase of molecular dispersion in the PLGA polymeric matrix and that the microencapsulation process did not interfere with the chemical structure of the polymer, mantaining the structural drug integrity.

Effect of disinfection and accelerated ageing on dimensional stability and detail reproduction of a facial silicone with nanoparticles

The aim of the present study was to evaluate the effect of disinfection and accelerated ageing on the dimensional stability and detail reproduction of a facial silicone with different types of nanoparticle. A total of 60 specimens were fabricated with Silastic MDX 4-4210 silicone and they were divided into three groups: colourless and pigmented with nanoparticles (make-up powder and ceramic powder). Half of the specimens of each group were disinfected with Efferdent tablets and half with neutral soap for 60 days. Afterwards, all specimens were subjected to accelerated ageing. Both dimensional stability and detail reproduction tests were performed after specimen fabrication (initial period), after chemical disinfection, and after accelerated ageing periods (252, 504 and 1008 hours). The dimensional stability test was conducted using AutoCAD software, while detail reproduction was analysed using a stereoscope magnifying glass. Dimensional stability values were statistically evaluated by analysis of variance (ANOVA) followed by Tukey's test (p < 0.01). Detail reproduction results were compared using a score. Chemical disinfection and also accelerated ageing affected the dimensional stability of the facial silicone with statistically significant results. The silicone's detail reproduction was not affected by these two factors regardless of nanoparticle type, disinfection and accelerated ageing. © 2012 Informa UK, Ltd.

Electrochemical studies based on local interfacial ph changes of gold nanoparticles immobilized on polystyrene brushes

The electrochemical behavior of polystyrene modified with gold nanoparticle (Au NPs) was investigated in terms of pH-responsive polymer brush. A pH-responsive of modified polymer brush from tethered polystyrene was prepared and used for selective gating transport of anions andcations across the thin-film. An ITO-coated glass electrode was used as substrate and applied to study the switchable permeability of the polymer brush triggered by changes in pH of the aqueous environment. The pH-sensitive behavior of the polymer brush interface has been demonstrated by means of cyclic voltammetry (CV) and Localized Surface Plasmon Resonance (LSPR). CV experiments showed at ph values of 4 and 8 induces swelling and shrinking of the grafted polymer brushes, respectively, and this behavior is fast and reversible. LSPR measurements showed a blue shift of 33 nm in the surface resonance band changes by local pH. The paper brings an easy methodology to fabrication a variety of nanosensors based on the polymer brushes-nanoparticle assemblies. © 2013 by ESG.

Comparison of the nanoparticles performance in the photocatalytic degradation of a styrene-butadiene rubber nanocomposite

Much has been talking about the advantages of polymeric nanocomposites, but little is known about the influence of nanoparticles on the stability of these materials. In this sense, we studied the influence of both oxides of zirconium and titanium, known to have photocatalytic properties, as well as the influence of synthetic clay Laponite on the photodegradation of styrene-butadiene rubber (SBR). SBR nanocomposites were prepared by the colloidal route by mixing commercial polymer lattices and nanometric anatase TiO2, monoclinic ZrO2 or exfoliated Laponite clays colloidal suspensions. To better understand the degradation mechanisms that occur in these nanocomposites, the efficiency of different photocatalysts under ultraviolet radiation was monitored by FT-IR and UV-vis spectroscopies and by differential scanning calorimetric. It was observed that TiO2 and ZrO2 nanoparticles undoubtedly acted as catalysts during the photodegradation process with different efficiencies and rates. However, when compared to pure SBR samples, the polymer degradation mechanism was unaffected. Unlike studies with nanocomposites montmorillonite, exfoliated laponite clay effectively acts as a photostabilizer of polymer UV photodegradation. Copyright © 2012 Wiley Periodicals, Inc.