Abstract In this work, polystyrene-b-poly (acrylic acid) (PS-b-PAA) nanovesicles were coated by modified chitosans aiming at studying its physicochemical parameters. The chitosan (CS) was chemically modified to add hydrophilic and/or hydrophobic groups, obtaining three modified chitosans. The PS-b-PAA nanovesicles were obtained by organic (1,4-dioxane) cosolvent method in water, resulting in nanovesicles with less than 150 nm of diameter (polydispersibility index - PDI at 90° = 0.106), measured by dynamic light scattering (DLS) and transmission electron microscopy (TEM), and negative zeta potential (-37.5 ± 3.2 mV), allowing the coating of its surface with oppositely charged polysaccharides, such as the CS and the modified chitosans. The coating process was made by mixing the colloidal suspensions with the CS and the modified chitosans at specific ENT#091;CS-xENT#093;/ENT#091;PS-b-PAAENT#093; ratios (0.001 to 1.0 wt %) and measuring the change in size and surface charge by DLS and zeta potential. Upon reaching maximum adsorption, the zeta potential parameter was positively stabilized (+26.7 ± 4.1 mV) with a hydrodynamic diameter slightly longer (< 200 nm of diameter). The encapsulation efficiency (EE) of minoxidil, quantified by capillary electrophoresis, was 50.7%, confirming their potential as drug delivery carriers and the coating process showed the possibility of controlling the surface charge nature of these nanovesicles.

<p>Three polymer-surfactant systems comprised of branched polyethylene imine (PEI) with an anionic surfactant (sodium dodecylsulfate; SDS), a cationic surfactant (tetradecyltrimethylammonium bromide; TTAB), and a zwitterionic surfactant (<italic>N</italic>-tetradecyl-<italic>N</italic>,<italic>N</italic>-dimethyl-3-ammonio-1-propanesulfonate; SB3-14) were studied based on the properties of surface tension, pyrene fluorescence emission, dynamic light scattering, pH, and zeta potential measurements. The critical aggregation concentration (<italic>cac</italic>) and polymer saturation point (<italic>psp</italic>) were determined for all three systems. The effect of these surfactants on the physico-chemical characteristics (diameter and surface charge) of the complexes formed was determined. Polymer-surfactant interactions occurred in all of the systems studied, with the strongest interactions, electrostatic in nature, occurring in the SDS-PEI system. After the neutralization of the polymer charges with the addition of the surfactant, the hydrophobic effect started to control the interlacing of the polymer chains. For the PEI-TTAB system, a very dense film was formed at surfactant concentrations above 2.0 mmol L^-1. In this case, the bromide counter-ion interacted with both the positively-charged PEI and the head of the surfactant, which is responsible for the formation of double layer coordination complexes. For the system composed of PEI and the zwitterionic surfactant, less cooperative associations occurred in comparison with the other systems.</p>

Soft nanoparticles of size 200-400 nm were obtained from soybean protein isolate (SPI). The particles were formed and suspended in water by the coacervation of aqueous suspensions of SPI in hostile buffered aqueous solutions in the presence of surfactants. We investigate the effect of storage, ionic strength, and concentrations of SPI and surfactant on nanoparticle size and zeta potential. Transmission electron microscopy images and scattering techniques (SLS/ DLS) revealed that the particles are spherical, with hydrophilic chains at the surface.

Neste artigo, as propriedades emulsificantes da proteína isolada de soja (SPI) foram evidenciadas mostrando que estas macromoléculas sofrem mudanças conformacionais quando adsorvidas em interfaces. Investigou-se a conformação das cadeias proteicas ancoradas nas regiões interfaciais de emulsões de óleo em água (o/a) através de técnicas de espalhamento de raios X (SAXS) e de imagem (microscopia eletrônica de varredura (SEM)). O valor médio do raio de giro (Rg) da SPI (aq) é 20 nm e aumenta para 30 nm em emulsões o/a; as proteínas atuam como moléculas anfifílicas expondo seus núcleos hidrofóbicos ao óleo e os resíduos hidrofílicos à fase aquosa. Este valor ainda é maior após o spray drying das emulsões, na interface o/ar das respectivas microcápsulas. As paredes das microcápsulas são fractais de objetos agregados com superfícies rugosas, que são alisadas pela presença de um agente de reticulação.

Herein, the emulsifying properties of soy protein isolate (SPI) were highlighted by showing that the macromolecules undergo conformational changes when adsorbed at interfaces. The conformation of protein chains nested at the interfacial region of oil in water (o/w) emulsions by means of X-ray scattering (SAXS) and direct imaging (scanning electron microscopy (SEM)) techniques was investigated. The mean radius of gyration (Rg) for SPI (aq) is 20 nm and increases up to 30 nm in o/w emulsions; the proteins act as amphiphilic molecules by exposing their hydrophobic core to the oil and their hydrophilic amino acid residues to the water phase. By spray drying the emulsions, it was also possible to measure the size (Rg = 40 nm) and to evaluate the morphology of these proteins at the oil/air interface of the respective microcapsules. The walls of microcapsules are fractals of clustered objects with rough surfaces, which are smoothed by the presence of a cross-linking agent.

A formação de complexos supramoleculares em solução aquosa pela associação do polieletrólito poli(etilenoimina) (PEI) com misturas do biossurfactante colato de sódio (NaC) e o surfactante aniônico dodecil sulfato de sódio (SDS) foi aqui investigado usando as técnicas de condutivimetria, tensiometria, fluorimetria, espalhamento de raios X a baixos ângulos (SAXS) e medidas de pH. Os resultados de fluorimetria, condutivimetria e medidas de pH levaram à conclusão de que os monômeros de NaC e SDS ligam-se primeiramente em sítios específicos das cadeias do polieletrólito PEI via interação eletrostática e posteriormente através de associação cooperativa. A interação do NaC com o PEI é mais fraca do que a interação do SDS com o PEI, porém, a adição de SDS ao sistema NaC-PEI levou à formação de micelas mistas SDS-NaC que interagiram fortemente com o polieletrólito PEI. Os resultados de SAXS sugeriram que o complexo supramolecular possui característica elipsoidal e essa forma não depende da concentração de surfactante nem da χNaC.

The formation of supramolecular complexes produced by association of poly(ethyleneimine) (PEI) and mixtures of sodium cholate (NaC) and sodium dodecyl sulfate (SDS) was investigated by pH, electrical conductivity, fluorescence spectroscopy and small angle X-ray scattering (SAXS) measurements. The fluorescence linked to previously measured values of pH and conductivity led to the conclusion that NaC and SDS molecules firstly bind to specific sites of the PEI chains via electrostatic interaction and secondly undergo self-assembly through regular cooperative association. The interaction of NaC with the polyelectrolyte PEI is weaker than that of SDS and the addition of SDS to the NaC-PEI system led to the formation of mixed NaC-SDS micelles which stronger interact with PEI. The SAXS results suggested that the micellar aggregates have a considerably ellipsoidal characteristic and the micellar shape is not affected by the surfactant concentration nor by χNaC.

Neste trabalho, os parâmetros estruturais, mecânicos, difratométricos e térmicos de filmes de quitosana e hidroxipropilmetilcelulose (HPMC), plastificados com sorbitol, foram estudados. Soluções de HPMC (2% m/m) em água, e quitosana (2% m/m) em uma solução de ácido acético 2%, foram preparadas. A concentração de sorbitol usada foi de 10% (m/m) para ambos os polímeros. Estas soluções foram misturadas em diferentes proporções (100/0; 70/30; 50/50; 30/70 e 0/100) de quitosana e HPMC, respectivamente, e 20 mL foram vertidos em placas de Petri de poliestireno, para posterior análise dos filmes prontos. A miscibilidade dos polímeros foi avaliada através da Difração por Raio-X, Microscopia Eletrônica de Varredura, Calorimetria Exploratória Diferencial (DSC) e Análise Termogravimétrica (TGA). Através dos resultados obtidos, os filmes não são totalmente miscíveis no estado seco, embora existam ligações fracas de hidrogênio entre os grupos funcionais dos biopolímeros.

In this work, the structural, mechanical, diffractometric, and thermal parameters of chitosan-hydroxypropylmethylcellulose (HPMC) films plasticized with sorbitol were studied. Solutions of HPMC (2% w/v) in water and chitosan (2% w/v) in 2% acetic acid solution were prepared. The concentration of sorbitol used was 10% (w/w) to both polymers. This solutions were mixed at different proportions (100/0; 70/30; 50/50; 30/70, and 0/100) of chitosan and HPMC, respectively, and 20 mL was cast in Petri dishes for further analysis of dried films. The miscibility of polymers was assessed by X-ray diffraction, scanning electronic microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The results obtained indicate that the films are not fully miscible at a dry state despite the weak hydrogen bonding between the polymer functional groups.

In this work, the interactions between the non-ionic polymer of ethyl(hydroxyethyl)cellulose (EHEC) and mixed anionic surfactant sodium dodecanoate (SDoD)-sodium decanoate (SDeC) in aqueous media, at pH 9.2 (20 mM borate/NaOH buffer) were investigated by electric conductivity and light transmittance measurements at 25 ºC. The parameters of the surfactant to polymer association processes such as the critical aggregation concentration and saturation of the polymer by surfactants were determined from plots of specific conductivity vs total surfactant concentration, [surfactant]tot = [SDoD] + [SDeC]. Through the results was not observed a specific link of polymer with the surfactant, implying therefore a phenomenon only cooperative association.

Um método fluorimétrico simples, rápido e sensível foi desenvolvido e validado para quantificação da curcumina em suspensões de nanocápsulas lipídicas e poliméricas, usando acetonitrila como solvente. Os comprimentos de onda de excitação e emissão foram 397 nm e 508 nm, respectivamente. Nas condições testadas, a curva de calibração demonstrou-se linear na faixa de 0,1 a 0,6 µg/mL, exibindo coeficiente de correlação de 0,9982. Os limites de detecção e quantificação foram 0,03 e 0,10 µg/mL, respectivamente. Os resultados da validação confirmaram que o método desenvolvido é específico, linear, exato e preciso para o uso proposto. O presente método foi aplicado com sucesso para a avaliação do teor de curcumina nas suspensões de nanocápsulas lipídicas e poliméricas durante o estágio inicial do desenvolvimento da formulação.

A simple, rapid, and sensitive fluorimetric method was developed and validated to quantify curcumin in lipid and polymeric nanocapsule suspensions, using acetonitrile as a solvent. The excitation and emission wavelengths were set at 397 nm and 508 nm, respectively. The calibration graph was linear from 0.1 to 0.6 µg/mL with a correlation coefficient of 0.9982. The detection and quantitation limits were 0.03 and 0.10 µg/mL, respectively. The validation results confirmed that the developed method is specific, linear, accurate, and precise for its intended use. The current method was successfully applied to the evaluation of curcumin content in lipid and polymeric nanocapsule suspensions during the early stage of formulation development.

Mixtures of ethyl(hydroxyethyl)cellulose (EHEC) and Sodium Dodecyl Sulfate (SDS) were investigated using surface tension, conductivity and viscosity measurements in aqueous solutions. The parameters of the surfactant to polymer association processes such as the critical aggregation concentration (cac) and saturation of the polymer by SDS (psp) were determined from the plots of surface tension and specific conductivity versus surfactant concentration. Through the final results we see that there was no specific link of polymer with the surfactant, implying therefore a phenomenon of only cooperative association.