Adsorption behavior of hydrophobically modified polyelectrolytes onto amino- or methyl-terminated surfaces.

The adsorption of hydrophobically modified polyelectrolytes derived from poly(maleic anhydride-alt-styrene) (P(MA-alt-St)) containing in their side chain aryl-alkyl groups onto amino- or methyl-terminated silicon wafers was investigated. The effect of the spacer group, the chemical nature of the side chain, molecular weight of polyelectrolyte, and ionic strength of solution on the polyelectrolyte adsorbed amount was studied by null ellipsometry. The adsorbed amount of polyelectrolyte increased with increasing ionic strength, in agreement with the screening-enhanced adsorption regime, indicating that hydrophobic interactions with the surface play an important role in the adsorption process. At constant ionic strength, the adsorbed amount was slightly higher for polyelectrolytes with larger alkyl side chain and decreased with the hydrophobicity of aryl group. The adsorption behavior is discussed in terms of the side chain flexibility of the polymer. Characteristics of the adsorbed layer were studied by atomic force microscopy (AFM) and contact angle measurements. AFM images show the presence of aggregates and closed globular structure of polyelectrolyte onto the amino- or methyl-terminated surface, which agrees with a 3D and 2D growth mechanism, respectively. Fluorescence measurements showed that the aggregation of polyelectrolyte containing the hydrophobic naphthyl group occurs already in the solution. However, the aggregation of polyelectrolytes containing the phenyl group in its side chain is not observed in solution but is induced by the amino-terminated surface. This difference can be explained in terms of the higher flexibility of side chain bearing the phenyl group. The polyelectrolyte films showed a high chemical heterogeneity and moderate hydrophobicity.

Conformational and physicochemical properties of quinoa proteins affected by different conditions of high-intensity ultrasound treatments.

Quinoa proteins (QP) have promise as a potential source of novel food ingredients, and it is of great interest to know how high-intensity ultrasound (HIUS) treatments affect the properties of QP. This work aimed to study the impact of on-off time-pulses of HIUS treatments on the structural and physicochemical properties of QP; samples were treated at 5, 10, 20, and 30 min with on-off pulses of 10 s/10 s, 5 s/1 s, and 1 s/5 s). Structural changes were evaluated using PAGE-SDS, circular dichroism, fluorescence spectroscopy, and differential scanning calorimetry. Meanwhile, physicochemical properties were also examined, including solubility, Z-average, polydispersity index PDI, and Z-potential. PAGE-SDS showed the appearance of polypeptides over 190 kDa in HIUS samples-treated. All samples presented 15.6% α-helices, 31.3% ß-sheets, 21.8% ß-rotations, and 31.4% random coils independent of the HIUS treatment. ß-Turn structures and "random coils" were not affected by HIUS. When US 10 s/10 s and 1 s/5 s were applied, an increase in the % α-helix and a decrease in ß-fold were observed, which could indicate a small conversion of ß-folds to α-helices. Fluorescence spectra for all HIUS showed a significant increase (23%) of average fluorescence intensity and a decrease of λmax in relation to that of the control (346 dnm and 340 nm average HIUS treatment). DSC showed one endotherm in all cases (81.6-99.8 °C), and an increase in Td was observed due to the effect of the HIUS treatment. HIUS caused a 48% increase in solubility. The Z-average of the HIUS samples compared to that of the controls showed an increase from 37.8 to 47.3 nm. PDI and Z-potential values from the QP controls and the HIUS samples did not show significance differences and presented average values of 0.466 ±â€¯0.021 (PDI) and -16.63 ±â€¯0.89 (Z-potential). It is possible to conclude that HIUS treatments affect the secondary and tertiary structure of quinoa proteins, and these changes resulted in an increase of solubility and particle size. HIUS treatment as a new and promising technology that can improve the QP solubility properties and in that way allow its use as an ingredient with a good source of protein to develop different types of beverages/protein sauces.

Studies on the compatibility of diethylpropion hydrochloride with carboxymethylcellulose and other dietary fibres.

The combination of diethylpropion hydrochloride with carboxymethylcellulose induces decomposition of the drug. The principal decomposition products obtained were 1-phenyl-1,2-propanedione, benzoic acid and diethylamine as hydrochloride and benzoate salts. These phenomena have been explained with reference to basic decomposition scheme of the diethylpropion. Additionally, the behaviour of diethylpropion in mixtures with other dietary fibres such as methylcellulose, wheat bran and wheat germ was examined. Diethylpropion in combination with methylcellulose is rather stable while in mixtures with wheat bran and wheat germ suffers degradation. An increase in the weight of the excipient, probably due to chemical binding of the drug and other degradation products by the excipient, was observed in all these cases. The decomposition reactions were studied by applying a sequence of selective solvent extractions and using high-performance liquid chromatography (HPLC).

Study of the prolonged release of theopylline from polymeric matrices based on grafted chitosan with acrylamide.

The aim of this work was to study the performance of chitosan (CB) grafted with acrylamide (CB-g-A) as prolonged drug release matrix as compared with unmodified chitosan. A non-pH dependent swelling behaviour for the matrix tablets based on grafted chitosan was observed. The overlaping between degree of swelling measured by weighing (DSw) and measured by increase of diameter (DSd) up to 240 minutes showed that the swelling process could be isotropic. The non-pH dependent swelling behaviour of these matrices could be explained by the partial substitution of amine groups of the chitosan chain by acrylamide. The grafting reaction provides an ionizable amine group by a neutral amide group which make the matrix non pH-dependent. On the contrary, the matrix tablet based on chitosan showed a pH dependent swelling behaviour where the swelling process could be anisotropic. The higher degree of erosion and swelling of the formulation based on CB-g-A600 (%G = 600) compared with the formulation based on chitosan and CB-g-A418 (%G = 418) could explain the higher fraction of theopylline released. For all formulations studied in this work, the amount of theopylline released from the matrix tablets was found to be controlled by a combination of the diffusion process and relaxation of the polymeric structure. These results match with the controlled swelling behaviour and low degree of erosion observed for these systems.

Evaluation of a multilayered chitosan-hydroxy-apatite porous composite enriched with fibronectin or an in vitro-generated bone-like extracellular matrix on proliferation and diferentiation of osteoblasts.

The use of extracellular matrix (ECM) molecules from tissues is an interesting way to induce specific responses of cells grown onto composite scaffolds to promote adhesion, proliferation and differentiation. There have been several studies on the effects on cell proliferation and differentiation of osteoprogenitor cells cultured onto composites, either adding some ECM molecules or grown in the presence of growth factors. Other studies involve the use of osteoblasts cultured on a three-dimensional (3D) matrix, enriched with ECM molecules produced by the same cells grown previously inside the composite. Here, the effect of enrichment of a novel multilayered chitosan-hydroxyapatite composite with ECM molecules produced by osteoblasts, or the addition of 25 or 50 µg/ml fibronectin to the composite, on proliferation and differentiation of osteoblasts cultured on these composites was studied. The results showed an increase in the number of osteoblasts from day 1 of culture, which was higher in the group grown onto composites enriched with the highest concentration of fibronectin or with ECM molecules produced naturally by osteoblasts cultured previously on them, when compared with the control group. However, this increment tended to decline in all groups after day 7 of culture, the day when they reached the highest peak of proliferation. Differentiation expressed as alkaline phosphatase activity followed the proliferation pattern of the cells cultivated on the scaffolds. The results demonstrate the potential offered by these enriched 3D multilayered composites for improving their ability as bone grafting material.

Study of the release mechanism of diltiazem hydrochloride from matrices based on chitosan-alginate and chitosan-carrageenan mixtures.

The aim of this work was to establish the diltiazem hydrochloride release mechanism from the chitosan-alginate matrix tablet (MCB/AS) and chitosan-carrageenan matrix tablet (MCS/CSI). The weight loss for MCS/CSI is mainly due to the weight loss of the matrix while for MCB/AS it is mainly due to the diltiazem hydrochloride released from the tablet. Using the Peppa's model the release order for MCS/CSI was n = 1.07 +/- 0.13 and for MCB/AS was n = 0.76 +/- 0.02. Thus, MCS/CSI has a transport mechanism, and for MCB/AS the drug release mechanism is a combined process of diffusion and relaxation. MCB/AS has an elastic modulus (G' = 10(5) Pa) one order of magnitude higher than MCS/CSI (G' = 10(4) Pa). MCB/AS is able to uptake solvent without disrupting the microstructure due to its high elastic modulus. Instead MCS/CSI showed a quick erosion process, which conducted to the tablet disintegration due to a fast solvent uptake process.