Polyvinyl alcohol-based hydrogel sorbent for extraction of parabens in human milk samples by in-tube SPME-LC-UV.

In this work, we developed an in-tube solid-phase microextraction (SPME) device consisting of a fused silica capillary modified with a polyvinyl alcohol (PVOH) hydrogel. Methylparaben, ethylparaben, propylparaben, and butylparaben were determined in human milk samples by using the in-tube SPME device coupled with liquid chromatography with spectrophotometric detection in the ultraviolet region (LC-UV). The inner surface of the fused silica capillary was silanized to allow covalent modification with the PVOH-hydrogel, using glutaraldehyde as cross-linking agent. The developed device was used up to 250 times with no reduction in the analytes' peak areas or carryover effect, besides having a low production cost. The human milk samples showed a significant matrix effect for parabens with higher logKo/w. Low limits of quantification (LLOQ) between 10.0 and 15.0 ng mL-1 were obtained with RSD values in the range of 1.18 to 18.3%. For the intra- and inter-day assays, RSD values from 5.6 to 16.5% and accuracy from 74.5 to 128.8% were achieved. The PVOH-based hydrogel sorbent allowed the use of water as desorption solvent, eliminating the use of organic solvents, which follows the principles of green chemistry. The results showed a great application potential of the PVOH-based hydrogel sorbent for the extraction of organic compounds from high-complexity samples.

In vitro biocompatibility screening of a colloidal gum Arabic-polyaniline conducting nanocomposite.

Although polyaniline (PANI) is a widely investigated conductive polymer for biological applications, studies addressing the biocompatibility of colloidal PANI dispersions are scarcely found in the literature of the area. Therefore, PANI nanoparticles stabilized by the natural polysaccharide gum Arabic (GA) were screened for their biocompatibility. The GA successfully stabilized the colloidal PANI-GA dispersions when exposed to a protein-rich medium, showing compatibility with the biological environment. The results obtained from a series of in vitro assays showed that, after up to 48 h of exposure to a range of PANI-GA concentrations (1-50 µg/mL), both mouse BALB/3T3 fibroblasts and RAW 264.7 macrophages showed no evidence of change in cellular proliferation, viability and metabolic activity. An increase in macrophage granularity poses as evidence of phagocytic uptake of PANI-GA, without resulting activation of this cell type. Additionally, the PANI-GA nanoparticles modulated the cell morphology changes induced on fibroblasts by GA in a concentration-dependent manner. Thus, this unprecedented biocompatibility study of PANI nanoparticles stabilized by a plant gum exudate polysaccharide showed promising results. This simple biomaterial might be further developed into colloidal formulations for biological and biomedical applications, taking advantage of its versatility, biocompatibility, and conductive properties.

Acacia mearnsii gum: A residue as an alternative gum Arabic for food stabilizer.

Acacia mearnsii gum is not commercially exploited, being characterized as residue from A. mearnsii cultivation. This work investigated the A. mearnsii gum polysaccharide composition, its cytotoxicity and the technological effect as a stabilizer in ice cream. A. mearnsii gum showed a similar chemical structure to commercial gum Arabic and did not decrease the viability and proliferation of fibroblast cells (Balb/3T3) and hepatocarcinoma (HepG2). Rheological tests showed that the ice cream stabilized by the A. mearnsii gum had a more structured system (more interactions between the mixture components) and the same melting characteristics as the ice cream samples made with commercial gum Arabic. The results showed that A. mearnsii gum, which is actually an agro-industrial residue from tannin production for industry, is a potential stabilizing gum for the food industry, contributing to the economic development of the exploitation chain of A. mearnsii products and by-products.

Beyond gold nanoparticles cytotoxicity: Potential to impair metastasis hallmarks.

Gold nanoparticle (AuNP)-based systems have been extensively investigated as diagnostic and therapeutic agents due to their tunable properties and easy surface functionalization. Upon cell uptake, AuNPs present an inherent cell impairment potential based on organelle and macromolecules damage, leading to cell death. Such cytotoxicity is concentration-dependent and completely undesirable, especially if unspecific. However, under non-cytotoxic concentrations, internalized AuNPs could potentially weaken cells and act as antitumor agents. Therefore, this study aimed to investigate the antitumor effect of ultrasmall AuNPs (~3 nm) stabilized by the anionic polysaccharide gum arabic (GA-AuNPs). Other than intrinsic cytotoxicity, the focus was downregulation of cancer hallmarks of aggressive tumors, using a highly metastatic model of melanoma. We first demonstrated that GA-AuNPs showed excellent stability under biological environment. Non-cytotoxic concentrations to seven different cell lines, including tumorigenic and non-tumorigenic cells, were determined by standard 2D in vitro assays. Gold concentrations ≤ 2.4 mg L-1 (16.5 nM AuNPs) were non-cytotoxic and therefore chosen for further analyses. Cells exposed to GA-AuNPs were uptaken by melanoma cells through endocytic processes. Next we described remarkable biological properties using non-cytotoxic concentrations of this nanomaterial. Invasion through an extracellular matrix barrier as well as 3D growth capacity (anchorage-independent colony formation and spheroids growth) were negatively affected by 2.4 mg L-1 GA-AuNPs. Additionally, exposed spheroids showed morphological changes, suggesting that GA-AuNPs could penetrate into the preformed tumor and affect its integrity. All together these results demonstrate that side effects, such as cytotoxicity, can be avoided by choosing the right concentration, nevertheless, preserving desirable effects such as modulation of key tumor cell malignancy features.

Production and characterization of bacterial cellulose membranes with hyaluronic acid from chicken comb.

The bacterial cellulose (BC), from Gluconacetobacter hansenii, is a biofilm with a high degree of crystallinity that can be used for therapeutic purposes and as a candidate for healing wounds. Hyaluronic acid (HA) is a constitutive polysaccharide found in the extracellular matrix and is a material used in tissue engineering and scaffolding for tissue regeneration. In this study, polymeric composites were produced in presence of hyaluronic acid isolated from chicken comb on different days of fermentation, specifically on the first (BCHA-SABT0) and third day (BCHA-SABT3) of fermentation. The structural characteristics, thermal stability and molar mass of hyaluronic acid from chicken comb were evaluated. Native membrane and polymeric composites were characterized with respect to their morphology and crystallinity. The optimized process of extraction and purification of hyaluronic acid resulted in low molar mass hyaluronic acid with structural characteristics similar to the standard commercial hyaluronic acid. The results demonstrate that the polymeric composites (BC/HA-SAB) can be produced in situ. The membranes produced on the third day presented better incorporation of HA-SAB between cellulose microfiber, resulting in membranes with higher thermal stability, higher roughness and lower crystallinity. The biocompatiblily of bacterial cellulose and the importance of hyaluronic acid as a component of extracellular matrix qualify the polymeric composites as promising biomaterials for tissue engineering.

Bacterial cellulose and hyaluronic acid hybrid membranes: Production and characterization.

In this study, the effect of the addition of hyaluronic acid (HA) on bacterial cellulose (BC) production, under static conditions was evaluated in terms of the properties of the resulting BC hybrid membranes. HA was added to the fermentation process in three distinct time points: first day (BC-T0), third day (BC-T3) and sixth day (BC-T6). Analyses of FT-IR and CP/MAS (13)C NMR confirmed the presence of HA in bacterial cellulose membranes. The crystal structure, crystallinity index (Ic) surface roughness, thermal stability and hybrophobic/hydrophilic character changed. Membranes with higher roughness were produced with HA added on the first and third day of fermentation process. The surface energy of BC/HA membranes was calculated and more hydrophilic membranes were produced by the addition of HA on the third and sixth day, also resulting in more thermally stable materials. The results demonstrate that bacterial cellulose/hyaluronic acid hybrid membranes can be produced in situ and suggest that HA interacts with the sub-elementary bacterial cellulose fibrils, changing the properties of the membranes. The study and understanding of the factors that affect those properties are of utmost importance for the safe and efficient use of BC as biomaterials in numerous applications, specifically in the biological field.

Bioactive nanocomposites of bacterial cellulose and natural hydrocolloids.

The aim of this work was to develop bioactive films from bacterial cellulose and hydrocolloids (guar gum and hyaluronic acid), coated or not with collagen. After mechanical treatment, a suspension of cellulose nanofibres was obtained which, combined with the dispersions of hydrocolloids, was used to produce bionanocomposite films by wet casting. The materials were stable in physiological solution and presented better swelling capacity than that of the bacterial cellulose. The films were coated with collagen by dipping. Cell adhesion tests and surface analysis by tensiometry, X-ray photoelectron spectroscopy and atomic force microscopy showed that the surface properties of the films can be adjusted by changing the proportions of the components. The collagen coating presented a self-assembling pattern resembling that of living tissues. The materials developed in this work showed potential for applications in the medical field as bioactive wound dressings, scaffolds for cellular growth and sustained drug release systems. The films were obtained by simple production and purification methods, including the use of low toxicity solvents. Thus, in addition to potential cost saving, the development of these bionanocomposites is in accordance with green chemistry principles.