Filipe E. Antunes

Polymer-vesicle association.

Mixed polymer-surfactant systems have been intensively investigated in the last two decades, with the main focus on surfactant micelles as the surfactant aggregate in interaction. The main types of phase behavior, driving forces and structural/rheological effects at stake are now fairly well understood. Polymer-vesicle systems, on the other hand, have received comparatively less attention from a physico-chemical perspective. In this review, our main goal has been to bridge this gap, taking a broad approach to cover a field that is in clear expansion, in view of its multiple implications for colloid and biological sciences and in applied areas. We start by a general background on amphiphile self-assembly and phase separation phenomena in mixed polymer-surfactant solutions. We then address vesicle formation, properties and stability not only in classic lipids, but also in various other surfactant systems, among which catanionic vesicles are highlighted. Traditionally, lipid and surfactant vesicles have been studied separately, with little cross-information and comparison, giving duplication of physico-chemical interpretations. This situation has changed in more recent times. We then proceed to cover more in-depth the work done on different aspects of the associative behavior between vesicles (of different composition and type of stability) and different types of polymers, including polysaccharides, proteins and DNA. Thus, phase behavior features, effects of vesicle structure and stability, and the forces/mechanisms of vesicle-macromolecule interaction are addressed. Such association may generate gels with interesting rheological properties and high potential for applications. Finally, special focus is also given to DNA, a high charge polymer, and its interactions with surfactants, and vesicles, in particular, in the context of gene transfection studies.

Aggregation and gelation in hydroxypropylmethyl cellulose aqueous solutions

In this work we present an analysis of the thermal behavior of hydroxypropylmethyl cellulose aqueous solutions, from room temperature to higher temperatures, above gelation. We focus on significant aspects, essentially overlooked in previous work, such as the correlation between polymer hydrophobicity and rheological behavior, and the shear effect on thermal gelation. Micropolarity and aggregation of the polymer chains were monitored by both UV/vis and fluorescence spectroscopic techniques, along with polarized light microscopy. Gel formation upon heating was investigated using rheological experiments, with both large strain (rotational) tests at different shear rates and small strain (oscillatory) tests. The present observations allow us to compose a picture of the evolution of the system upon heating: firstly, polymer reptation increases due to thermal motion, which leads to a weaker network. Secondly, above 55 degrees C, the polymer chains become more hydrophobic and polymer clusters start to form. Finally, the number of physical crosslinks between polymer clusters and the respective lifetimes increase and a three-dimensional network is formed. This network is drastically affected if higher shear rates, at non-Newtonian regimes, are applied to the system.

Gels of Pluronic F127 and nonionic surfactants from rheological characterization to controlled drug permeation.

The role of nonionic vesicles on the rheological behavior of Pluronic F127 is investigated above the dilute regime and below the cloud point of the nonionic surfactant. F127 is a copolymer possessing sol-gel transition by heating attributed to a phase transition from micellar to cubic. The presence of surfactant vesicles is expected to enhance the compartmentalization of a variety of drugs, independently of their affinity to the solvent. Such entrapment would be suitable for controlled release of the drugs in different applications. We address here a mixed Pluronic-nonionic surfactant system with particular emphasis to the effects of the surfactant on the rheological properties of the Pluronics, and the correlation between these properties and drug release control. The results show that the rheological properties of the mixed system are mainly governed by the behavior of the polymer alone and that the mixed system can be useful to control the percutaneous permeation of a small drug, such as Diclofenac Sodium salt.

Impact of organic and inorganic nanomaterials in the soil microbial community structure

In this study the effect of organic and inorganic nanomaterials (NMs) on the structural diversity of the soil microbial community was investigated by Denaturing Gradient Gel Electrophoresis, after amplification with universal primers for the bacterial region V6-V8 of 16S rDNA. The polymers of carboxylmethyl-cellulose (CMC), of hydrophobically modified CMC (HM-CMC), and hydrophobically modified polyethylglycol (HM-PEG); the vesicles of sodium dodecyl sulphate/didodecyl dimethylammonium bromide (SDS/DDAB) and of monoolein/sodium oleate (Mo/NaO); titanium oxide (TiO(2)), titanium silicon oxide (TiSiO(4)), CdSe/ZnS quantum dots, gold nanorods, and Fe/Co magnetic fluid were the NMs tested. Soil samples were incubated, for a period of 30 days, after being spiked with NM suspensions previously characterized by Dynamic Light Scattering (DLS) or by an ultrahigh-resolution scanning electron microscope (SEM). The analysis of similarities (ANOSIM) of DGGE profiles showed that gold nanorods, TiO(2), CMC, HM-CMC, HM-PEG, and SDS/DDAB have significantly affected the structural diversity of the soil bacterial community.

Toxicity and genotoxicity of organic and inorganic nanoparticles to the bacteria Vibrio fischeri and Salmonella typhimurium

The present work aimed at evaluating the toxicity and genotoxicity of two organic (vesicles composed of sodium dodecyl sulphate/didodecyl dimethylammonium bromide—SDS/DDAB and of monoolein and sodium oelate—Mo/NaO) and four inorganic (titanium oxide—TiO2, silicon titanium—TiSiO4, Lumidot™-CdSe/ZnS, and gold nanorods) nanoparticles (NP), suspended in two aqueous media (Milli Q® water and American Society for Testing and Materials (ASTM) hardwater), to the bacteria Vibrio fischeri (Microtox® test) and Salmonella typhimurium-his− (Ames® test with strains TA98 and TA100). Aiming a better understanding of these biological responses physical and chemical characterization of the studied NP suspensions was carried out. Results denoted a high aggregation state of the NP in the aqueous suspensions, with the exception of SDS/DDAB and Mo/NaO vesicles, and of nanogold suspended in Milli Q water. This higher aggregation was consistent with the low values of zeta potential, revealing the instability of the suspensions. Regarding toxicity data, except for nano TiO2, the tested NP significantly inhibited bioluminescence of V. fischeri. Genotoxic effects were only induced by SDS/DDAB and TiO2 for the strain TA98. A wide range of toxicity responses was observed for the six tested NP, differing by more than 5 orders of magnitude, and suggesting different modes of action of the tested NP.

Starch-based Pickering emulsions for topical drug delivery: A QbD approach.

Pickering emulsions are stabilized by solid particles instead of surfactants and have been widely investigated in pharmaceutical and cosmetic fields since they present less adverse effects than the classical emulsions. A quality by design (QbD) approach was applied to the production of w/o emulsions stabilized by starch. A screening design was conducted to identify the critical variables of the formula and the process affecting the critical quality properties of the emulsion (droplet size distribution). The optimization was made by establishing the Design Space, adjusting the concentration of starch and the quantity of the internal aqueous phase. The emulsion production process was, in turn, adjusted by varying the time and speed of stirring, to ensure quality and minimum variability. The stability was also investigated, demonstrating that an increase in starch concentration improves the stability of the emulsion. Rheological and mechanical studies indicated that the viscosity of the emulsions was enhanced by the addition of starch and, to a higher extent, by the presence of different lipids. The developed formulations was considered non-irritant, by an in vitro assay using human cells from skin (Df and HaCat) with the cell viability higher than 90% and, with self-preserving properties. Finally, the QbD approach successfully built quality in Pickering emulsions, allowing the development of hydrophilic drug-loaded emulsions stabilized by starch with desired organoleptic and structural characteristics. The results obtained suggest that these systems are a promising vehicle to be used in products for topical administration.

Screening evaluation of the ecotoxicity and genotoxicity of soils contaminated with organic and inorganic nanoparticles: The role of ageing

This study aimed to evaluate the toxicity and genotoxicity of soils, and corresponding elutriates, contaminated with aqueous suspensions of two organic (vesicles of sodium dodecyl sulphate/didodecyl dimethylammonium bromide and of monoolein and sodium oleate) and five inorganic nanoparticles (NPs) (TiO(2), TiSiO(4), CdSe/ZnS quantum dots, Fe/Co magnetic fluid and gold nanorods) to Vibrio fischeri and Salmonella typhimurium (TA98 and TA100 strains). Soil samples were tested 2h and 30 days after contamination. Suspensions of NPs were characterized by Dynamic Light Scattering. Soils were highly toxic to V. fischeri, especially after 2h. After 30 days toxicity was maintained only for soils spiked with suspensions of more stable NPs (zeta potential>30 mV or <-30 mV). Elutriates were particularly toxic after 2h, except for soil spiked with Fe/Co magnetic fluid, suggesting that ageing may have contributed for degrading the organic shell of these NPs, increasing the mobility of core elements and the toxicity of elutriates. TA98 was the most sensitive strain to the mutagenic potential of soil elutriates. Only elutriates from soils spiked with gold nanorods, quantum dots (QDs) and TiSiO(4) induced mutations in both strains of S. typhimurium, suggesting more diversified mechanisms of genotoxicity.

DNA-lipid systems: A physical chemistry study

It is well known that the interaction of polyelectrolytes with oppositely charged surfactants leads to an associative phase separation; however, the phase behavior of DNA and oppositely charged surfactants is more strongly associative than observed in other systems. A precipitate is formed with very low amounts of surfactant and DNA. DNA compaction is a general phenomenon in the presence of multivalent ions and positively charged surfaces; because of the high charge density there are strong attractive ion correlation effects. Techniques like phase diagram determinations, fluorescence microscopy, and ellipsometry were used to study these systems. The interaction between DNA and catanionic mixtures (i.e., mixtures of cationic and anionic surfactants) was also investigated. We observed that DNA compacts and adsorbs onto the surface of positively charged vesicles, and that the addition of an anionic surfactant can release DNA back into solution from a compact globular complex between DNA and the cationic surfactant. Finally, DNA interactions with polycations, chitosans with different chain lengths, were studied by fluorescence microscopy, in vivo transfection assays and cryogenic transmission electron microscopy. The general conclusion is that a chitosan effective in promoting compaction is also efficient in transfection.

A rheological investigation of the association between a non-ionic microemulsion and hydrophobically modified PEG. Influence of polymer architecture

Hydrophobically modified polymers (HM-P) typically behave as thickeners in a wide range of systems. The thickening effect in an aqueous solution of this kind of polymer depends on intermolecular hydrophobic associations and also on chain entanglements if the polymer concentration is significantly above the overlap concentration. In the present investigation a rather short end-capped polymer has been investigated at concentrations that are significantly below the overlap concentration. Despite the rather low polymer concentration, polymer chains were connected into a three-dimensional network by using microemulsion droplets as cross-linking points. The simple structure of the solution simplifies interpretations of results since chain entanglements can be expected to be of low importance and only intermolecular hydrophobic associations have to be considered. In particular the rheological response is in most cases well characterized by one single relaxation time and, then, the solution can be rationalized within the framework of the Maxwell model. We have found that the length of the polymer chains hydrophobic end-groups, as well as the temperature, have a large influence on dynamics of the system, while the length of the hydrophilic mid-block has a relatively small significance. On the other hand, the connectivity in the system depends critically on the microemulsion concentration. Thus, a maximum was found in viscosity as a function of volume fraction, interpreted as being due to a decrease in crosslink lifetime.

Dissolution state of cellulose in aqueous systems. 1. Alkaline solvents

The understanding of the state of dissolution of cellulose in a certain solvent is a critical step forward in the development of new efficient solvent systems for cellulose. Nevertheless, obtaining such information is not trivial. Recently, polarization transfer solid-state NMR (PTssNMR) was shown to be a very promising technique regarding an efficient and robust characterization of the solution state of cellulose. In the present study, combining PTssNMR, microscopic techniques and X-ray diffraction, a set of alkaline aqueous systems are investigated. The addition of specific additives, such as urea or thiourea, to aqueous NaOH based systems as well as the use of an amphiphilic organic cation, is found to have pronounced effects on the dissolution efficiency of cellulose. Additionally, the characteristics of the regenerated material are strongly dependent on the dissolution system; typically less crystalline materials, presenting smoother morphologies, are obtained when amphiphilic solvents or additives are used.