When dispersed in biological fluids, engineered nanoparticles are selectively coated with proteins, resulting in the formation of a protein corona. It is suggested that the protein corona is critical in regulating the conditions of entry into the cytoplasm of living cells. Recent reports describe this phenomenon as ubiquitous and independent of the nature of the particle. For nanomedicine applications, however, there is a need to design advanced and cost-effective coatings that are resistant to protein adsorption and that increase the biodistribution in vivo. In this study, phosphonic acid poly(ethylene glycol) copolymers were synthesized and used to coat iron oxide particles. The copolymer composition was optimized to provide simple and scalable protocols as well as long-term stability in culture media. It is shown that polymers with multiple phosphonic acid functionalities and PEG chains outperform other types of coating, including ligands, polyelectrolytes, and carboxylic acid functionalized PEG. PEGylated particles exhibit moreover exceptional low cellular uptake, of the order of 100 femtograms of iron per cell. The present approach demonstrates that the surface chemistry of engineered particles is a key parameter in the interactions with cells. It also opens up new avenues for the efficient functionalization of inorganic surfaces.

Recent studies have pointed out the importance of polyelectrolyte assembly in the elaboration of innovative nanomaterials. Beyond their structures, many important questions on the thermodynamics of association remain unanswered. Here, we investigate the complexation between poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium acrylate) (PANa) chains using a combination of three techniques: isothermal titration calorimetry (ITC), static and dynamic light scattering and electrophoresis. Upon addition of PDADMAC to PANa or vice-versa, the results obtained by the different techniques agree well with each other, and reveal a two-step process. The primary process is the formation of highly charged polyelectrolyte complexes of size 100 nm. The secondary process is the transition towards a coacervate phase made of rich and poor polymer droplets. The binding isotherms measured are accounted for using a phenomenological model that provides the thermodynamic parameters for each reaction. Small positive enthalpies and large positive entropies consistent with a counterion release scenario are found throughout this study. Furthermore, this work stresses the importance of the underestimated formulation pathway or mixing order in polyelectrolyte complexation.

We report the synthesis of complex salts made from the cationic surfactant dodecyltrimethylammonium and diblock copolymers poly(acrylic acid)-block-poly(acrylamide) of different molecular weights. In water, the complex salts self-assemble into stable hierarchical aggregates with a dense core and a diffuse shell. In contrast to earlier reports, the surfactant/polymer aggregates exhibit a liquid crystalline structure of 3 cubic symmetry. The crystal structure is analogous to that obtained with homopolymer. Size and aggregation numbers were estimated from a combination of light and small-angle x-ray scattering experiments. It is found that the size of the aggregates decreases with increasing diblock asymmetry. The complex salt methodology presents many advantages, among which to be insensitive to the preparation conditions and to the mixing pathway.

Abstract:The electrostatic charge density of particles is of paramount importance for the control of the dispersion stability. Conventional methods use potentiometric, conductometric or turbidity titration but require large amount of samples. Here we report a simple and cost--effective method called polyelectrolyte assisted charge titration spectrometry or PACTS. The technique takes advantage of the propensity of oppositely charged polymers and particles to assemble upon mixing, leading to aggregation or phase separation. The mixed dispersions exhibit a maximum in light scattering as a function of the volumetric ratio , and the peak position !"# is linked to the particle charge density according to ~ ! !"# where ! is the particle diameter. The PACTS is successfully applied to organic latex, aluminum and silicon oxide particles of positive or negative charge using poly(diallyldimethylammonium chloride) and poly(sodium 4--styrenesulfonate). The protocol is also optimized with respect to important parameters such as pH and concentration, and to the polyelectrolyte molecular weight. The advantages of the PACTS technique are that it requires minute amounts of sample and that it is suitable to a broad variety of charged nano--objects.

Neste trabalho, foi avaliada a influência dos estádios de maturação sobre as características químicas do suco de maracujá-amarelo (Passiflora edulis f. flavicarpa Degener), durante o período que antecedeu a mudança de cor da casca até o período de abscisão dos frutos, quando apresentavam coloração da casca totalmente amarelada. Durante o amadurecimento dos frutos, foi observado aumento progressivo dos parâmetros de Hunter L e b, sendo que a região inferior do fruto apresentou aumento de luminosidade e do amarelecimento mais rapidamente do que a superior. O conteúdo de Sólidos Solúveis Totais (SST) aumentou progressivamente, desde a condição de frutos imaturos, com 52 Dias Após Antese (DAA), até os 76 DAA, quando apresentaram cerca de 65% de cor amarela, permanecendo constante após este período. As medidas de acidez titulável e de pH indicaram pequeno acúmulo de ácidos orgânicos até os 60 DAA e, posteriormente, durante o amadurecimento dos frutos de maracujazeiro, ocorreu um consumo parcial desses ácidos, confirmados pela redução da acidez titulável e aumento de pH. Observou-se também, neste período, que a relação SST/AT aumentou progressivamente.

Este trabalho teve como objetivo determinar uma escala de coloração da casca para identificar o estádio de maturação do maracujá-amarelo e avaliar o rendimento em suco, em diferentes épocas de colheita. Os experimentos foram constituídos de 2 épocas de colheita, contemplando a estação de menor temperatura e menor precipitação de chuvas (EP1-Maio/Setembro), a estação de maior temperatura e precipitação de chuvas (EP2-Outubro/Dezembro) e 7 estádios de maturação, com 10 repetições. Os resultados foram avaliados pelo teste de Tukey, a 5% de significância. O parâmetro b de Hunter foi utilizado como o indexador da mudança da coloração amarela. Verificou-se que a mudança de coloração ocorreu no sentido da base para o pedúnculo do fruto. Os frutos da época EP2 apresentaram a maior espessura de casca e o menor rendimento em suco, nos estádios iniciais de amadurecimento. Nos frutos com mais de 65,9% da casca amarelada, a época de colheita não influenciou na espessura da casca e no rendimento em suco, apresentando níveis máximos de suco. Frutos da época EP1 apresentaram o máximo rendimento a partir do estádio com 21,3% de cor amarela.

Interaction between engineered nanoparticles and natural organic matter is investigated by measuring the exchanged heat during binding process with isothermal titration calorimetry. TiO2 anatase nanoparticles and alginate are used as engineered nanoparticles and natural organic matter to get an insight into the thermodynamic association properties and mechanisms of adsorption and agglomeration. Changes of enthalpy, entropy and total free energy, reaction stoichiometry and affinity binding constant are determined or calculated at a pH value where the TiO2 nanoparticles surface charge is positive and the alginate exhibits a negative structural charge. Our results indicate that strong TiO2-alginate interactions are essentially entropy driven and enthalpically favorable with exothermic binding reactions. The reaction stoichiometry and entropy gain are also found dependent on the mixing order. Finally correlation is established between the binding enthalpy, the reaction stoichiometry and the zeta potential values determined by electrophoretic mobility measurements. From these results two types of agglomeration mechanisms are proposed depending on the mixing order. Addition of alginate in TiO2 dispersions is found to form agglomerates due to polymer bridging whereas addition of TiO2 in alginate promotes a more individually coating of the nanoparticles.

The association processes between engineered TiO 2 nanoparticles and Suwannee River humic acids are investigated by isothermal titration calorimetry and by measuring the exchanged heat during binding process allowing the determination of thermodynamic (change of enthalpy, Gibbs free energy and entropy) and reaction (binding affinity constant, reaction stoichiometry) parameters. Our results indicate that strong TiO 2 -Suwannee River humic acid interactions are entropically and enthalpically favorable with exothermic binding reactions and that the mixing order is also an important parameter. High humic acid concentrations induce homoagglomeration ("self" assembly) and are shown to favor an enthalpically driven association process. Light scattering techniques are also considered to investigate the influence of TiO 2 surface charge modifications and agglomeration mechanisms. Patch and bridging mechanisms are found to result into the formation of large agglomerates once charge inversion of TiO 2 -humic acid complexes is achieved. Moreover van der Waals interactions are also found to play a significant role during interaction processes due to the amphiphilic character of humic acids.