RESUMO
Low intrinsic toxicity, high solubility, and stability are important and necessary features of gold nanoparticles to be used in the biomedical field. In this context, charged nanoparticles proved to be very versatile, and among them charged mixed-monolayer gold nanoparticles, displaying monolayers with well-defined morphologies, represent a paradigm. By using mixtures of hydrogenated and fluorinated thiols, the formation of monolayer domains may be brought to an extreme because of the immiscibility of fluorinated and hydrogenated chains. Following this rationale, mixed monolayer gold nanoparticles featuring ammonium, sulfonate, or carboxylic groups on their surface were prepared by using amphiphilic hydrogenated thiols and 1H,1H,2H,2H-perfluoro-alkanethiols. The toxicity of these systems was assessed in HeLa cells and was found to be, in general, low even for the cationic nanoparticles which usually show a high cytotoxicity and is comparable to that of homoligand gold nanoparticles displaying amphiphilic-charge neutral-hydrogenated or fluorinated thiolates in their monolayer. These properties make the mixed ligand monolayer gold nanoparticles an interesting new candidate for medical application.
Assuntos
Ouro/química , Nanopartículas Metálicas/química , Compostos de Sulfidrila/química , Corantes Fluorescentes/química , Halogenação , Células HeLa , HumanosRESUMO
The use of binary blends of hydrogenated and fluorinated alkanethiolates represents an interesting approach to the construction of anisotropic hybrid organic-inorganic nanoparticles since the fluorinated and hydrogenated components are expected to self-sort on the nanoparticle surface because of their reciprocal phobicity. These mixed monolayers are therefore strongly non-ideal binary systems. The synthetic routes we explored to achieve mixed monolayer gold nanoparticles displaying hydrogenated and fluorinated ligands clearly show that the final monolayer composition is a non-linear function of the initial reaction mixture. Our data suggest that, under certain geometrical constraints, nucleation and growth of fluorinated domains could be the initial event in the formation of these mixed monolayers. The onset of domain formation depends on the structure of the fluorinated and hydrogenated species. The solubility of the mixed monolayer nanoparticles displayed a marked discontinuity as a function of the monolayer composition. When the fluorinated component content is small, the nanoparticle systems are fully soluble in chloroform, at intermediate content the nanoparticles become soluble in hexane and eventually they become soluble in fluorinated solvents only. The ranges of monolayer compositions in which the solubility transitions are observed depend on the nature of the thiols composing the monolayer.
RESUMO
Two structurally different water-soluble homoligand gold nanoparticle systems, one featuring a rigid fluorous monolayer in the proximity of the gold core and the other featuring a flexible fluorinated region in a distal position, were studied as putative hosting systems by determining their binding constants for a series of fluorinated and non-fluorinated radical probes by means of ESR spectroscopy. Comparison of the binding constants obtained with hydrogenated homoligand nanoparticles of similar structure used as the reference evidenced that the binding of both hydrogenated and fluorinated guests is favoured in the presence of fluorinated nanoparticles. In addition, a flexible fluorinated monolayer acts as a better hosting system than the more rigid counterpart. In the latter case decreasing the size of the nanoparticles causes a small decrease of the binding affinities for both hydrogenated and fluorinated guests. The same nanoparticle systems were analysed for their ability to retard the phase transfer of a fluorescent dye from an aqueous solution to a toluene layer. All of the nanoparticles studied produced a significant decrease of the phase transfer rate of the dye because of the efficient interaction with the monolayer. These data support the introduction of fluorinated moieties in the monolayer of gold nanoparticles as a novel design tool for the development of drug delivery systems.
RESUMO
Self-assembled monolayers composed of a mixture of thiolate molecules, featuring hydrocarbon or perfluorocarbon chains (H- and F-chains) terminating with a short poly(oxoethylene) (PEG) moiety, are the most extreme example of surfactant immiscibility on gold nanoparticles reported so far. The phase segregation between H-chains and F-chains and the consequent, peculiar folding of PEG chains are responsible for the increased affinity of a selected radical probe for the fluorinated region, which increases as the size of the fluorinated domains decrease, independently of the shape of such domains. This feature has been revealed by ESR measurements and an in silico innovative multiscale molecular simulations approach in explicit water. Our results reveal an underlying mechanism of a transmission of the organization of the monolayer from the inner region close to the gold surface toward the external hydrophilic PEG region. Moreover, this study definitively proves that a mixed monolayer is a complex system with properties markedly different from those characterizing the parent homoligand monolayers.
Assuntos
Cristalização/métodos , Fluorocarbonos/química , Ouro/química , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Polietilenoglicóis/química , Compostos de Sulfidrila/química , Interações Hidrofóbicas e Hidrofílicas , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Bovine and human serum albumins catalyze the aldol reaction of aromatic aldehyedes and acetone, with saturation kinetics and moderate and opposite enantioselectivity. The reaction occurs at the binding site in domain IIa, and is inhibited by warfarin. Kinetic data are consistent with an enamine mechanism. The activity is conserved in a 103 aminoacid peptide derived from the albumin sequence.