Cristina Gentilini

Water-Soluble Gold Nanoparticles Protected by Fluorinated Amphiphilic Thiolates

The preparation and the properties of gold nanoparticles (Au NPs) protected by perfluorinated amphiphiles are described. The thiols were devised to form a perfluorinated region close to the gold surface and to have a hydrophilic portion in contact with the bulk solvent to impart solubility in water. The monolayer protected clusters were prepared, in an homogeneous phase using sodium thiolates because of the low nucleophilicity of the alpha-perfluorinated thiols, and fully characterized with (1)H, (19)F NMR spectrometry, IR and UV-vis absorption spectroscopies, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). Au NPs with core diameters ranging from 1.6 to 2.9 nm, depending on the reaction conditions, were obtained. Water-soluble NPs (MPC-F8-PEGs) were obtained with the thiol HS-F8-PEG ending with a short poly(ethylene glycol) unit (PEG-OMe 550), whereas thiols with shorter PEG chains give rise to NPs insoluble in water. MPC-F8-PEGs undergo an exchange reaction with amphiphilic alkyl thiols. ESR investigations, using a hydrophobic radical probe, indicate that the MPC-F8-PEG monolayer shows a greater hydrophobicity compared to the analogous hydrogenated monolayer.

Morphology of mixed-monolayers protecting metal nanoparticles

Anisotropic nanoparticles with precisely controlled chemical functionality are attractive building blocks for the assembly of sophisticated new materials and devices. Metal nanoparticles protected by self-assembled organic monolayers (MPCs) have drawn increasing attention due to potential applications in biosensing, catalysis, electronics and nanotechnology. However, a significant challenge remaining in nanoscience research is the capability to break symmetry in the isotropic ligand shell passivating these metal particles. Here we present recent strategies exploited to control the topology of multi-component self-assembled monolayers on metal nanoparticles.

Functionalized Poly(γ‐Glutamic Acid) Fibrous Scaffolds for Tissue Engineering

Poly(γ-glutamic acid) (γ-PGA) is a biocompatible, enzymatically-degradable, natural polymer with a higher resistance to hydrolysis than polyesters commonly used for tissue engineering scaffolds such as poly(L-lactide) (PLLA). Notably, γ-PGAs free carboxyl side groups allow for simple chemical functionalization, making it a versatile candidate for producing scaffolds. Here, a series of water-resistant fibrous scaffolds were engineered from ethyl (Et), propyl (Pr) and benzyl (Bn) esterifications of γ-PGA. All scaffolds were non-cytotoxic and γ-PGA-Bn showed an increase in cell adhesion of hMSCs compared to γ-PGA-Et and γ-PGA-Pr. Moreover, cells on γ-PGA-Bn showed three-fold higher viability at day 14 and significantly higher adhesion when compared with PLLA scaffolds, despite having a similar hydrophobicity. Cell attachment decreased by 40% when the polymer was only partially modified with benzyl groups (γ-PGA-Bn-77%), but was restored when integrin-binding RGD peptide was conjugated to the remaining free carboxylic groups, indicating the peptide was accessible and able to bind integrins. The mechanism behind the cell-material interactions on γ-PGA-Bn scaffolds was further investigated through protein adsorption and fibronectin conformation experiments. These results, in addition to the cell-adhesion studies, suggest an inherent effect of the benzyl modification in the mechanism of cell attachment to γ-PGA-Bn scaffolds. Finally, γ-PGA-Bn scaffolds cultured in osteogenic media were also efficient in supporting hMSCs differentiation towards an osteogenic lineage as determined by alkaline phosphatase and Runx2 gene expression. Taken together these data suggest that esterified γ-PGA polymer scaffolds are new and versatile candidates for tissue engineering applications and that, intriguingly, aromatic functionality plays a key role in the cell-scaffold interaction.

Peptide-directed spatial organization of biomolecules in dynamic gradient scaffolds.

Specific binding peptides are used to spatially organize biomolecule gradients within an electrospun fiber scaffold. Different biomolecule-binding peptide-polymer conjugates are sequentially co-electrospun with a fiber-forming host polymer to generate opposing gradients of peptide functionalization. The binding peptides specifically and non-covalently guide the spatial arrangement of biomolecules into dynamic gradients within the scaffold, mimicking biological gradients found in native tissues.

Self-Organization of Mixtures of Fluorocarbon and Hydrocarbon Amphiphilic Thiolates on the Surface of Gold Nanoparticles

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.

Responsive poly (γ-glutamic acid) fibres for biomedical applications

A novel responsive system using a protein-based biopolymer was designed to undergo structural, geometric, and chemical changes upon temperature change or solvent interaction. Poly(γ-glutamic acid) (γ-PGA) is an attractive candidate for various biomedical applications as it is naturally produced, biocompatible and enzymatically degradable. The responsive material was fabricated using an electrospun modified γ-PGA to create a sub-micron fibrous mat. By modulating the environment responsive behaviour in a controlled manner, exciting applications such as wound dressing, compression materials and self-tightening knots are envisaged.

Tailoring of mechanical properties of derivatized natural polyamino acids through esterification and tensile deformation

Tensile deformation was applied to the naturally produced poly-γ-glutamic acid, which can be enzymatically degraded and is, therefore, of interest for biomedical use. However, natural polyamino acids have a similar chemical structure to synthetic polyamides (“nylons”), which are known to feature strong inter-molecular hydrogen bonding that prevents large-scale molecular motion in their solid state. Through esterification, this hydrogen bonding was partially shielded, allowing orientation of the polyamino acid macromolecules through tensile deformation. An increase in Youngs modulus and tensile strength was achieved of solution-cast films of the chemically modified poly-γ-glutamic acids, consistent with enhanced uniaxial polymer chain orientation. The latter was confirmed by both wide-angle X-ray scattering and polarized Raman spectroscopy. The films thus produced were found to be non-cytotoxic. These mechanically tailorable, biocompatible polymers may be excellent candidates for use in musculoskeletal tissue engineering applications that have different loading requirements within the body.

Self-sorting in mixed fluorinated/hydrogenated assemblies

Abstract Mixtures of fluorinated and hydrogenated compounds display peculiar properties arising from their mutual phobicity and the same applies to semifluorinated species in which a reciprocal phobicity pattern exists within the same molecule. The interest in assemblies comprising these species stems from the ease in which self-sorting can take place, allowing the preparation of compartmentalised molecular aggregates with unique hydrophobic patterns or surface features. Most importantly, this is the result of molecular properties rather than specifically designed fabrication techniques. This brief overview describes some examples that are instrumental to present the features of fluorinated/hydrogenated supramolecular assemblies in which self-sorting of the dislike units takes place at different length scales. This review is focussed on flat assemblies such as self-assembled monolayers on gold surfaces, Langmuir Blodgett films and on three dimensional assemblies such as micelles, vesicles and nanoparticles.