Tamara Posati

The Interplay of Monolayer Structure and Serum Protein Interactions on the Cellular Uptake of Gold Nanoparticles

A critical factor for controlling serum albumin binding is surface hydrophobicity, which in turn decreases the cellular uptake of gold nanoparticles. Hydrophobic nanoparticles bind albumin more tightly, inhibiting particle uptake, with a direct correlation observed between uptake and surface hydrophobicity.

Structure and catalytic behavior of myoglobin adsorbed onto nanosized hydrotalcites.

The adsorption of myoglobin (Mb) onto nanosized nickel aluminum hydrotalcite (NiAl-HTlc) surface was studied, and the structural properties of the resulting protein layer were analyzed by using FT-IR, Raman, and fluorescence spectroscopies. Upon adsorption onto the nanoparticle surface, the protein molecules maintained their secondary structure, while the tertiary structure was altered. The fluorescence spectra and anisotropy values of adsorbed Mb revealed that the emitting amino acid residues are affected by different microenvironments when compared to the native protein behavior. Moreover, the decrease of fluorescence decay times of tryptophan indicated the occurrence of interactions among the fluorophores and the constituents of the nanoparticles, such as the metal cations, which can take place when conformational changes of Mb occur. Raman spectra indicated that the interaction of Mb molecules with NiAl-HTlc nanoparticles modified the porphyrin core, changing the spin state of the heme iron from high spin (HS) to low spin (LS). The enzymatic activity of the nanostructured biocomposite was evaluated in the oxidation of 2-methoxyphenol by hydrogen peroxide and discussed on the basis of structural properties of adsorbed myoglobin.

Synthesis of colloidal dispersions of NiAl, ZnAl, NiCr, ZnCr, NiFe, and MgFe hydrotalcite-like nanoparticles

Colloidal aqueous dispersions of nanometric NiAl, ZnAl, NiCr, ZnCr, NiFe, and MgFe hydrotalcite-like compounds were prepared in a water/cetyltrimethylammonium bromide/n-butanol/isooctane microemulsion. Particle sizes were analyzed with different techniques, and the results confirm dimensions between 10 and 30 nm, except for ZnAl-HTlc (150-200 nm). A good colloidal stability of HTlc-NPs aqueous dispersions, investigated with DLS and Pz measurements, was obtained without the need for any stabilizing agent. SEM images clearly showed that the obtained HTlc posses a high tendency to spontaneously form homogeneous and dense stacking of plate-like HTlc crystals directly from aqueous solution, giving rise to the developing of functional materials in optical, electrical and magnetic fields.

New insights on the incorporation of lanthanide ions into nanosized layered double hydroxides.

Nanosized Layered Double Hydroxides (LDH) were prepared in confined environment through the microemulsion method in the presence of different lanthanide cations (Ln(III) = Eu(III), Yb(III), Tb(III), and Nd(III)). To investigate the effects of lanthanide insertion in the sheets of LDH materials, several samples were prepared upon progressively increasing the content of Ln ions and properly reducing the Al(III) amount; the samples were characterized in terms of metal content, structure, morphology, thermal behavior, and spectroscopic properties. The data revealed that Ln(III) content in the LDH samples depends on the ionic radius of the lanthanide cations and on its concentration in the starting microemulsion. X-ray powder diffraction (XRPD) indicated that Eu(III) can be inserted into the LDH structure in average atomic percentages lower than 2.7%, leading to the formation of a low symmetry phase, as confirmed by steady state luminescence spectra; while Yb(III) can be incorporated into the layer structure up to about 10% forming a pure layered phase containing the lanthanide in the sheet. The incorporation of Yb(III) and Eu(III) into the LDH sheets is also supported by FT-IR measurements. Coupled thermogravimetrical (TG) and differential scanning calorimetric (DSC) studies indicated that water molecules are essential in the coordination sphere of incorporated Ln cations; this observation accounts for the lower thermal stability of Ln-doped LDH compared to the undoped ones. Furthermore, Eu-luminescence measurements indicates that the lanthanide inclusion does not compromise its luminescence although the spectral position and brightness can be tuned by the loading.

Eciency enhancement of P3HT:PCBM solar cells containing scattering Zn-Al hydrotalcite nanoparticles in the PEDOT:PSS layer

Abstract In this article we report on a new hybrid (organic-inorganic) composite material based on hydrophilic, electrically inert and semi-transparent hydrotalcite (HT) nanoparticles and a pHneutral formulation of PEDOT:PSS. The application of this composite material as electrically and optically active buffer layer in P3HT:PC61BM bulk heterojunction (BHJ) solar cells is reported. Two different synthetic routes are explored to obtain HTs having discoid shape, with a diameter of around 150- 200 nm and a thickness of ~20 nm, to be easily embedded in ~50 nm thick PEDOT:PSS films. The good affinity between HTs and the sulfonate groups of the PEDOT:PSS allows to obtain homogeneous HTs/PEDOT:PSS films, for HT concentrations of 0.25% and 0.50% by weight (vs. PEDOT:PSS). At these particle loads the electrical and morphological features of doped and undoped PEDOT:PSS films are nearly identical, while providing a significant effect on the visible light scattering properties of the composite films. We demonstrate ~12% improvement in power conversion efficiency (PCE) for P3HT:PC61BM solar cells incorporating HTs in the PEDOT: PSS layer, which mainly originates from increased shortcircuit current densities (JSC).

Innovative multifunctional silk fibroin and hydrotalcite nanocomposites: a synergic effect of the components.

Novel hybrid functional materials are formed by combining hydrotalcite-like compounds and silk fibroin (SF-HTlc) via an environmental friendly aqueous process. The nanocomposites can be prepared with different weight ratio of the constituting components and preserve the conformational properties of the silk protein and the lamellar structure of hydrotalcites. Optical microscopy, scanning electron microscopy, and atomic force microscopy analyses show a good dispersion degree of the inorganic nanoparticles into the organic silk matrix. A mutual benefit on the stability of both organic and inorganic components was observed in the nanocomposites. SF-HTlc displayed limited dissolution of hydrotalcite in acidic medium, enhanced mechanical properties, and higher protease resistance of silk protein. The transparency, flexibility, and acidic environment resistance of silk fibroin combined to the protective and reinforcing properties of hydrotalcites generate a hybrid material, which is very attractive for applications in recently reported silk based opto-electronic and photonics technologies.

Protein interactions with nanosized hydrotalcites of different composition

Nanosized hydrotalcite-like compounds (HTlc) with different chemical composition were prepared and used to study protein adsorption. Two soft proteins, myoglobin (Mb) and bovine serum albumin (BSA), were chosen to investigate the nature of the forces controlling the adsorption and how these depend on the chemical composition of the support. Both proteins strongly interact with HTlc exhibiting in most cases a Langmuir-type adsorption. Mb showed a higher affinity for Nickel Chromium (NiCr-HTlc) than for Nickel Aluminum (NiAl-HTlc), while for BSA no significant differences between supports were found. Adsorption experiments in the presence of additives showed that proteins exhibited different types of interactions onto the same HTlc surface and that the adsorption was strongly suppressed by the addition of disodium hydrogen phosphate (Na(2)HPO(4)). Atomic force microscopy images showed that the adsorption of both proteins onto nanoparticles was followed by the aggregation of biocomposites, with a more disordered structure for BSA. Fluorescence measurements for adsorbed Mb showed that the inorganic nanoparticles induced conformational changes in the biomolecules; in particular, the interactions with HTlc surface quenched the tryptophan fluorescence and this process was particularly efficient for NiCr-HTlc. The adsorption of BSA onto the HTlc nanoparticles induced a selective quenching of the exposed fluorescent residues, as indicated by the blue-shift of the emission spectra of tryptophan residues and by the shortening of the fluorescence decay times.

Integration of a silk fibroin based film as a luminescent down-shifting layer in ITO-free organic solar cells

We report here a study on the integration of the silk fibroin (SF) protein in organic solar cells. The intrinsic low toxicity, natural availability, biodegradability, water processing, good film forming properties and capability to be doped with functional molecules of SF biopolymer inspired us to integrate it as a transparent and inert or functional bottom layer in organic solar cells. Water stable, optically transparent, smooth and homogeneous SF thin films (thickness ∼400 nm) were successfully prepared on glass and characterized. Then ITO-free bulk heterojunction (BHJ) solar cells employing P3HT:PC61BM as a standard active layer and a highly conductive PEDOT:PSS formulation as a semi-transparent anode were deposited over the SF films. As a result, the power conversion efficiency (PCE) of all silk-integrated BHJ solar cells was comparable to the references on bare glass. The ability of SF to act as a host matrix for functional moieties was exploited to give to the SF layer the functionality of a Luminescent Down-shifting film (LDS), as confirmed by the spectral response measurements, by using a water soluble stilbene derivative (Stb). The photovoltaic performance of all SF-based devices was significantly stable over time, overcoming the problems of the ITO-based reference cells after 70 days. Finally, flexible SF-integrated ITO-free solar cells were successfully fabricated on PET substrates.

A nanostructured conductive bio-composite of silk fibroin–single walled carbon nanotubes

Silk fibroin (SF), a protein core fibre from the silkworm Bombyx mori, has huge potential to become a sustainable, biocompatible, and biodegradable material platform that can pave the way towards the replacement of plastic in the fabrication of bio-derived materials for a variety of technological and biomedical applications. SF has remarkable mechanical flexibility, controllable biodegradability, biocompatibility and is capable of drug/doping inclusion, stabilization and release. However, the dielectric properties of SF limit its potential as a direct bioelectronic interface in biomedical devices intended to control the bioelectrical activity of the cell for regenerative purposes. In this work, a novel wet templating method is proposed to generate nanostructured, conductive Silk Fibroin (SF) composite films. We combine the unusual properties of SF, such as its mechanical properties, its convenience and biocompatibility with the electrical conductivity and stiffness of Single Walled Carbon Nanotubes (SWCNTs). The presented SF-SWCNT composite displays a periodic architecture where SWCNTs are regularly and homogeneously distributed in the SF protein matrix. The morphological and chemo-physical properties of the nanocomposite are analysed and defined by SEM, Raman Spectroscopy, ATR-IR, UFM and contact angle analyses. Notably, the SF-SWCNT composite film is conductive, showing additional functionality compared to the dielectric properties of the bare SF film. Finally, SF-SWCNT is biocompatible and enables the growth of primary rat Dorsal Root Ganglion (DRG) neurons. Collectively our results demonstrate that the nanostructured, conductive, robust and biocompatible SF-SWCNT composite can be fabricated using a wet templating method, paving the way towards the fabrication and development of silk-based electronic devices for use in bioelectronic and biomedical applications.

A lysinated thiophene-based semiconductor as a multifunctional neural bioorganic interface.

Lysinated molecular organic semiconductors are introduced as valuable multifunctional platforms for neural cells growth and interfacing. Cast films of quaterthiophene (T4) semiconductor covalently modified with lysine-end moieties (T4Lys) are fabricated and their stability, morphology, optical/electrical, and biocompatibility properties are characterized. T4Lys films exhibit fluorescence and electronic transport as generally observed for unsubstituted oligothiophenes combined to humidity-activated ionic conduction promoted by the charged lysine-end moieties. The Lys insertion in T4 enables adhesion of primary culture of rat dorsal root ganglion (DRG), which is not achievable by plating cells on T4. Notably, on T4Lys, the number on adhering neurons/area is higher and displays a twofold longer neurite length than neurons plated on glass coated with poly-l-lysine. Finally, by whole-cell patch-clamp, it is shown that the biofunctionality of neurons cultured on T4Lys is preserved. The present study introduces an innovative concept for organic material neural interface that combines optical and iono-electronic functionalities with improved biocompatibility and neuron affinity promoted by Lys linkage and the softness of organic semiconductors. Lysinated organic semiconductors could set the scene for the fabrication of simplified bioorganic devices geometry for cells bidirectional communication or optoelectronic control of neural cells biofunctionality.