Pietro La Manna

Engineering poly(ethylene oxide) buccal films with cyclodextrin: a novel role for an old excipient?

Inspired by the multiple roles cyclodextrins can play in polymeric systems, here we engineered poly(ethylene oxide) (PEO) films with (2-hydroxypropyl)-β-cyclodextrin (CD) as multipurpose ingredient. To shed light on the potential of CD in formulating PEO buccal films for the delivery of poorly water-soluble drugs, we preliminarily assessed thermal and mechanical properties as well as wettability of films prepared at different PEO/CD ratios. PEO/CD platform containing 54% by weight of CD was chosen as the optimized composition since it matched acceptable mechanical properties, in terms of tensile strength and elasticity, with a good wettability. The platform was tested as buccal delivery system for triamcinolone acetonide (TrA), a lipophilic synthetic corticosteroid sparely water soluble. Confocal Raman imaging clearly showed that CD was homogeneously (i.e. molecularly) dispersed in PEO. Nevertheless, homogenous drug distribution in the film without TrA crystallization occurred only in the presence of CD. Finally, CD-containing PEO film placed in simulated buccal fluids provided a useful speed-up of TrA release rate while showing slower dissolution as compared to PEO film. These results, as well as compliance with quality specifications of pharmaceutical manufacturing products, strongly support the soundness of the strategy and prompt toward further applications of PEO/CD films in buccal drug delivery.

Triamcinolone solubilization by (2-hydroxypropyl)-β-cyclodextrin: A spectroscopic and computational approach

The molecular foundations of the use of (2-hydroxypropyl)-β-cyclodextrin (HPβCD) as solubility promoter of triamcinolone acetonide (TrA), a corticosteroid with very low aqueous solubility, was investigated by a multidisciplinary spectroscopic and computational approach. Aqueous solutions of TrA and HPβCD were investigated by UV and NMR spectroscopies. The association constant was determined by phase solubility diagrams and by the Foster-Fyfe method whereas the nature of the drug/cyclodextrin aggregates was probed by using the NMR DOSY technique. ROE measurements in solution led to stereochemical information regarding the nature of inclusion processes. TrA/HPβCD powders were prepared and investigated by Raman spectroscopy supported by computational methods. A molecular interaction of the hydroxyacyl chain with cyclodextrin, not identified in solution, was detected. Raman imaging experiments confirmed the attainment of a molecularly homogeneous system when the TrA/HPβCD molar ratio was 1:7 whereas TrA crystallized for mixtures richer in TrA (1:3.5) forming domains with size in the range of 10-15μm. We demonstrate that the combined use of several spectroscopical techniques with specific responsivities allows a detailed depiction of drug/cyclodextrin interaction useful in the development of novel pharmaceutical formulation.

Plasmonic octagonal quasicrystals for surface enhanced Raman sensing

Abstract Surface enhanced Raman scattering (SERS) on eight-fold quasicrystal arrays with precisely controlled size and spacing fabricated via electron beam lithography was investigated. This SERS substrate shows high efficiency at 785 nm excitation in the detection of p-mercaptoaniline (pMA), and a SERS enhancement factor (EF ) of 107 is achieved. SERS behavior of the realized engineered SERS substrate indicates that the present engineered metamaterial may be used as an ultrasensitive Raman probe and could open up interesting new opportunities in biosensing.

Diffusion and molecular interactions in a methanol/polyimide system probed by coupling time-resolved FTIR spectroscopy with gravimetric measurements.

In this contribution the diffusion of methanol in a commercial polyimide (PMDA-ODA) is studied by coupling gravimetric measurements with in-situ, time-resolved FTIR spectroscopy. The spectroscopic data have been treated with two complementary techniques, i.e., difference spectroscopy (DS) and least-squares curve fitting (LSCF). These approaches provided information about the overall diffusivity, the nature of the molecular interactions among the system components and the dynamics of the various molecular species. Additional spectroscopic measurements on thin film samples (about 2 μm) allowed us to identify the interaction site on the polymer backbone and to propose likely structures for the H-bonding aggregates. Molar absorptivity values from a previous literature report allowed us to estimate the population of first-shell and second-shell layers of methanol in the polymer matrix. In terms of diffusion kinetics, the gravimetric and spectroscopic estimates of the diffusion coefficients were found to be in good agreement with each other and with previous literature reports. A Fickian behavior was observed throughout, with diffusivity values markedly affected by the total concentration of sorbed methanol.

Thermodynamics of water sorption in high performance glassy thermoplastic polymers

Sorption thermodynamics of water in two glassy polymers, polyetherimide (PEI) and polyetheretherketone (PEEK), is investigated by coupling gravimetry and on line FTIR spectroscopy in order to gather information on the total amount of sorbed water as well as on the different species of water molecules absorbed within the polymers, addressing the issue of cross- and self-interactions occurring in the polymer/water systems. Water sorption isotherms have been determined at temperatures ranging from 30 to 70°C while FTIR spectroscopy has been performed only at 30°C. The experimental analysis provided information on the groups present on the polymer backbones involved in hydrogen bonding interactions with absorbed water molecules. Moreover, it also supplied qualitative indications about the different “populations” of water molecules present within the PEEK and a quantitative assessment of these “populations” in the case of PEI. The results of the experimental analysis have been interpreted using an equation of state theory based on a compressible lattice fluid model for the Gibbs energy of the polymer-water mixture, developed by extending to the case of out of equilibrium glassy polymers a previous model intended for equilibrium rubbery polymers. The model accounts for the non-equilibrium nature of glassy polymers as well as for mean field and for hydrogen bonding interactions, providing a satisfactory quantitative interpretation of the experimental data.

Morphology, molecular interactions and H 2 O diffusion in a poly(lactic-acid)/graphene composite: A vibrational spectroscopy study

A composite system made of poly(l-lactic acid) (PLLA) and graphene nanoplatelets (GNP) was investigated by Raman and FTIR spectroscopy. Two compositions were prepared and characterized in comparison to the pristine polymer: they contained, respectively, 0.25 and 0.75 wt% of the nanofiller. The study was focused on the morphological properties of the system, and, in particular, on the level of dispersion and the homogeneity obtainable with the adopted preparation protocol. Furthermore, the possible molecular interactions taking place between the nanofiller and the polymer matrix were considered. Both the above issues were investigated by confocal Raman spectroscopy, with the aid of first-principle calculations to strengthen the spectral interpretation. Finally, the effect of the nanofiller on water diffusion was investigated by time-resolved FTIR spectroscopy, which provided accurate equilibrium and kinetic data, as well as molecular level information on the penetrant-to-substrate interactions. It was found that, for a 0.25 wt% composition, the adopted preparation protocol allowed us to achieve a dispersion at the level of single nanoplatelets, while for a 0.75 wt% composition, the GNPs aggregate into a co-continuous phase. PLLA/GNP interactions were detected by Raman spectroscopy, producing a detectable perturbation of the PLLA conformational equilibrium. Both the diffusivities and the equilibrium water uptake were found to decrease significantly by increasing the filler content.

Infrared Spectroscopy of Polybenzimidazole in the Dry and Hydrate Forms: A Combined Experimental and Computational Study

In the present article, the infrared spectrum of polybenzimidazole (PBI) in the dry and hydrate forms has been studied both experimentally and theoretically to improve the interpretation of its complex features, especially in the ν(NH)/ν(OH) range, which is extensively affected by sorbed water and temperature. Time-resolved Fourier-transform infrared spectroscopy measurements were performed to monitor H2O sorption, whereas the temperature behavior was investigated by in situ measurements in the 100–450 °C range. Density functional theory calculations on simplified models of dry and hydrated PBI showed good agreement with experimental results and allowed a reliable interpretation of the observed effects. The combined experimental/computational analysis provided relevant structural information which suggested the possibility of modifying the diffusion properties of PBI and motivated further experimental activities.

Surface-enhanced Raman spectroscopy on engineered plasmonic metamaterials for “label free” biosensing

The last decade has been characterized by artificial electromagnetic (EM) materials, including photonic crystals (PCs) and photonic quasi-crystals (PQCs), making these very attractive given that there are new possibilities to control the EM field in innovative way. Quasiperiodic crystals (QCs) are a new class of materials that have fascinating optical properties lying somewhere between those of disordered and period structures. With the use of PCs and PQCs, it is possible to synthesize novel artificial structures characterized by selective EM responses, which, in turn, undergo significant frequency shifts, in presence of biological material. In the present work we studied artificial EM nanomaterials to develop innovative plasmonic nanobiosensors based on Surface Enhanced Raman Scattering (SERS) substrates and working in the visible and NIR frequency bands. A fabricated gold PQC in a Thue Morse arrangement is proposed for the engineering of reproducible SERS substrates. Structural characterization of this surface is performed by SEM and AFM. Optical properties of this plasmonic nanostructure are evaluated via UV/ Vis absorption spectroscopy and surface–enhanced Raman spectroscopy (SERS). Using a molecular monolayer of pMA (p-mercaptoaniline) as a Raman reporter, we show that a high value of SERS enhancement factor (measured up to 1.4 x 107) can be achieved in a properly optimized photonic structure, in good agreement with FDTD calculations. SERS enhancement factor is dependent on the plasmon absorption wavelength and laser wavelength used in these experiments.

Graphene oxide-based nanohybrid for label-free optical sensing

In this study we report on optical sensor, based on the sorption properties of graphene film reduced on the tip of a standard single mode optical fiber. Reflectance measurements will be carried out to investigate the changes in the graphene refractive index due to sorption when the sensor probe was exposed to gas molecules.