Mariachiara Trapani

Supramolecular hybrid assemblies based on gold nanoparticles, amphiphilic cyclodextrin and porphyrins with combined phototherapeutic action

Gold nanoparticles (AuNPs), amphiphilic cyclodextrin (SC6NH2) and anionic porphyrin (TPPS4) spontaneously self-assemble in aqueous basic solution forming nanostructures with controlled size and shape. Spectroscopic techniques such UV-Vis, fluorescence emission and Dynamic Light Scattering (DLS) demonstrate that AuNPs are covered by SC6NH2, and TPPS4 is strongly entrapped within, forming assemblies with size of 4 and 50 nm. Scanning Near-Field Optical Microscopy (SNOM) and Scanning Near-Field Optical Luminescence (SNOL) assess the presence of luminescent vescicular structures incorporating porphyrin with dimensions of about 150 nm. Transmission electron microscopy (TEM) indicates AuNPs with sizes of 20–30 nm can be located inside the largest cyclodextrin/porphyrin aggregates (≅150 nm) or interact externally with the smallest cyclodextrin/porphyrin vesicles (≅ 40 nm). The generation of an appreciable quantum yield of singlet oxygen (ΦΔ = 0.25) guarantees the photodynamic action excluding mostly strong interactions between gold and porphyrin. These hybrid systems are fairly stable at physiological conditions (pH = 7.4) and can be taken up by HeLa cancer cells which, upon treatment, show co-localization of gold and porphyrins in the cytoplasm. After intracellular delivery, these assemblies induce low dark toxicity and a combined photothermal–photodynamic effect upon proper irradiation, showing promising properties as dual-action phototherapeutics.

Poly(carboxylic acid)-Cyclodextrin/Anionic Porphyrin Finished Fabrics as Photosensitizer Releasers for Antimicrobial Photodynamic Therapy

In the development of new antibacterial therapeutic approaches to fight multidrug-resistant bacteria, antimicrobial photodynamic therapy (aPDT) represents a well-known alternative to treat local infections caused by different microorganisms. Here we present a polypropylene (PP) fabric finished with citrate-hydroxypropyl-βCD polymer (PP-CD) entrapping the tetra-anionic 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphine (TPPS) as photosensitizer-eluting scaffold (PP-CD/TPPS) for aPDT. The concept is based on host-guest complexation of porphyrin in the cavities of CDs immobilized on the PP fibers, followed by its sustained and controlled delivery in release medium and simultaneous photoinactivation of microorganisms. Morphology of fabric was characterized by optical (OM) and scanning electron microscopies (SEM). Optical properties were investigated by UV-vis absorption, steady- and time-resolved fluorescence emission spectroscopy. X-ray photoelectron spectroscopy (XPS) and FT-IR revealed the surface chemical composition and the distribution map of the molecular components on the fabric, respectively. Direct 1O2 determination allowed to assess the potential photodynamic activity of the fabric. Release kinetics of TPPS in physiological conditions pointed out the role of the CD cavity to control the TPPS elution. Photoantimicrobial activity of the porphyrin-loaded textile was investigated against both Gram-positive Staphylococcus aureus ATCC 29213 (S. aureus) and Gram-negative Pseudomonas aeruginosa ATCC 27853 (P. aeruginosa). Optical microscopy coupled with UV-vis extinction and fluorescence spectra aim to ascertain the uptake of TPPS to S. aureus bacterial cells. Finally, PP-CD/TPPS fabric-treated S. aureus cells were photokilled of 99.98%. Moreover, low adhesion of S. aureus cells on textile was established. Conversely, no photodamage of fabric-treated P. aeruginosa cells was observed, together with their satisfying adhesion.

The role of counter-anions in the kinetics and chirality of porphyrin J-aggregates.

Kinetics of the growth of TPPS4 porphyrin J-aggregates slow down in the order H2SO4 > HCl > HBr > HNO3 > HClO4, in agreement with the Hofmeister series. The rate constants and the extent of chirality correlate with the structure-making or breaking abilities of the different anions with respect to the hydrogen bonding network of the solvent.

Two-Dimensional Electronic Spectroscopy Reveals Dynamics and Mechanisms of Solvent-Driven Inertial Relaxation in Polar BODIPY Dyes

In this work, we demonstrate the use of two-dimensional electronic spectroscopy (2DES) to study the mechanism and time scale of the femtosecond Stokes shift dynamics in molecules characterized by intramolecular charge transfer, such as distyryl-functionalized boron dipyrromethene (BODIPY) molecules. The obtained results demonstrate that 2DES allows clear and direct visualization of the phenomenon. The analysis of the 2D data in terms of 2D frequency–frequency decay associated maps provides indeed not only the time scale of the relaxation process but also the starting and the final point of the energy flow and the associated reorganization energy, identified by looking at the coordinates of a negative signature below the diagonal. The sensitivity of the 2DES technique to vibrational coherence dynamics also allowed the identification of a possible relaxation mechanism involving specific interaction between a vibrational mode of the dye and the solvent.

Aggregates of a cationic porphyrin as supramolecular probes for biopolymers

The copper(II) derivative of the dicationic trans-bis(N-methylpyridinium-4-yl)diphenylporphyrin (t-CuPagg) forms large fractal aggregates in aqueous solution under moderate ionic strength conditions. A kinetic investigation of the aggregation process allows for a choice of experimental conditions to quickly obtain stable assemblies in solution. These positively charged aggregates are able to interact efficiently with negatively charged chiral species, (including bacterial spores) leading to induced circular dichroism signals in the Soret region of the porphyrin, now acting as a sensitive chiroptical probe.

Spectroscopic investigation on porphyrins nano-assemblies onto gold nanorods.

The interaction between gold nanorods (Au NRs), synthesized by a conventional seeded growth protocol, and the anionic tetrakis-(4-sulfonatophenyl)porphyrin (TPPS4) has been investigated through various spectroscopic techniques. At neutral pH, the formation of H-aggregates and the inclusion of porphyrin monomers in CTAB micelles covering the nanorods have been evidenced. Under mild acidic conditions (pH=3) a nano-hybrid assembly of porphyrin J-aggregates and Au NRs has been revealed. For the sake of comparison, Cu(II) and Zn(II) metal porphyrin derivatives as well as a cationic porphyrin have been studied in the same experimental conditions, showing that: i) CuTPPS4 forms porphyrin H-dimers onto the Au NRs; ii) ZnTPPS4 undergoes to demetallation, followed by acidification of the central core and eventually aggregation onto Au NRs; iii) cationic porphyrin does not interact with Au NRs.

Investigation of the Aggregation Properties of a Chiral Porphyrin Bearing Citronellal Meso Substituent Groups.

A new porphyrin bearing four R or S hydrogenated citronellal units directly bound to the meso positions of the porphyrin ring was synthesized and fully characterized through MALDI-TOF, NMR, UV/Vis absorption, and fluorescence emission spectroscopies. Both enantiomers exhibit a monomeric nature in a series of organic solvents. Acting on the polarity of the solvent, i.e., increasing the amount of water in mixture with acetone, aggregation occurs, as revealed by UV/Vis absorption, fluorescence emission, and resonance light scattering. The occurrence of both H- and J-type aggregates was suggested by fluorescence lifetime measurements. In contrast to the monomeric species, these aggregates exhibit CD spectra reflecting the chirality of the building blocks. AFM microscopy shows that micrometer ribbon-like structures form by the casting solution of these porphyrins in acetone/water onto a glass surface.

Multichannel near-field nanoscopy of circular and linear dichroism at the solid-state

We investigate the optical response of individual porphyrin (TPPS3) nanoaggregates anchored onto a glass substrate by using a specific configuration of Polarization-Modulation Scanning Near-Field Optical Microscopy (PM-SNOM). Subdiffraction spatial resolution and sensitivity to the chiroptical properties of the material is reported. By demodulating the transmitted signal at the first and the second harmonics, the response of the nanoggregates to circular and linear polarization is simultaneously acquired in the same scan. In order to evaluate the relevant dichroic coefficients, we analyze a sample comprising several tens of individual nanoaggregates by using a model based on the Mueller matrix formalism. Circular dichroism in the nanoaggregates is demonstrated to stem from their molecular structure, whereas linear dichroism occurs as a consequence of the strongly anisotropic shape of the deposited nanoaggregates.