Angelo Domenico Quartarolo

A Computational Study (TDDFT and RICC2) of the Electronic Spectra of Pyranoanthocyanins in the Gas Phase and Solution

The conformational structures and UV-vis absorption electronic spectra of a class of derived anthocyanin molecules (pyranoanthocyanins) have been investigated mainly by means of density functional (DFT) and time-dependent DFT methods. Pyranoanthocyanins are natural pigments present in aged wines and absorb at shorter wavelengths (around 500 nm) than the parent anthocyanin compounds, giving an orange-brown colored solution. The investigated molecules are derived from the reaction of glycosylated malvidin, peonidin, and petunidin with enolizable molecules (acetaldehyde and pyruvic acid) and vinyl derivatives. During wine storage, the concentration of pyranoanthocyanins increases with time, and analytical measurements (e.g., UV-vis spectroscopy) can characterize aged wines by color analysis. The prediction of absorption electronic spectra from TDDFT results, with the inclusion of water bulk solvation effects through the conductor-like polarizable continuum model, gives an absolute mean deviation from experimental absorption maxima of 0.1 eV and a good reproduction of the spectra line shape over the visible range of the spectrum. TDDFT calculated excitation energies agree with those obtained from ab initio multireference coupled cluster with the resolution of identity approximation (RICC2) methods, calculated at DFT gas-phase geometries.

Theoretical Determination of Electronic Spectra and Intersystem Spin-Orbit Coupling: The Case of Isoindole-BODIPY Dyes.

Density functional theory and its time-dependent extension (DFT, TDDFT) has been herein employed to elucidate the structural and electronic properties for a series of isoindole-boron dipyrromethene (isoindole-BODIPY) derivatives. The role played by both the nature and the positions of the substituents on intersystem spin-crossing has been investigated computing the spin-orbit matrix elements between singlet and triplet excited state wave functions weighted by the TDDFT transition coefficients. Their potential therapeutic use as photosensitizers in photodynamic therapy (PDT) is proposed on the basis of their strong absorbance in the red part of the visible spectrum, vertical triplet energies resulting higher than 0.98 eV, and the spin-orbit matrix elements that result to be comparable with different drugs already used in PDT.

On the Potential Use of Squaraine Derivatives as Photosensitizers in Photodynamic Therapy: A TDDFT and RICC2 Survey.

A time-dependent density functional theory (TDDFT) and the second-order approximated coupled-cluster model with the resolution of identity approximation (RICC2) studies are reported here for some classes of squaraine derivatives. These compounds have a sharp electronic band, ranging from the visible to near-red part of the spectrum, with an high molar absorption coefficient. These features make them potential photosensitizers in the photodynamic therapy of cancer (PDT), in which a light source, a photosensitizer, and molecular oxygen ((3)O2) are combined to give cytotoxic singlet oxygen ((1)O2) as a final result in a photochemical process. For the examined structures, the introduction of different substituents (electron donating, electron withdrawing, or fused rings) in the parent molecule, in order to give different squaraine derivatives, changes the maximum absorption wavelength (λmax) from 620 to 730 nm, giving a near-red absorbing photosensitizer that can better penetrate human tissue to damage tumor cells. Theoretical results, obtained from both TDDFT/PBE0 and RICC2, are able to reproduce qualitatively the substitution effect on λmax, resulting in a useful tool for testing different structure modifications and, in general, for the molecular design of PDT photosensitizers. Calculated vertical excitation energies (singlet-singlet transitions) generally agree with experimental data within 0.3 eV. The singlet oxygen generation ability of these compounds requires that their triplet energy, for a type II reaction mechanism, should be greater than 0.98 eV. Theoretical triplet energies from the RICC2 method suggests that this requisite is fulfilled for all compounds, though the results are generally overestimated with respect to experiment by 0.7 eV, whereas TDDFT/PBE0 triplet energies, which are underestimated within 0.2 eV in few cases, lie close to the above-mentioned limit and can be considered suitable for PDT applications.

Spectrophotometric study of the copigmentation of malvidin 3-O-glucoside with p-coumaric, vanillic and syringic acids

Anthocyanins are a natural source of pigments in plants and their processed food products have become attractive and excellent candidates to replace the synthetic colourants due to their characteristic intense colours and associated health benefits. The intermolecular copigmentation between anthocyanins and other colourless compounds has been reported to be an important way to enhance and stabilise the colour intensity of aqueous solutions. In the present work we report the equilibrium constant, stoichiometric ratio and the thermodynamic parameters (ΔG°, ΔH° and ΔS°) related to the intermolecular copigmentation reactions of the anthocyanin malvidin 3-O-glucoside with one hydroxycinnamic acid (p-coumaric acid) and two O-methylated hydroxybenzoic acids (vanillic and syringic acid). Different factors which affect their interactions such as copigment concentration, pH and temperature of the medium are examined at two pH levels (pH=2.50 and 3.65) corresponding to those of the major food mediums where these reactions take place (fruit juices, wine, jams etc.).

Absorption Spectra of the Potential Photodynamic Therapy Photosensitizers Texaphyrins Complexes: A Theoretical Analysis †

A systematic study of a class of divalent transition-metal texaphyrin complexes (M-Tex(+), M = Mn, Fe, Co, Ni, Cu, Zn), recently proposed as active photosensitizers in photodynamic therapy (PDT), was undertaken for the ground and excited electronic states. Geometry optimizations were performed by using the PBE0 exchange-correlation functional coupled with the 6-31G(d) basis set, while electronic excitations energies were evaluated by means of time-dependent density functional response theory (TD-DFT) at the PBE0/6-31+G(d) // PBE0/6-31G(d) level of theory. Solvent effects on excitation energies were taken into account in two ways:  by considering solvent molecules explicitly coordinated to the metal center and as bulk effects, within the conductor-like polarizable continuum model (C-PCM). The influence of the metal cation on the so-called Q-band, localized in the near-red visible region of the spectrum, was carefully examined since it plays a basic role in the drug design of new photodynamic therapy photosensitizers. The differences between experimental and computed excitation energies were found to be within 0.3 eV.

Photophysical origin of the reduced photodynamic therapy activity of temocene compared to Foscan®: insights from theory

In order to explain the reduced photodynamic (PDT) activity of a recently proposed m-tetra (hydroxyphenyl) porphycene derivative (temocene or THPPo) in terms of singlet oxygen quantum yields compared to porphyrin analogue Foscan (m-THPC), a time dependent DFT investigation has been carried out. Computed electronic transitions, singlet-triplet energy gaps and spin-orbit coupling matrix elements (SOCME) can be related to the reduced PDT activity.

Electronic spectra and intersystem spin-orbit coupling in 1,2- and 1,3-squaraines

The main photophysical properties of a series of recently synthetized 1,2‐ and 1,3‐squaraines, including absorption electronic spectra, singlet‐triplet energy gaps, and spin‐orbit matrix elements, have been investigated by means of density functional theory (DFT) and time‐dependent DFT approaches. A benchmark of three exchange‐correlation functionals has been performed in six different solvent environments. The investigated 1,2 squaraines have been found to possess two excited triplet states (T1 and T2) that lie below the energy of the excited singlet one (S1). The radiationless intersystem spin crossing efficiency is thus enhanced in both the studied systems and both the transitions could contribute to the excited singlet oxygen production. Moreover, they have a singlet‐triplet energy gap higher than that required to generate the cytotoxic singlet oxygen species. According to our data, these compounds could be used in photodynamic therapy applications that do not require high tissue penetration.

Bisanthracene bis(dicarboxylic imide)s as potential photosensitizers in photodynamic therapy: a theoretical investigation.

The electronic structures and spectroscopic properties of four bisanthracene bis(dicarboxylic imide)s (M1-M4) have been investigated theoretically by using density functional theory (DFT) and its time-dependent extension (TDDFT) in view of their potential use as photosensitizers in photodynamic therapy (PDT). The optimized geometries, electronic absorption transitions, singlet-triplet energy gaps, spin-orbit matrix elements, ionization potentials, and electron affinities have been determined in gas phase and in solvent. Both type I and II PDT mechanisms have been considered. In addition, the variation of a series of relevant properties upon heavy atom substitution (Br and I) have been determined and discussed. Results show that only M4 is able to support the type I reaction, and one of its brominated and iodinated derivatives can produce cytotoxic singlet oxygen (type II reaction).

Can phthalocyanines and their substituted α-para-(methoxy)phenyl derivatives act as photosensitizers in photodynamic therapy? A TD-DFT study

A time-dependent density functional theory study (TD-DFT) is presented regarding the substituent effects on the Q-bands of two classes of non-planar phthalocyanines: the alpha-octaphenyl and p-alpha-octamethoxyphenyl substituted compounds, in their free-base and zinc complex forms. Singlet vertical excitation energies, computed at the PBE0/SVP//BP86/SVP level of theory also including bulk solvent effects (COSMO model), resulted within 0.1 eV of experiment. The experimental red-shift for the Q-band, going from the phenylated to the methoxyphenylated case, was well-reproduced theoretically and in the latter case it was found to depend mainly on the nature of the substituents and partly on structure distortion effects. The energetic gap between the singlet ground and first triplet excited state was calculated in solvent to be 1.28 eV for the free-base phthalocyanine (H2Pc) and 1.45 eV for the unsubstituted zinc complex (ZnPc) and lower than 0.98 eV for all the other compounds, which is the energetic lower limit for a molecule to act as photosensitiser in photodynamic therapy according to a Type II reaction mechanism. As a consequence, since this property-requirement for drugs used in photodynamic therapy is not fulfilled by the investigated near-infrared photosensitizers, they cannot be proposed as candidates for their use in this medical treatment.

A TDDFT investigation of bay substituted perylenediimides: Absorption and intersystem crossing

The conformational structure and electronic spectra properties of a series of bay substituted perylenediimides (PDI) derivatives have been investigated by means of density functional theory (DFT) and time‐dependent DFT. The B3LYP and PBE0 hybrid exchange‐correlation functionals were applied in conjunction with the double‐ζ quality SVP basis set. These compounds are interesting for organic materials science and as photosensitizers in cancer phototherapy (PDT), because of their intense absorption in the visible region. Results show that the substitution at the bay position of the PDI parent molecule with N‐alkyl groups shifts the absorption maxima towards the red part of the visible spectrum (around 650–700 nm) as required for the applications in PDT. The main PDT action mechanisms have been investigated by computing of electron affinities, ionization potentials, triplet energies and spin‐orbit matrix elements between singlet and triplet excited states.