CONTENTS

Unsymmetrical functionalization of phthalocyanines has opened a wide range of new applications of this type of aromatic compounds in materials science. In particular, the functionalization of preformed macrocycles and further functional group interconversion offer several synthetic advantages. Transition-metal mediated reactions proved to be the most helpful tool for expanding the synthetic versatility of phthalocyanines. Emergent new synthetic methods such as "click" chemistry are just starting to be successfully applied to the functionalization of these macrocycles.

This mini-review deals with the use of pyrrolic macrocycles in Diels-Alder reactions (as dienes and dienophiles) and in 1,3-dipolar cycloadditions (as 1,3-dipoles and dipolarophiles).

New methods for β-functionalization of meso-triarylcorroles are reviewed.

Porphyrin- and phthalocyanine-based multichromophoric systems are appealing architectures to exploit electronic and photonic interactions between individual subunits. Herein, a brief overview of the contribution made by the organic chemistry groups of Cavaleiro in Aveiro and Torres in Madrid on the preparation of homo- and heteroarrays of porphyrins and phthalocyanines is presented.

Novel approaches for synthesis and peripheric subtitution of meso-substituted porphyrins opened the way to the modeling of efficient oxidation catalysts and photo-diagnostic and therapeutic methodologies.

This review article gives a brief overview of the latest development regarding all aspects of subphthalocyanines. The most recent progresses in their synthesis, reactivity, characterization, self-organization, properties and applications are detailed from a Spanish standpoint.

Easily available from the synthetic point of view, triazolehemiporphyrazines could be the answer to specific problems that require the design of D_2h symmetric, orange-red azaporphyrinoids. Recent advances on the chemistry of these compounds are highlighted.

The formation and structure of the J-aggregates of diprotonated porphyrins are paradigms of the self-assembly of amphiphilic molecular building blocks in supramolecular chemistry. This review summarizes the research done on this area in the University of Barcelona.

The application of phthalocyanines in different technological fields is often tied to the possibility of organizing these macrocycles at the molecular level using supramolecular interactions such as hydrogen-bonding, donor-acceptor interactions or the formation of mesophases, to mention a few. In this microreview a brief overview of the contribution made by some research groups in Spain towards the preparation of organized phthalocyanine-based supramolecular architectures is presented.

We describe the preparation and characterization of several multicomponent assemblies. In all cases, the prepared supramolecular structures constitute the thermodynamic outcome of a self-assembly process induced by coordination of a diamine ligand with a Zn-oligoporphyrin. We also present examples of the functionality that can be derived from the structures of such assemblies in applications such as molecular recognition or light-induced electron and energy transfer processes.

Porphyrin-based conjugates (with interest in the so-called artificial photosynthesis) and, subphthalocyanine aggregates (including nanometer-sized fully aromatic fullerene-like molecular architectures) — with potential applications as new materials for optoelectronics, solar energy and other uses — have been theoretically investigated.

Self-assembly and aggregation phenomena and photoinduced electron transfer of porphyrins and phthalocyanines were investigated in organized media of reverse micelles, vesicles and Langmuir-Blodgett films as well as in dendrimer supramolecular complexes by electronic absorption and emission studies along with time-resolved fluorescence techniques.

Electrospray ionization mass spectrometry (ESI-MS) and electrospray ionization tandem mass spectrometry (ESI-MS/MS) were used to investigate the non-covalent adducts of small oligonucleotide duplexes (6 to 10 base pairs and different

The use of electrospray tandem mass spectrometry (ESI-MS/MS) in the structural characterization of neutral and cationic meso-tetraarylporphyrins is reviewed.

This highlight reviews our contributions to the PDT field: development of porphycenes as photosensitizers, photophysical screening of potential PDT agents, and spectroscopic studies on singlet oxygen production, diffusion, and reactivity in biological media.

Photodynamic therapy is an emerging modality of cancer treatment based on the use of photosensitizing drugs accumulated selectively in tumor cells. At present, one of the goals sought in the development of new photosensitizers is their selective targeting to tumor cells. In this way, the use of liposomes, as targeted carriers, constitutes an interesting strategy for photosensitizers vectorization.

The evaluation of cell death mechanisms is an important parameter to determine the efficacy and potential toxicity of a treatment, allowing better adjustment of protocol. Using cell cultures, our research team has studied the mechanisms of cell damage and death implicated in the photodynamic processes, as well as the relationship between the cellular localization of the PS and the organelle damage during photosensitization.

Tumor cell death induced by photodynamic therapy (PDT) with different photosensitizers (PSs) is due to the selective damage of several organelles. Other cell structures such as the cytoskeleton (microtubules, actin microfilaments and cytokeratin intermediate filaments) and the cell-adhesion components (cadherins and integrins) are also implicated in cell death induced by PSs. Both cytoskeleton and cell adhesion components are as considered very important targets for anticancer therapies including PDT.

Murine LM3 tumors were subjected to PDT using intratumoral injection of meso-tetrakis (4-N,N,N-trimethylanilinium) porphine (TMAP) followed by irradiation with blue-red light. Control (light, saline, and TMAP alone) and PDT treatments were made on the depilated and glycerol-covered skin over intradermal tumors and repeated 4 times (every 2 days). Only PDT-tumors showed complete and long-term regression, and the survival of PDT-mice was significantly longer than that of control animals.

This paper summarizes our recent contribution to the synthesis of stable amphiphilic halogenated meso-tetraarylbacteriochlorins. The photophysics and in vitro cytotoxicity and phototoxicity are presented. Amphiphilic halogenated meso-tetraarylbacteriochlorins are very promising templates for a next generation of totally synthetic photosensitizer for PDT, with lower costs and higher synthetic flexibility.

An overview of the advances performed by the Aveiro group on the design and synthesis of tetrapyrrolic photosensitizers with potential photodynamic antimicrobial activity is presented.

The viral safety of blood derived products relies in properly chosen inactivation procedures. This study demonstrates the successful inactivation of the enveloped virus BVDV by immobilized chlorin-containing liposomes in culture medium and that the reduction factor of the virus titer in human blood plasma depends on the sample thickness. The more outstanding aspect of this paper is the design of a system useful for blood sterilization that can be applied in manufacturing processes.

One of the approaches for the functionalization of natural products is oxidation in the presence of an oxygen atom donor, under the influence of a suitable catalyst. Metalloporphyrins are amongst the catalysts commonly studied. The porphyrin complexes have demonstrated to be efficient catalysts in the oxygenation of several natural products. These transformations have been studied in the presence of different oxygen atom donors.

Monomer, twisted dimer and slipped dimers, and tetramer patterns in mixed films containing ionic water-soluble or insoluble porphyrins and amphiphilic anchors at the air-water interface and on solid support (Langmuir-Blodgett, LB) have been achieved as a function of the central metal-ion of water-soluble porphyrins, the lipid host-matrix and the applied surface pressure. Moreover, by increasing the monomer porphyrin moieties for water-insoluble porphyrins, its gas-sensing response has been notably enhanced.

The group of the University of Valladolid has dedicated their activity to the study of thin films based on phthalocyanines. Rare earth bisphthalocyanines have permitted to develop electrochromic displays and sensors.

This paper shows the research that is currently undergoing in the Universities of Granada and Almería towards the development of optical sensing layers based on iron(II) phthalocyanine complexes immobilized on nanostructured solid supports. Thus, the analytical figures of merit of several FePc-N donor ligands incorporated in different nanostructured metal oxides are reported, finishing with future tendencies.

This article aims at highlighting the efforts of Portuguese and Spanish research groups on the design, synthesis and photophysical study of molecular and supramolecular donor-acceptor systems based on phthalocyanines, subphthalocyanines, or porphyrins.

The combination of SWNTs with macrocyclic chromophores, namely phthalocyanines and porphyrins, leads to nanoscale systems that hold great potential in the conversion of solar energy into electricity. The aim of this paper is to review the contribution of some Spanish research groups on the preparation of phthalocyanine-SWNT and porphyrin-SWNT nanoconjugates. Photophysical caharacterization and device fabrication are also discussed in some examples.

Phthalocyanines, porphyrins and related systems are very attractive molecules for their incorporation into solar cells. The strong extinction coefficient of these materials is an intrinsically added value for applications in photovoltaic devices where they can act also as antennas due to their strong absorption in the range of the terrestrial solar emission spectrum. The most significant results by the Spanish groups in this field are given in this account.

The most relevant advances achieved in the field of nonlinear optics in relation to phthalocyanines and other related compounds achieved by Portuguese and Spanish research groups are reviewed. Several aspects in which these teams were pioneers are described in detail.

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