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					Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2009; 13: April/May


About the Cover

                                                           Guest Editors: Gema de la Torre and Tomás Torres

                                                           AFM topographic image of a supramolecularly organized phthalocyanine-fullerene
                                                           dyad in micrometer-size fibers as background of the map of the Iberian Peninsula.
                                                           Porphyrins, Porphycenes, Phthalocyanines and Subphthalocyanines are the main tar-
                                                           gets of research in this Mediterranean region.


Unsymmetrically functionalized phthalocyanines: ver­
satile platforms for the preparation of molecular ma­
M. Victoria Martínez-Díaz* and David Díaz Díaz

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 me-
diated 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.

Porphyrins and other pyrrolic macrocycles in cyclo­
addition reactions
Augusto C. Tomé, Maria G.P.M.S. Neves and José A.S.

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

Recent advances on the functionalization of meso­tri­
arylcorroles via cycloaddition reactions
Joana F.B. Barata, Maria G.P.M.S. Neves, Augusto C. Tomé and
José A.S. Cavaleiro*

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

Recent developments on the synthesis of homo­ and
heteroarrays of porphyrins and phthalocyanines
Ana M.V.M. Pereira, Ana R.M. Soares, Mário J.F. Calvete* and
Gema de la Torre*

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

The small stones of Coimbra in the huge tetra­
pyrrolic chemistry building
António M.d’A. Rocha Gonsalves*, Arménio C. Serra and
Marta Pineiro

Novel approaches for synthesis and peripheric subtitution of meso-sub-
stituted porphyrins opened the way to the modeling of efficient oxida-
tion catalysts and photo-diagnostic and therapeutic methodologies

Subphthalocyanines: synthesis, self­organization, pro­
perties and applications
Anaïs Medina Martín and Christian G. Claessens*

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

                                                                                     J. Porphyrins Phthalocyanines 2009; 13: April/May
                                                                                                                     CONT E NT S

Triazolehemiporphyrazines: azaporphyrins with intrin­
sic low symmetry
Uwe Hahn* and M. Salomé Rodríguez-Morgade*

Easily available from the synthetic point of view, triazolehemiporphyrazines
could be the answer to specific problems that require the design of D2h symme-
tric, orange-red azaporphyrinoids. Recent advances on the chemistry of these
compounds are highlighted.

Case history of porphyrin J­aggregates: a personal                                     J-aggregates
point of view
Joaquim Crusats, Zoubir El-Hachemi, Carlos Escudero and                           H2TPPS4                   H2TPPS3
Josep M. Ribó*

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. The review summarizes the work performed in this
topic in the University of Barcelona.

Supramolecular organization of phthalocyanines: from
solution to surface
M. Victoria Martínez-Díaz* and Giovanni Bottari*

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 micro-
review a brief overview of the contribution made by some research groups in
Spain towards the preparation of organized phthalocyanine-based supramo-
lecular architectures is presented.

Metal­mediated multiporphyrin functional assemblies
Laura P. Hernández, Almudena González-Álvarez, Ana I. Oliva
and Pablo Ballester*

We describe the preparation and characterization of several multi-component
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 form the structures of such assemblies in ap-
plications such as molecular recognition or light-induced electron and energy
transfer processes.

                                                                                            J. Porphyrins Phthalocyanines 2009; 13: April/May

Molecular modelling features on the aggregation of
porphyrins and subphthalocyanines
V.R. Ferro, L.A. Poveda, R. Lopez and J.M. García de la Vega*


Optical spectroscopy and photochemistry of porphy­
rins and phthalocyanines
Sílvia M.B. Costa*, Suzana M. Andrade, Denísio M. Togashi,
Pedro M.R. Paulo, César A.T. Laia, M. Isabel Viseu and Amélia
M. Gonçalves da Silva

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 mass spectrometry for the study of the
non­covalent interactions of porphyrins and duplex
Catarina I.V. Ramos* and M.G. Santana-Marques

Electrospray ionization mass spectrometry (ESI-MS) and electrospray ioniza-
tion 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 motifs) with five meso(N-methylpyridynium-4-yl)porphyrins with 1
to 4 positive charges. The results obtained point to outside binding of the por-
phyrins, and to an increase of binding strength with the number of positive

Recent developments in the structural characterization
of substituted meso­tetraarylporphyrins by electrospray
tandem mass spectrometry
M. Rosário M. Domingues*, Pedro Domingues, Maria G.P.M.S.
Neves, Augusto C. Tomé and José A.S. Cavaleiro

The use of electrospray tandem mass spectrometry (ESI-MS/MS) in the struc-
tural characterization of neutral and cationic meso-tetraarylporphyrins is re-

                                                                                   J. Porphyrins Phthalocyanines 2009; 13: April/May
                                                                                                               CONT E NT S

Preclinical photodynamic therapy in Spain. 1: Chemical
and photophysical studies on porphycenes and other
David Sánchez-García, José I. Borrell, Xavier Batllori, Jordi
Teixidó, Xavier Tomás and Santi Nonell*

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

Preclinical photodynamic therapy in Spain. 2: Liposome
vectorization of photosensitisers. Different strategies,
different outcomes
Margarita Mora* and M. Lluïsa Sagristá

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 estrategy for photosensitizers vec-

Preclinical photodynamic therapy research in Spain.
3. Localization of photosensitizers and mechanisms of
cell death in vitro
Magdalena Cañete*, Juan C. Stockert and Angeles Villanueva

The evaluation of cell death mechanisms is an important parameter to determine
the efficacy and the potential toxicity of a treatment, allowing to adjust the bet-
ter 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.

Preclinical photodynamic therapy research in Spain.
4. Cytoskeleton and adhesion complexes of cultured
tumor cells as targets of photosensitizers
Francisco Sanz-Rodríguez*, Adriana Casas, Salvador González,
Jesús Espada, Pedro Jaén, Javier Regadera, Alfonso Blázquez-
Castro, Alicia Zamarrón, Lorea Bagazgoitia, Carmen Iglesias de
la Cruz and Ángeles Juarranz

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

                                                                                      J. Porphyrins Phthalocyanines 2009; 13: April/May

Regression of the murine LM3 tumor by repeated photo­
dynamic therapy with meso­tetrakis(4­N,N,N­trimethylanili­
Juan C. Stockert*, Silvia I. Vanzulli, Magdalena Cañete, Angeles
Villanueva, Angeles Juarranz, Santiago Nonell and Lucas L. Colombo

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.

Synthesis and photophysical properties of am­
phiphilic halogenated bacteriochlorins: new op­
portunities for photodynamic therapy of cancer
Mariette M. Pereira*, Carlos J.P. Monteiro, Ana V.C. Simões,
Sara M.A. Pinto, Luís G. Arnaut, Gonçalo F.F. Sá, Elsa F.F.
Silva, Luís B. Rocha, Sérgio Simões and Sebastião J.

This paper summarizes our recent contribution to the synthesis of sta-
ble amphiphilic halogenated meso-tetraarylbacteriochlorins. The photo-
physics and in vitro cytotoxicity and phototoxicity are presented. Am-
phiphilic halogenated meso-tetraarylbacteriochlorins are very promi-
sing templates for a next generation totally synthetic photosensitizer
for PDT, with lower costs and higher synthetic flexibility.

Antimicrobial photodynamic activity of porphyrin
derivatives: potential application on medical and
water desinfection
Carla M.B. Carvalho, João P.C. Tomé, Maria A.F. Faustino,
Maria G.P.M.S. Neves, Augusto C. Tomé, José A.S.
Cavaleiro,* Liliana Costa, Eliana Alves, Anabela Oliveira,
Ângela Cunha and Adelaide Almeida

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.

Photodynamic inactivation of viruses by immobilized
chlorin­containing liposomes
M. Lluïsa Sagristá*, Fernado Postigo, M. Africa De Madariaga,
Rosa M. Pintó, Santiago Caballero, Albert Bosch, M. Asunción
Vallés and Margarita Mora

The viral safety of blood derived products relies in properly chosen inactivation pro-
cedures. 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 sterilisation that can be able to be applied in manufacturing processes.

                                                                                         J. Porphyrins Phthalocyanines 2009; 13: April/May
                                                                                                                              CONT E NT S

Metalloporphyrins in the biomimetic oxidative valori­
zation of natural and other organic substrates
Mário M.Q. Simões, Rodrigo De Paula, M. Graça P.M.S. Neves                                                         H2O2
and José A.S. Cavaleiro*                                                                    S                                               SO
                                                                                    (organic compound)
One of the approaches for the functionalization of natural products is the oxida-                              M = Mn, Fe
tion in the presence of an oxygen atom donor, under the influence of a suitable                                co-catalyst
catalyst. Metalloporphyrins are amongst the catalysts commonly studied. The
porphyrin complexes have demonstrated to be efficient catalysts in the oxyge-
nation of several natural products. These transformations have been studied in
the presence of different oxygen atom donors.

Controlling the molecular organization of porphy­
rins by hosting in amphiphilic matrix
Gustavo de Miguel, María T. Martín-Romero, Marta Pérez-
Morales, Eulogia Muñoz and Luis Camacho*

Monomer, twisted dimer and slipped dimers, and tetramer patterns in
mixed films containing ionic water-soluble or insoluble porphyrins and am-
phiphilic 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, increasing the monomer porphyrin moieties for water-
insoluble porphyrins, its gas-sensing response notably enhances.

Nanostructured thin films based on phthalocyanines:
electrochromic displays and sensors
Maria Luz Rodriguez-Mendez* and José Antonio de Saja

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

Iron­phtalocyanine complexes immobilized in na­
nostructured metal oxide as optical sensors of
NOx and CO: NMR and photo­physical studies
Angel Valero-Navarro, Jorge F. Fernandez-Sanchez*,
Antonio Segura-Carretero, Ursula E. Spichiger-Keller and
Alberto Fernandez-Gutierrez*

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

                                                                                                     J. Porphyrins Phthalocyanines 2009; 13: April/May

Phthalocyanines, subphthalocyanines and porphyrins
for energy and electron transfer applications
David González-Rodríguez* and Giovanni Bottari*

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

SWNT ensembles with porphyrins and phtha­
locyanines: new arquitectures for energy con­
Gema de la Torre

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 overview the contribution of some Spanish research
groups on the preparation of phthalocyanine-SWNT and porphyrin-
SWNT nanoconjugates. Photophysical caharacterization and device fa-
brication are also discussed in some examples.

Extended π-aromatic systems for energy con-
version: phthalocyanines and porphyrins in mo­
lecular solar cells
Yannick Rio, Purificación Vázquez* and Emilio Palomares*

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 applica-
tions 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.

Nonlinear optical properties of phthalocyanines and re­
lated compounds
María A. Díaz-García*

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.

                                                                                   J. Porphyrins Phthalocyanines 2009; 13: April/May

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