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Click chemistry has been successfully applied to prepare a conjugate of zinc(II) porphyrin with four boron dipyrromethene moieties. Upon excitation at the latter, an efficient excitation energy transfer to the porphyrin core occurs with an energy transfer quantum yield of 0.98, making this conjugate a promising light-harvesting system.

Photodynamic tumour therapy (PDT) on the basis of a sequential two-photon excitation of suitable sensitizers is expected 1) to prevent skin phototoxicity caused by day-light and 2) may occur via an oxygen-independent mechanism of photosensitization. Here we investigated cellular uptake, localization and phototoxicity of ( t-butyl )4- PcMg , a promising dye for a sequential two-step activation, in Jurkat cells (human T cell line) and murine hybridoma cells (B cells) in vitro. Pheophorbide a (pheo) was used as a classical Type II reference sensitizer. Excitation of higher singlet states was performed both by direct UV-excitation and by sequential two-step laser excitation in the Q-band with maximum photon flux densities of about 1026 phot.cm−2.s−1. Irradiation of ( t-butyl )4- PcMg in cells in vitro is accompanied by a rapid destruction of the dye, as was proved by confocal fluorescence microscopy. Irradiated cells exhibit a less pronounced decrease of viability and a transient cell cycle arrest of about 24 h. Pheo incubated cells are characterized by a complete stop of proliferation. In contrast, no long-lasting phototoxicity was observed with ( t-butyl )4- PcMg . Low fluorescence levels and rapid photobleaching prevented the identification of intracellular dye-localization. Our data indicate the presence of a radical mechanism as origin of an irreversible dye destruction that accounts for the low phototoxicity of ( t-butyl )4- PcMg .

The photodynamic therapy (PDT) related photophysical properties of five palladium(II) porphyrins with increasing steric demand of the meso-substituents were investigated by steady state and time-resolved absorption and luminescence spectroscopy. The steric strain of the meso-substituents is reflected in a bathochromic shift of the B-band in the absorption spectra. In contrast to free-base porphyrins, the palladium(II) complexes exhibit only a very weak fluorescence with Φ Fl ~ 10-4. Instead, the corresponding triplet states of the porphyrins are formed via inter system crossing (ISC) with a quantum yield ΦISC of nearly unity. A phosphorescence quantum yield ΦISC of 10-4 was determined assuming dynamic quenching. The triplet state of all compounds is efficiently quenched by molecular oxygen, generating singlet molecular oxygen with a quantum yield of ΦΔ ~ 0.85. The various substitution patterns exerted no significant influence on the ISC rates or singlet oxygen quantum yields. Significant differences, on the other hand, were observed with respect to the triplet lifetimes, with a tendency of longer lifetimes for the porphyrins with sterically more demanding substituents (in air-saturated solution). All porphyrins were successfully incorporated into liposomes. The phototoxic activity of three compounds was investigated in cell suspensions. The use of the new porphyrinato-palladium(II) in PDT applications is discussed.

A total of 21 different porphyrins, some of them closely related to the photosensitizer meta-tetrahydroxyphenylchlorin (m-THPC) with a varied degree of hydrophilic/lipophilic substitution were synthesized employing conventional porphyrin condensation procedures and modern functionalization via organolithium reagents. For 14 of them, the photodynamic therapy (PDT) related photophysical properties were determined in isotropic solution and in liposome membrane-model systems. The photophysical data indicate that the localization of m-THPC may be fine-tuned by carefully changing the substitution pattern.

In this work we report on the influence of the polarity of the environment on the optical properties of octa-α-butyloxy-H2phthalocyanine ( H 2 PC ( OBu )8) in organic solvents and liposomes using steady-state absorption as well as time correlated single photon counting (TCSPC). A change was found in Q-band absorption in various solvents. Taking into account that the absorption properties of H 2 PC ( OBu )8 are modulated by the polarity of the direct surrounding, polarities inside micro-heterogeneous systems can be probed. This was demonstrated for liposomes of dipalmitoylphosphatidylcholine (DPPC), with regard to the behavior during the phase transition between the gel and liquid-crystal state. Absorption spectra of H 2 PC ( OBu )8 embedded in DPPC-liposomes have been recorded in the temperature range from 15 to 70 °C, covering the phase transition region at about 36–39 °C. The Q-band absorption at temperatures below and above the phase transition resembles those in polar and non-polar solvents, respectively. Measurements of fluorescence lifetime confirm this equivalence. We explain this behavior by a change of the localization of the dye molecules inside the membrane. For H 2 PC ( OBu )8 embedded in DPPC-liposomes we demonstrated by using optical methods that the position of the dye molecules strongly depends on the phase-state of the phospholipid. In addition, H 2 PC ( OBu )8 can be used as a probe for phase transition processes taking advantage of the specific behavior in surroundings with different polarity.

Pheophorbide a (Pheo) is a well-known hydrophobic photosensitizer used for photodynamic treatment of various diseases. The influence of the surroundings on the electronic properties of photosensitizers mainly accumulating in membrane structures is of relevance for their photoactivity. In this paper the current knowledge about the electronic properties of Pheo in different microheterogeneous environments is summarized and new findings about its incorparation in different model membranes are discussed.

The singlet oxygen luminescence method and the photochemical methods using 1,3-diphenylisobenzofuran ( DPBF ) or bilirubin ditaurate ( BDT ) as chemical quenchers were employed to determine the single oxygen quantum yields (ΦΔ) of different phthalocyanines and tris(2,2″-bipyridyl)ruthenium(II) dichloride in dimethylformamide ( DMF ) or aqueous micellar solution of 0.1 M CTAC (cetyltrimethylammonium chloride). Additionally, a perylenetetracarboxylic acid diimide derivative was examined in DMF . In a series of tetrasulfonated phthalocyanines ( PTS ) the following order was found: ZnPTS > GaPTS > AlPTS ≈ H 2 PTS > CoPTS . In general, the singlet oxygen quantum yields are higher in DMF than in 0.1 M CTAC/H 2 O . The results obtained with the photochemical systems are comparable with those obtained by the photophysical method. The photochemical DPBF method results in absolute values of ΦΔ. However, in micellar solution, chain reactions occur when DPBF is used as chemical quencher in the photo-oxidative process. This problem can be overcome by adding sodium thiosulphate which is able to destroy the endoperoxide initially formed. BDT can be used as quencher in different solvents to determine ΦΔ relative to a photosensitizer with known singlet oxygen quantum yield in the respective solvent. In comparison to the chemical methods the luminescence method exhibits the advantage that side reactions of the quencher are excluded. But normally the ΦΔ values obtained are relative to a reference, since absolute determinations need much larger efforts.