Correlation of photodynamic activity and singlet oxygen quantum yields in two series of hydrophobic monocationic porphyrins

The photodynamic properties of eight hydrophobic monocationic methyl and ruthenium polypyridine complex derivatives of free-base and zinc(II) meso-triphenyl-monopyridylporphyrin series were evaluated and compared using HeLa cells as model. The cream-like polymeric nanocapsule formulations of marine atelocollagen/xanthan gum, prepared by the coacervation method, exhibited high phototoxicity but negligible cytotoxicity in the dark. Interestingly, the formulations of a given series presented similar photodynamic activities but the methylated free-base derivatives were significantly more phototoxic than the respective ruthenated photosensitizers, reflecting the higher photoinduced singlet oxygen quantum yields of those monocationic porphyrin dyes.

Cytochrome c-promoted cardiolipin oxidation generates singlet molecular oxygen

The interaction of cytochrome c (cyt c) with cardiolipin (CL) induces protein conformational changes that favor peroxidase activity. This process has been correlated with CL oxidation and the induction of cell death. Here we report evidence demonstrating the generation of singlet molecular oxygen [O-2((1)Delta(g))] by a cyt c-CL complex in a model membrane containing CL. The formation of singlet oxygen was directly evidenced by luminescence measurements at 1270 nm and by chemical trapping experiments. Singlet oxygen generation required cyt c-CL binding and occurred at pH values higher than 6, consistent with lipid-protein interactions involving fully deprotonated CL species and positively charged residues in the protein. Moreover, singlet oxygen formation was specifically observed for tetralinoleoyl CL species and was not observed with monounsaturated and saturated CL species. Our results show that there are at least two mechanisms leading to singlet oxygen formation: one with fast kinetics involving the generation of singlet oxygen directly from CL hydroperoxide decomposition and the other involving CL oxidation. The contribution of the first mechanism was clearly evidenced by the detection of labeled singlet oxygen [O-18(2)((1)Delta(g))] from liposomes supplemented with 18-oxygen-labeled CL hydroperoxides. However quantitative analysis showed that singlet oxygen yield from CL hydroperoxides was minor (<5%) and that most of the singlet oxygen is formed from the second mechanism. Based on these data and previous findings we propose a mechanism of singlet oxygen generation through reactions involving peroxyl radicals (Russell mechanism) and excited triplet carbonyl intermediates (energy transfer mechanism).

Cytometric quantification of singlet oxygen in the human malaria parasite Plasmodium falciparum

The malaria parasite Plasmodium falciparum proliferates within human erythrocytes and is thereby exposed to a variety of reactive oxygen species (ROS) such as hydrogen peroxide, hydroxyl radical, superoxide anion, and highly reactive singlet oxygen (1O2). While most ROS are already well studied in the malaria parasite, singlet oxygen has been neglected to date. In this study we visualized the generation of 1O2 by live cell fluorescence microscopy using 3-(p-aminophenyl) fluorescein as an indicator dye. While 1O2 is found restrictively in the parasite, its amount varies during erythrocytic schizogony. Since the photosensitizer cercosporin generates defined amounts of 1O2 we have established a new cytometric method that allows the stage specific quantification of 1O2. Therefore, the parasites were first classified into three main stages according to their respective pixel-area of 200600 pixels for rings, 7001,200 pixels for trophozoites and 1,4002,500 pixels for schizonts. Interestingly the highest mean concentration of endogenous 1O2 of 0.34 nM is found in the trophozoites stage, followed by 0.20 nM (ring stage) and 0.10 nM (schizont stage) suggesting that 1O2 derives predominantly from the digestion of hemoglobin. (c) 2012 International Society for Advancement of Cytometry

Revision of Singlet Quantum Yields in the Catalyzed Decomposition of Cyclic Peroxides

The chemiluminescence of cyclic peroxides activated by oxidizable fluorescent dyes is an example of chemically initiated electron exchange luminescence (CIEEL), which has been used also to explain the efficient bioluminescence of fireflies. Diphenoyl peroxide and dimethyl-1,2-dioxetanone were used as model compounds for the development of this CIEEL mechanism. However, the chemiexcitation efficiency of diphenoyl peroxide was found to be much lower than originally described. In this work, we redetermine the chemiexcitation quantum efficiency of dimethyl-1,2-dioxetanone, a more adequate model for firefly bioluminescence, and found a singlet quantum yield (Phi(s)) of 0.1%, a value at least 2 orders of magnitude lower than previously reported. Furthermore, we synthesized two other 1,2-dioxetanone derivatives and confirm the low chemiexcitation efficiency (Phi(s) < 0.1%) of the intermolecular CIEEL-activated decomposition of this class of cyclic. peroxides. These results are compared with other chemiluminescent reactions, supporting the general trend that intermolecular CIEEL systems are much less efficient in generating singlet excited states than analogous intramolecular processes (Phi(s) approximate to 50%), with the notable exception of the peroxyoxalate reaction (Phi(s) approximate to 60%).

Theoretical study of the absorption and nonradiative deactivation of 1-nitronaphthalene in the low-lying singlet and triplet excited states including methanol and ethanol solvent effects

The photophysics of the 1-nitronaphthalene molecular system, after the absorption transition to the first singlet excited state, is theoretically studied for investigating the ultrafast multiplicity change to the triplet manifold. The consecutive transient absorption spectra experimentally observed in this molecular system are also studied. To identify the electronic states involved in the nonradiative decay, the minimum energy path of the first singlet excited state is obtained using the complete active space self-consistent field//configurational second-order perturbation approach. A near degeneracy region was found between the first singlet and the second triplet excited states with large spin-orbit coupling between them. The intersystem crossing rate was also evaluated. To support the proposed deactivation model the transient absorption spectra observed in the experiments were also considered. For this, computer simulations using sequential quantum mechanic-molecular mechanic methodology was used to consider the solvent effect in the ground and excited states for proper comparison with the experimental results. The absorption transitions from the second triplet excited state in the relaxed geometry permit to describe the transient absorption band experimentally observed around 200 fs after the absorption transition. This indicates that the T-2 electronic state is populated through the intersystem crossing presented here. The two transient absorption bands experimentally observed between 2 and 45 ps after the absorption transition are described here as the T-1 -> T-3 and T-1 -> T-5 transitions, supporting that the intermediate triplet state (T-2) decays by internal conversion to T-1. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4738757]

Novel properties of melanins include promotion of DNA strand breaks, impairment of repair, and reduced ability to damage DNA after quenching of singlet oxygen

Melanins have been associated with the development of melanoma and its resistance to photodynamic therapy (PDT). Singlet molecular oxygen (102), which is produced by ultraviolet A solar radiation and the PDT system, is also involved. Here, we investigated the effects that these factors have on DNA damage and repair. Our results show that both types of melanin (eumelanin and pheomelanin) lead to DNA breakage in the absence of light irradiation and that eumelanin is more harmful than pheomelanin. Interestingly, melanins were found to bind to the minor grooves of DNA, guaranteeing close proximity to DNA and potentially causing the observed high levels of strand breaks. We also show that the interaction of melanins with DNA can impair the access of repair enzymes to lesions, contributing to the perpetuation of DNA damage. Moreover, we found that after melanins interact with 102, they exhibit a lower ability to induce DNA breakage; we propose that these effects are due to modifications of their structure. Together, our data highlight the different modes of action of the two types of melanin. Our results may have profound implications for cellular redox homeostasis, under conditions of induced melanin synthesis and irradiation with solar light. These results may also be applied to the development of protocols to sensitize melanoma cells to PDT. (c) 2012 Elsevier Inc. All rights reserved.

Study of singlet excited state absorption spectrum of lutetium bisphthalocyanine using the femtosecond Z-scan technique

In this study we investigate the singlet excited state absorption of lutetium bisphthalocyanine (LuPc2) over a wide spectral range. It was observed distinct nonlinear absorption behaviors; saturable (SA) and reverse saturable absorption (RSA). The RSA effect was observed below 640 and above 680 nm, while SA occurs around the Q-band region, located around 660 nm. To describe the main singlet-singlet transitions, we employed the rate equation model considering the simplified three-energy level diagram. Our results reveal a ratio between excited and ground state absorption smaller than 0.05 at the Q-band region, and of approximately 4 for the other regions. (C) 2012 Elsevier B.V. All rights reserved.

Luminous efficiency enhancement of PVK based OLEDs with fac-[ClRe(CO)(3)(bpy)]

The luminous efficiency of organic light-emitting diodes based on poly(N-vinylcarbazole), PVK, was improved by adding fac-[ClRe(CO)(3)(bpy)], bpy = 2,2`-bipyridine, to PVK host. Emissive layers with various Re(I) complex/host ratio were employed and optoelectronic properties were compared with the single PVK device. The single PVK device exhibits a characteristic electroluminescence with blue emission, lambda(max) 420 nm, assigned to the PVK excimer. On the other hand, the intense and broad band at lambda(max) 580 nm of the Re(I) complex/PVK OLEDs is ascribed to the metal-to-ligand charge transfer excited state emission of fac-[ClRe(CO)(3)(bpy)]. At 30 V, the device luminous efficiency increased from 16 mcd/A for the single PVK device to 211 mcd/A for the 11% (w/w) Re(I) complex/PVK OLED, in which fac-[ClRe(CO)(3)(bpy)] acts as an electron-trap in PVK films. The device current is space-charge limited and exhibits typical emissive layer thickness dependence. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis and Photodynamic Effect of New Highly Photostable Decacationically Armed [60]- and [70]Fullerene Decaiodide Monoadducts To Target Pathogenic Bacteria and Cancer Cells

Novel water-soluble decacationically armed C-60 and C-70 decaiodide monoadducts, C-60- and C-70[>M(C3N6+C3)(2)], were synthesized, characterized, and applied as photosensitizers and potential nano-PDT agents against pathogenic bacteria and cancer cells. A high number of cationic charges per fullerene cage and H-bonding moieties were designed for rapid binding to the anionic residues displayed on the outer parts of bacterial cell walls. In the presence of a high number of electron-donating iodide anions as parts of quaternary ammonium salts in the arm region, we found that C-70[>M(C3N6+C3)(2)] produced more HO center dot than C-60[>M(C3N6+C3)(2)], in addition to O-1(2). This finding offers an explanation of the preferential killing of Gram-positive and Gram-negative bacteria by C-60[>M(C3N6+C3)(2)] and C-70[>M(C3N6+C3)(2)], respectively. The hypothesis is that O-1(2) can diffuse more easily into porous cell walls of Gram-positive bacteria to reach sensitive sites, while the less permeable Gram-negative bacterial cell wall needs the more reactive HO center dot to cause real damage.

Excited-state dynamics of meso-tetrakis(sulfonatophenyl) porphyrin J-aggregates

The excited-state dynamics of free-base meso-tetrakis(sulfonatophenyl) porphyrin J-aggregates obtained by the Z-scan technique in femto- and picosecond time scales, along with UV-Vis spectroscopy and flash photolysis is reported. Besides obtaining the S-1 state lifetime, the discrimination between internal conversion and intersystem crossing nonradiative processes from that state was also possible, and their rates and respective quantum yields were found. The aggregates present reverse saturable absorption at 532 nm for both singlet and triplet excited states. The data shown is important for several applications such as optical limiting, photodynamic therapy and others. (C) 2011 Elsevier B.V. All rights reserved.

Phototransients of 2-ethylaminodiphenylborinate generated by direct photolysis and photosensitization

Ground state interactions and excited states and transients formed after photolysis and photosensitization of 2-ethylaminodiphenylborinate (2APB) were studied by various techniques. The UV spectrum shows a large absorption band at 235 nm (epsilon = 14,500 M-1 cm(-1)) with a shoulder at 260 nm. The fluorescence spectra show increasing emission intensity with maximum at 300 nm, which shifts to the red up to 10(-3) M concentrations. At higher concentrations, the emission intensity decreases, probably due to the formation of aggregates. UV excitation in deareated solutions shows the formation of two transients at 300 and 360 nm. The latter has a lifetime of 5.7 mu s in ethanol and is totally quenched in the presence of oxygen and assigned to the triplet state of 2APB. The 300 nm peak is not affected by oxygen, has a lifetime in the order of milliseconds, and corresponds to a boron-centered radical species originated from the singlet state. A boron radical can also be obtained by electron transfer from triplet Safranine to the borinate (k(q) = 9.7 x 10(7) M-1 s(-1)) forming the semioxidized form of the dye. EPR experiments using DMPO show that dye-sensitized and direct UV-photolysis of 2ABP renders initially arylboron-centered radicals. (C) 2012 Elsevier B.V. All rights reserved.

Spin coherence generation in negatively charged self-assembled (In,Ga)As quantum dots by pumping excited trion states

Spin coherence generation in an ensemble of negatively charged (In,Ga)As/GaAs quantum dots was investigated by picosecond time-resolved pump-probe spectroscopy measuring ellipticity. Robust coherence of the ground-state electron spins is generated by pumping excited charged exciton (trion) states. The phase of the coherent state, as evidenced by the spin ensemble precession about an external magnetic field, varies relative to spin coherence generation resonant with the ground state. The phase variation depends on the pump photon energy. It is determined by (a) pumping dominantly either singlet or triplet excited states, leading to a phase inversion, and (b) the subsequent carrier relaxation into the ground states. From the dependence of the precession phase and the measured g factors, information about the quantum dot shell splitting and the exchange energy splitting between triplet and singlet states can be extracted in the ensemble.

On the Mechanisms of Triplet Excited State Population in 8-Azaadenine

The photophysics of 8-azaadenine (8-AA) has been studied with the CASPT2//CASSCF protocol and ANO-L double-zeta basis sets. Stationary equilibrium structures, surface crossings, minimum energy paths, and linear interpolations have been used to study possible mechanisms to populate the lowest triplet state, T-1 (3)(pi pi*), capable of sensitizing molecular oxygen. Our results show that two main mechanisms can occur after photoexcitation to the S-2 (1)(pi pi*) state. The first one is through the S-2/S-1 conical intersection (((1)pi pi*/(1)n pi*)(Cl)), leading to the S-1 ((1)n pi*) state minimum, (S-1 ((1)n pi*))(min), where a singlet-triplet crossing, ((1)n pi*/(3)pi pi*)(STC), is accessible. The second one starts with the ((1)pi pi*/(3)n pi*)(STC) at the (S-2((1)pi pi*))(min), from which the system can evolve to the (T-2 ((3)n pi*))(min), with subsequent population of the T-1 excited electronic state, due to the ((3)n pi*/(3)pi pi*)(Cl) conical intersection.

Theoretical study of the XP3 (X = Al, B, Ga) clusters

The lowest singlet and triplet states of AlP3, GaP3 and BP3 molecules with C-s, C-2v and C-3v symmetries were characterized using the B3LYP functional and the aug-cc-pVTZ and aug-cc-pVQZ correlated consistent basis sets. Geometrical parameters and vibrational frequencies were calculated and compared to existent experimental and theoretical data. Relative energies were obtained with single point CCSD(T) calculations using the aug-cc-pVTZ, aug-cc-pVQZ and aug-cc-pV5Z basis sets, and then extrapolating to the complete basis set (CBS) limit. (C) 2011 Elsevier B.V. All rights reserved.

Comparative study of beta-carotene and microencapsulated beta-carotene: Evaluation of their genotoxic and antigenotoxic effects

beta-Carotene (BC) is one of the natural pigments that is most commonly added to food; however, the utilization of BC is limited due to its instability. Microencapsulation techniques are commonly used because they can protect the microencapsulated material from oxidization. Nevertheless, the properties of the encapsulated compounds must be studied. We compared the antigenotoxic potential of pure and microencapsulated beta-carotene (mBC) in Wistar rats. Two doses of BC or mBC (2.5 or 5.0 mg/kg) were administered by gavage over a period of 14 days. The final gavage was followed by an injection of doxorubicin (DXR). After 24 h the animals were euthanized. The micronucleus test results showed that when both mBC and DXR were given, only the higher dose was antigenotoxic. The results of the comet assay show that when given in association with DXR, mBC had protective effects in the liver. The differences between the results obtained with BC and mBC suggest that possibly the carotenoid biodisponibility was modified by the process of microencapsulation. In conclusion, mBC does not lose its protective properties, but higher doses must be used to observe antigenotoxic effects. This is the first time that the genotoxicity and antigenotoxicity of a microencapsulated compound was evaluated in vivo. (C) 2012 Elsevier Ltd. All rights reserved.