On the localization of water-soluble porphyrins in micellar systems evaluated by static and time-resolved frequency-domain fluorescence techniques

Fluorescence quenching of meso-tetrakis-4-sulfonatophenyl (TPPS4) and meso-tetrakis-4-N-methylpyridil (TMPyP) porphyrins is studied in aqueous solution and upon addition of micelles of sodium dodecylsulfate (SDS), cetyltrimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and t-octylphenoxypolyethoxyethanol (Triton X-100). Potassium iodide (KI) was used as quencher. Steady-state Stern-Volmer plots were best fitted by a quadratic equation, including dynamic (K-D) and static (K-s) quenching. Ks was significantly smaller than K-D. Frequency-domain fluorescence lifetimes allowed estimating bimolecular quenching constants, k(q). At 25 degrees C, in aqueous solution, TMPyP shows k(q), values a factor of 2-3 higher than the diffusional limit. TPPS4 shows collisional quenching with pH dependent k(q) values. For TMPyP quenching results are consistent with reported binding constants: a significant reduction of quenching takes place for SDS, a moderate reduction is observed for H PS and almost no change is seen for Triton X-100. Similar data were obtained at 50 C. For CTAC-TPPS4 system an enhancement of quenching was observed as compared to pure buffer. This is probably associated to accumulation of iodide at the cationic micellar interface. The attraction between CTAC headgroups and 1(-), and repulsion between SDS and 1(-), enhances and reduces the fluorescence quenching, respectively, of porphyrins located at the micellar interface. The small quenching of TPPS4 in Triton X-100 is consistent with strong binding as reported in the literature. (C) 2008 Elsevier B.V. All rights reserved.

Major determinants of photoinduced cell death: Subcellular localization versus photosensitization efficiency

We present a study on whether and to what extent subcellular localization may compete favorably with photosensitization efficiency with respect to the overall efficiency of photoinduced cell death. We have compared the efficiency with which two cationic photosensitizers, namely methylene blue (MB) and crystal violet (CV), induce the photoinduced death of human cervical adenocarcinoma (HeLa) cells. Whereas MB is well known to generate singlet oxygen and related triplet excited species with high quantum yields in a variety of biological and chemical environments (i.e., acting as a typical type II photosensitizer), the highly mitochondria-specific CV produces triplet species and singlet oxygen with low yields, acting mostly via the classical type I mechanism (e.g., via free radicals). The findings described here indicate that the presumably more phototoxic type II photosensitizer (MB) does not lead to higher degrees of cell death compared to the type I (CV) photosensitizer. In fact, CV kills cells with the same efficiency as MB, generating at least 10 times fewer photoinduced reactive species. Therefore, subcellular localization is indeed more important than photochemical reactivity in terms of overall cell killing, with mitochondrial localization representing a highly desirable property for the development of more specific/efficient photosensitizers for photodynamic therapy applications. (C) 2011 Elsevier Inc. All rights reserved.

Taurine bromamine: A potent oxidant of tryptophan residues in albumin

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Factors affecting nucleolytic efficiency of some ternary metal complexes with DNA binding and recognition domains. Crystal and molecular structure of Zn(phen)(edda)

The binding selectivity of the M(phen)(edda) (M = Cu, Co, Ni, Zn; phen = 1,10-phenanthroline, edda = ethylenediaminediacetic acid) complexes towards ds(CG)(6), ds(AT)(6) and ds(CGCGAATTCGCG) B-form oligonucleotide duplexes were studied by CD spectroscopy and molecular modeling. The binding mode is intercalation and there is selectivity towards AT-sequence and stacking preference for A/A parallel or diagonal adjacent base steps in their intercalation. The nucleolytic properties of these complexes were investigated and the factors affecting the extent of cleavage were determined to be: concentration of complex, the nature of metal(11) ion, type of buffer, pH of buffer, incubation time, incubation temperature, and the presence of hydrogen peroxide or ascorbic acid as exogenous reagents. The fluorescence property of these complexes and its origin were also investigated. The crystal structure of the Zn(phen)(edda) complex is reported in which the zinc atom displays a distorted trans-N4O2 octahedral geometry; the crystal packing features double layers of complex molecules held together by extensive hydrogen bonding that inter-digitate with adjacent double layers via pi...pi interactions between 1,10-phenanthroline residues. The structure is compared with that of the recently described copper(II) analogue and, with the latter, included in molecular modeling. (C) 2008 Elsevier B.V. All rights reserved.

Assessing the role of vertical leaves within the photosynthetic function of Styrax camporum under drought conditions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Photoacclimation in a tropical population of Cladophora glomerata (L.) Kützing 1843 (Chlorophyta) from southeastern Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Energy spectrum and eigenfunctions through the Quantum Section Method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Light-related photosynthetic characteristics of freshwater rhodophytes

Photosynthetic characteristics in response to irradiance were analysed in 21 field and culture populations of thirteen freshwater red algal species applying two distinct techniques (chlorophyll fluorescence and oxygen evolution). Photosynthesis-irradiance (PI) curves indicated adaptations to low irradiances in all species analysed, essentially characterized by occurrence of photoinhibition, low values of the saturation parameter (I-k < 225 mu mol m(-2) s(-1)) and compensation irradiance (I-c < 20 mu mol m(-2) s(-1)) and relatively high values of the effective quantum yield of photosystem II (Delta F/F'(m) >= 45). These characteristics have been reported in freshwater red algae and were confirmed from data based on the two techniques, indicating they are typically shade-adapted plants. on the other hand, some species (e.g. Batrachospermum delicatulum) can tolerate high irradiances (up to 2400 mu mol m(-2) s(-1)), suggesting they have mechanisms that enable them to avoid photodarnage of the photosynthetic apparatus. One of these mechanisms is the increase in dissipation of excessive energy captured by reaction centres after exposure to continuous irradiance, as reflected by the non-photochemical quenching fluorescence parameter in dark/light induction curves. Photo-inhibition occurred in all algae tested by both techniques. Light acclimation was evident particularly in field populations, as revealed by lower values of the saturation parameter (Ik) and the compensation irradiance (I-c) and higher values of Delta F/F'(m) in algae under low irradiances (shaded or heavily shaded stream segments), and vice-versa. Forms living within the boundary layer (e.g. crusts), in a region of reduced current velocity, tended to be more shade-adapted than semi-erect plants (e.g. non-mucilaginous or mucilaginous filaments), as indicated by highest values of photosynthetic efficiency (alpha = 0.31) and effective quantum yield (Delta F/F'(m) = 0.88) under natural conditions. Higher photo- synthetic rates (P-max) for the same species or population were observed under culture than field conditions when measured with the oxygen evolution technique, whereas the opposite trend was observed using chlorophyll fluorescence. (c) 2005 Elsevier B.V. All rights reserved.

Upconversion fluorescence spectroscopy of Er3+/Yb3+-doped heavy metal Bi2O3-Na2O-Nb2O5-GeO2 glass

Upconversion fluorescence emission of Er3+/Yb3+-doped Bi2O3-Na2O-Nb2O5-GeO2 heavy metal glass samples excited at 1.06 mu m is experimentally investigated. The results reveal the existence of intense emission bands centered around 520, 545, and 655 nm. The germano-niobate based host glass presents high transparency in the region of 400-2700 nm, the capability of incorporating high dopant concentrations, high melting temperature, and large resistance to atmospheric moisture. The observed intensity of the green fluorescence emission, suggested that the niobium based host glass material plays an important role in the efficiency of the upconversion process. Emission lines centered at 425, 483, 503, 608, and 628 nm were also observed. (C) 1997 American Institute of Physics.

Thermal behaviour of intercalated 8-hydroxyquinoline (oxine) in montmorillonite clay

The composite montmorillonite-8-hydroxyquinoline (Swy-1-8-HQ) was prepared by two different processes and studied by using thermogravimetric analysis (TG/DTG and DSC), as well as helpful techniques as fluorescence in the UV-visible region and X-ray diffraction. The composites developed fluorescent appearance, however with quantum poor efficiency and they exhibited distinct TG and DSC thermal behavior. The fluorescence data of spectra associated to the TG/DT curves allowed to suggest that the 8-HQ was present in the composites in two different circumstances: 1 - intercalated in the interlayer spaces (Swy-1-8-HQ2), rigidly associated to the Substrate feasible as a monolayer with the aromatic rings parallel to the silica layer; and/or, 2 - adsorbed on the Surface (Swy-1-8-HQ1), either as a bilayer formation or tilting of the molecules to the silicate layer sheet. All results confirmed above are in agreement with X-ray diffraction patterns, once the interlayer space increases when 8-HQ is incorporated. The experimental results confirm the formation of the composites in agreement with the method used in the preparation.

Light-related photosynthetic characteristics of lotic macroalgae

Photosynthetic characteristics in response to irradiance were analysed in 42 populations of 33 macroalgal species by two distinct techniques (chlorophyll fluorescence and oxygen evolution). Photosynthesis-irradiance (PI) curves based on the two techniques indicated adaptations to low irradiance reflected by low saturation values, high to moderate values of photosynthetic efficiency (alpha) and photoinhibition (beta), for Bacillariophyta and Rhodophyta, which suggests they are typically shade-adapted algae. In contrast, most species of Chlorophyta were reported as sun adapted algae, characterized by high values of I-k and low of alpha, and lack of or low photoinhibition. Cyanophyta and Xanthophyta were intermediate groups in terms of light adaptations. Photoinhibition was observed in variable degrees in all algal groups, under field and laboratory conditions, which confirms that it is not artificially induced by experimental conditions, but is rather a common and natural phenomenon of the lotic macroalgae. Low values of compensation irradiance (I-c) were found, which indicate that these algae can keep an autotrophic metabolism even under very low irradiances. High ratios (>2) of photosynthesis/respiration were found in most algae, which indicates a considerable net gain. These two physiological characteristics suggest that macroalgae may be important primary producers in lotic ecosystems. Saturation parameters (I-k and I-s) occurred in a relatively narrow range of irradiances (100-400 mumol photons m(-2) s(-1)), with some exceptions (higher in some filamentous green algae or lower in red algae). These parameters were way below the irradiances measured at collecting sites for most algae, which means that most of the available light energy was not photochemically converted via photosynthesis. Acclimation to ambient PAR was observed, as revealed by lower values of I-k and I-c and higher values of alpha and quantum yield in algae from shaded streams, and vice versa. Forms living within the boundary layer (crusts) showed responses of shade-adapted species and had the highest values of P-max, alpha and quantum yield, whereas the opposite trend was observed in gelatinous forms (colonies and. laments). These results suggests adaptation to the light regime rather than functional attributes related to the growth form.

The effect of chilling on the photosynthetic activity in coffee (Coffea arabica L.) seedlings. The protective action of chloroplastid pigments

Coffea arabica is considered to be sensitive to low temperatures, being affected throughout its entire life cycle. Injury caused by chilling (low temperatures above zero degree centigrade) is characterized primarily by inhibition of the photosynthetic process. The objective of this work was to evaluate the role of photosynthetic pigments in the tolerance of coffee (C. arabica L.) seedlings to chilling. The evaluation the photosynthetic activity was made by emission of Chl a fluorescence at room temperature (25°C) in vivo and in situ, using a portable fluorometer. The pigment content was obtained by extraction with 80% acetone, while estimation of membrane lipid peroxidation was determined by measuring the MDA content in leaf tissue extracts. The results indicated a generalized reduction in the quantum yield of PSII when the seedlings were maintained in the dark. The reduction occurred in the seedlings submitted to chilling treatment as well as in the control ones. This demonstrates that not only chilling acts to cause an alteration in PSII. It is possible that the tissue storage reserves had been totally exhausted, with the respiratory rate exceeding the photosynthetic rate; the later was nil, since the seedlings were kept in the dark. The efficiency in the capture, transfer and utilization of light energy in PS11 photochemical reactions requires a sequence of photochemical, biochemical and biophysical events which depend on the structural integrity of the photosynthetic apparatus. However, this efficiency was found to be related to the protective action of chloroplastid pigments, rather than to the concentration of these pigments.

Alterations in chlorophyll a fluorescence, pigment concentrations and lipid peroxidation to chilling temperature in coffee seedlings

Coffea arabica L. is considered to be sensitive to low temperatures throughout its life cycle. In some Brazilian regions, seedling production occurs under shade conditions and during the winter, with average temperatures of around 10 °C. The formation and functioning of the photosynthetic apparatus are strongly controlled by temperature. This study aimed to assess the changes that occurred in pigment contents, lipid peroxidation and variables of chlorophyll a fluorescence during the greening process of coffee seedlings submitted to chilling. Results indicate that saturation of the photosynthetic activity of coffee seedlings occurred before saturation of the accumulation of chloroplastid pigments. Pigment accumulation during the greening process is far beyond the metabolic needs for the maintenance of photosynthetic activity, more specifically of photosystem II. Coffee seedlings attained a quantum yield equivalent to that of the control with approximately half the chlorophyll a and b contents and around 40% of the carotenoid. Low temperature decreases the metabolism of seedlings, consequently reducing free radical production and lipid peroxidation. The chilling temperature (10 °C) used inhibited the accumulation of chloroplast pigments, in turn altering the capacity of the photosynthetic tissue of etiolated coffee seedlings to capture and transfer photon energy to the photosystem II reaction centre. These alterations were better demonstrated by O-J-I-P chlorophyll a fluorescence transients, rather than F v/F m and F v/F 0 ratios. © 2009 Elsevier B.V. All rights reserved.

Dimensionality effects in the local density of states of ferromagnetic hosts probed via STM: Spin-polarized quantum beats and spin filtering

We theoretically investigate the local density of states (LDOS) probed by an STM tip of ferromagnetic metals hosting a single adatom and a subsurface impurity. We model the system via the two-impurity Anderson Hamiltonian. By using the equation of motion with the relevant Green's functions, we derive analytical expressions for the LDOS of two host types: a surface and a quantum wire. The LDOS reveals Friedel-like oscillations and Fano interference as a function of the STM tip position. These oscillations strongly depend on the host dimension. Interestingly, we find that the spin-dependent Fermi wave numbers of the hosts give rise to spin-polarized quantum beats in the LDOS. Although the LDOS for the metallic surface shows a damped beating pattern, it exhibits the opposite behavior in the quantum wire. Due to this absence of damping, the wire operates as a spatially resolved spin filter with a high efficiency. © 2013 American Physical Society.

Luminescence Enhancement of Carboxyl-Coated CdTe Quantum Dots by Silver Nanoparticles

Metallic nanoparticles (NPs) have been used to improve the sensibility of biosensors and bioassays either by enhancing radiative emission or inducing quenching process on fluorescent probes. The aim of this research was to study the interaction of silver and silver-pectin NPs with water-dispersed carboxyl-coated cadmium telluride (CdTe) quantum dots (QDs). Metallic NPs were observed to change the emission of these fluorophores through local field effects. In a solution-base platform, an increase of 82 % was observed for the CdTe emission due to the interaction of QDs and silver-pectin NPs. QDs interaction with silver NPs without pectin was also investigated and a smaller emission enhancement of 20 % was detected. We observed that the NPs' nature and QDs' surface charge and concentration are important parameters for NPs-QDs interaction. Moreover, the presence of the pectin polymer shows to be a key component to the observed fluorescence enhancement. © 2013 Springer Science+Business Media New York.