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PubMed1996

Photosensitization of bilirubin on proliferation and DNA synthesis in ascitic hepatoma cells.

AIM: To observe the effects and its mechanism of photosensitization of bilirubin on ascitic hepatoma (Hep A) cells. METHODS: After the cells were illuminated under the light (1.0 x 10(5) lx) for 10 min, deoxy[3H]thymidine was added for DNA synthesis assay. The cells were dyed with 0.5% trypan blue and were counted. RESULTS: The cell mortality of illuminated groups were much higher than that of dark groups (P < 0.01). The inhibitions of DNA synthesis of illuminated groups were stronger than that of dark groups (P < 0.01). The cell mortality and inhibition of DNA synthesis of illuminated groups were positively dependent upon the concentrations of bilirubin and illuminating time. No difference of DNA synthesis between room light illumination groups and dark groups (P < 0.05). CONCLUSION: The photosensitization of bilirubin killed Hep A cells obviously. Bilirubin under room light had no effect on inhibition of DNA synthesis. The photosensitization of bilirubin was closely related to 1O2 and H2O2 and not to OH. and O2-. Bilirubin, the end product of heme catabolism in mammals, is a potentially cytotoxic, lipid soluble waste product that needs to be excreted. However, bilirubin at micromolar concentration in vitro, efficiently scavenges peroxyl radicals. In liposomes, bilirubin suppresses the antioxidation more than alpha-tocopherol, which is regarded as the best antioxidant of lipid peroxidation. Thus bilirubin is a physiological, chain-breaking antioxidant. Bilirubin exhibited antitumor activity and acted as a photosensitizer with four pyrrole rings. Many photosensitizers have been used to treat cancer due to their photosensitization. In this paper, the photosensitization of bilirubin on DNA synthesis in ascitic hepatoma (Hep A) cells and on cell mortality were studied.

Animals↗
PubMed1993

Uptake and distribution of intravenously or intravesically administered photosensitizers in the rat.

Photodynamic therapy using i.v. injected porphyrin photosensitizers have been used to treat selected cases of superficial bladder cancer. Since cutaneous photosensitivity, lasting 6-8 weeks, is a well known undesirable side effect of this therapy, we instilled the photosensitizers intravesically in rats and compared the uptake of photosensitizers in different tissues by this route of administration with the uptake after intravenous injection. The intravesical mode of delivery enhanced photosensitizer uptake in the bladder wall, while giving low concentrations in extravesical organs. Intravesical instillation of the photosensitizers may therefore increase their efficacy and reduce phototoxicity as compared with intravenous injection. Comparing the results obtained by two assays, one based on porphyrin fluorescence and the other based on the application of radioactively labelled photosensitizers, it was concluded that the i.v. administration route may result in tissue uptake of significant amounts of aggregated non-fluorescent, supposedly inactive drug, while the intravesical administration led to less uptake of aggregates relative to active drug monomers.

Animals↗
PubMed2003

Photostimulated fos-like immunoreactivity in tuberal hypothalamus of photosensitive vs. photorefractory turkey hens.

Photorefractoriness in commercial turkey hens can be viewed as a failure of previously sexually stimulatory photoperiods to maintain egg production via activation of cGnRH I neurons, but the neural locus of photorefractoriness, i.e., where in the brain failure occurs, is not known. We used a c-fos antiserum that detects c-Fos and Fos-related antigens to characterize Fos-like immunoreactivity (FLI) as a measure of neuronal activation. FLI was measured in somatically mature, photosensitive hens (held on short photoperiods [8L:16D] for at least 10 weeks) before (non-photostimulated-photosensitive group) and after 48 h of exposure to long photoperiods (16L:8D; photostimulated-photosensitive group). We also measured FLI in hens that had become photorefractory, transferred to short photoperiods for 1 week--an insufficient time period to reverse photorefractoriness--and then exposed to long photoperiods for 48 h (photostimulated-photorefractory group). FLI was nearly absent in the tuberal hypothalamus of non-photostimulated-photosensitive hens but FLI was abundant in photostimulated-photosensitive hens. FLI was greatly reduced (P<0.01) in the rostral tuberal hypothalamus of photostimulated-photorefractory hens. All hens showed variable extra-tuberal FLI in locations associated with stress, e.g., paraventricular nucleus, lateral septal area, and nucleus taenia. Double-label fluorescence immunohistochemistry with c-fos antiserum and anti-Neu-N, a neuron-specific protein, showed that a substantial fraction of tuberal FLI-positive cells in photostimulated-photosensitive hens were neuronal. These results implicate neurons in the rostral tuberal hypothalamus as a potential neural locus of photorefractoriness, as FLI in this region appears coupled with cGnRH I activation in photostimulated-photosensitive but not photostimulated-photorefractory turkey hens.

Animals↗
PubMed1999

Lymphocyte stimulation test with drug-photomodified cells in patients with quinolone photosensitivity.

Quinolone antibacterial agents, known to elicit photosensitive dermatitis as an adverse effect, have both phototoxicity and photoallergenicity. The latter potency is mainly derived from their photohaptenic moiety; quinolones covalently bind to protein and cells upon exposure to ultraviolet A (UVA) light. Our previous study has shown the in vivo and in vitro antigenicity of quinolone-photomodified cells in mice. Here, we examined the presence of sensitized lymphocytes that react with quinolone-photomodified autologous cells in patients with photosensitivity to quinolones. A flow cytometric analysis using a monoclonal antibody specific to quinolone photoadducts demonstrated that peripheral blood mononuclear cells (PBMC) were successfully photomodified with quinolones upon exposure to UVA. PBMC from quinolone-photosensitive patients were cocultured with autologous PBMC photomodified with the causative drug. Modest but significant proliferative responses of responder lymphocytes were found in patients photosensitive to lomefloxacin, fleroxacin, and enoxacin, indicating photoallergic mechanism in these patients. On the other hand, sparfloxacin-photosensitive patients exhibited negative lymphocyte stimulation test, suggesting that its photosensitivity is mainly phototoxic. When UVA-preirradiated quinolones were used as stimulators, only fleroxacin exceptionally stimulated patients' PBMC, indicating its prohaptenic as well as photohaptenic properties. These findings suggest the presence of circulating sensitized T cells in patients with photosensitivity to certain quinolones.

Aged↗
PubMed2005

Photosensitivity in idiopathic generalized epilepsies.

Photosensitivity is an abnormal visual sensitivity of the brain in reaction to flickering light sources or patterns and is expressed in the electroencephalogram as generalized spike-and-wave discharge and in more susceptible individuals as clinical seizures. The most common types of seizures are generalized tonic-clonic, followed by myoclonic and absence. The photosensitive epilepsies are classified as pure photosensitive, where seizures occur only with the flickering light source/pattern or during intermittent photic stimulation (IPS) in the laboratory, and epilepsy with photosensitivity, where spontaneous seizures also occur. Positive response to IPS in idiopathic epilepsy syndromes, which are included in the International Classification or are in development, is reported to range from 7.5% in juvenile absence epilepsy to 100% in pure photosensitive epilepsy. The treatment of photosensitivity and pure photosensitive epilepsy with rare seizures includes general and specific protective measures. For most patients, however, combination treatment with antiepileptic drugs is necessary. Valproic acid monotherapy has a success rate of 73-86%. Levetiracetam appears to be a new alternative therapeutic option. Clobazam, lamotrigine, ethosuximide, and topiramate also have been recommended as second-choice therapies.

Anticonvulsants↗
PubMed1991

Chlorin and porphyrin derivatives as potential photosensitizers in photodynamic therapy.

In order to find a photosensitizer with better optical properties and pharmacokinetics than Photofrin II, a series of new photosensitizers related to methyl pheophorbide-a and chlorin-e6 were synthesized. These compounds absorb at substantially longer wavelengths (lambda max 660 nm) than does Photofrin II (630 nm) and show promise for use in photodynamic therapy. Among the porphyrins, we observed that long carbon chain ether derivatives are better photosensitizers than their ester analogs. These sensitizers were tested for in vivo photosensitizing activity vis-a-vis Photofrin II, using the standard screening system of DBA/2 mice bearing transplanted SMT/F tumors. Most of these photosensitizers were found to have better tumoricidal photosensitizing activity than Photofrin II and demonstrated more rapid attenuation of normal tissue photosensitivity with time after administration vis-a-vis Photofrin II.

Molecular Structure↗
PubMed1997

Increased photosensitivity in HL60 cells expressing wild-type p53.

Loss of p53 function has been correlated with decreased sensitivity to chemotherapy and radiation therapy in a variety of human tumors. Comparable analysis of p53 status with sensitivity to oxidative stress induced by photodynamic therapy has not been reported. In the current study we examined photosensitivity in human promyelocytic leukemia HL60 cells exhibiting either wild-type p53, mutated p53 or deleted p53 expression. Experiments were performed using a purpurin, tin ethyl etiopurpurin (SnET2)-, or a porphyrin, Photofrin (PH)-based photosensitizer. Total SnET2 accumulation was comparable in all three cell lines. Uptake of PH was highest in cells expressing wild-type p53 but incubation conditions could be adjusted to achieve equivalent cellular PH levels during experiments that analyzed photosensitivity. Survival measurements demonstrated that HL60 cells expressing wild-type p53 were more sensitive to PH- and SnET2-mediated photosensitization, as well as to UVC irradiation, when compared to HL60 cells exhibiting deleted or mutated p53 phenotypes. A rapid apoptotic response was observed following purpurin- and porphyrin-induced photosensitization in all cell lines. Results of this study indicate that photosensitivity is increased in HL60 cells expressing wild-type p53 and that photosensitizer-mediated oxidative stress can induce apoptosis through a p53-independent mechanism in HL60 cells.

Cell Survival↗
PubMed1990

Tissue distribution and photosensitizing properties of mono-L-aspartyl chlorin e6 in a mouse tumor model.

Mono-L-aspartyl chlorin e6 (NPe6) is a photosensitizer that possesses properties such as chemical purity and a major absorption band at 664 nm which are potentially exploitable for photodynamic therapy (PDT). The current investigation examined pharmacological and photosensitizing parameters of NPe6 in tumor and normal tissues in mice. [14C]NPe6 was used to obtain quantitative tissue distributions of the photosensitizer as a function of: (a) time following administration; (b) drug dose; (c) mode of drug administration; and (d) tumor size. The in vivo photosensitizing efficiency of NPe6 was compared directly to Photofrin II in experiments which evaluated tumor responses and induction of normal skin damage. Initial PDT experiments demonstrated that NPe6 was ineffective at inducing tumor cures when a 24-h time interval (between drug administration and light treatment) was used. However, PDT-induced tumor cures were obtained when NPe6 was administered 4-6 h prior to light exposure, and these NPe6-PDT treatment parameters were as effective as standard Photofrin II-mediated PDT. Interestingly, the level of PDT-induced normal skin damage was significantly greater for Photofrin II than for NPe6 at comparable drug and light doses. An analysis of pharmacological data and PDT time interval requirements suggests that plasma concentrations of NPe6 may be a more important predictive factor than tumor tissue levels of the photosensitizer for the production of PDT-mediated tumor cures. The results of this investigation indicate that NPe6 is an effective tumor photosensitizer with in vivo clearance properties that eliminate the side effect of prolonged normal skin photosensitization.

Animals↗
PubMed1988

Differential cell photosensitivity following porphyrin photodynamic therapy.

Experiments were performed to determine if differences in porphyrin photosensitivity could be observed for cells with varying efficiency in DNA damage repair, as well as for cells which make up components of the vasculature. Photofrin II is undergoing current clinical evaluation for photodynamic therapy of solid tumors, and therefore the retention, dark toxicity, and photosensitizing effects of this drug on human DNA repair-deficient fibroblasts (ataxia telangiectasia and xeroderma pigmentosum) were compared to normal human fibroblasts. In addition, bovine cells of endothelial, smooth muscle, and fibroblast origin were compared for porphyrin retention, toxicity, and photosensitivity. All human fibroblasts exhibited porphyrin-induced dark toxicity, but there were no significant differences in photosensitization or porphyrin retention for any of these cell lines. However, bovine endothelial cells were considerably more photosensitive than smooth muscle or fibroblast cells treated under identical conditions. All bovine cells accumulated similar levels of porphyrin, and therefore the increased sensitivity of the endothelial cells was not due to differences in porphyrin retention. These results provide additional evidence that nuclear damage and/or repair is not a dominant factor in the cytotoxicity induced by porphyrin photosensitization. In addition, these results indicate that endothelial cell photosensitivity may play a role in the vascular damage observed following photodynamic therapy.

Animals↗
PubMed1996

TCRV beta 7+ Th2 cells mediate UVB-induced suppression of murine contact photosensitivity by releasing IL-10.

In murine contact photosensitivity, a cutaneous delayed-type hypersensitivity reaction, preirradiation of the photosensitization site with UVB induced Ag-specific, afferent limb-acting, CD4+CD8- suppressor T cells (Ts). The present study examined usage of TCR V beta and production of immunosuppressive cytokines in Ts propagated in vitro. Spleen cells from UVB-preirradiated, 3,3',4',5- tetracholorosalicylanilide (TCSA)-photosensitized mice were stimulated with 3000-rad-irradiated lymph node cells (LNC) from TCSA/UVA-sensitized mice (LNCTCSA) in the presence of rIL-t. After several rounds of antigenic stimulation, a T cell line (B+TCL) consisted exclusively of CD3+CD4+CD8- V beta 7+ and V beta 13+ populations. Transfer to naive recipients of B+TCL treated with anti-V beta mAb plus complement revealed that the V beta 7+ cells suppressed both the in vivo and the in vitro aspects of contact photosensitivity to TCSA in an Ag-specific manner. The in vitro suppressive activity of B+TCL was neutralized by anti-IL-10 mAb, but not by anti-IL-4 mAb, indicating a crucial role of IL-10 in UBV-induced suppression. Upon stimulation with 3000-rad-irradiated-LNCTCSA, B+TCL released IL-4 and IL-10 but not IL-2, and V beta 7+ cells produced IL-10. The reverse transcriptase-PCR detected mRNA for IL-4 and IL-10 but not that for IL-2, IFN-gamma, or TGF-beta in B+TCL stimulated with or without concanavalin A. In accordance with the findings in B+TCL, spleen cells from UVB preirradiation plus TCSA/UVA mice contained V beta 7+ T cells that suppressed contact photosensitivity to TCSA and produced substantial amounts of IL-4 that provided a microenvironment for Th2 cell generation. We conclude that UVB preirradiation and photosensitization result in the generation of V beta 7+ Th2 cells that suppress contact photosensitivity by releasing IL-10. The dysfunction of effector Th1 cells underlying UVB suppression of delayed-type hypersensitivity seems to be due not only to altered APC function but also to counteraction of Th2 cells by Th1 cells.

Animals↗
PubMed1998

Environmental effects on cellular photosensitization: correlation of phototoxicity mechanism with transient absorption spectroscopy measurements.

Little is directly known about the influence of the local environment experienced by a photosensitizer in a biological system on its photophysics and photochemistry. In this paper, we have addressed this issue by correlating mechanistic studies using laser flash photolysis with cellular phototoxicity data, obtained under the same experimental conditions. In particular, we have focused on the interaction between local concentrations of photosensitizer (deuteroporphyrin) and oxygen in determining the mechanism of phototoxicity in L1210 cells. In cells, as well as in models such as liposomes and red blood cell ghosts, hypochromicity and a reduction in fluorescence and intersystem crossing yields are observed on increasing the photosensitizer concentration between 0.5 and 20 microM, which illustrates the onset of a self-association. In aerated cellular preparations, the phototoxicity is predominantly type II (singlet oxygen) for all concentrations studied but an oxygen-independent mechanism occurs at the higher concentrations in deaerated samples. These observations are readily explained by consideration of triplet state kinetics as a function of oxygen and photosensitizer concentrations in cells. The rate constant for quenching of the photosensitizer triplet state by oxygen in cells was measured as 6.6 x 10(8) M-1 s-1 and by photosensitizer ground state as approximately 10(6) M-1 s-1 (in terms of local concentration). The latter reaction gave rise to a long-lived species that is presumably responsible for the oxygen-independent phototoxicity observed at the higher photosensitizer concentrations used. This self-quenching of the triplet state is postulated to arise from electron transfer resulting in radical ion formation. Under conditions where no self-quenching contributes, the phototoxicity measured as a function of oxygen concentration correlates well with a model based on the determined kinetic parameters, thus, unambiguously proving the intermediacy of singlet oxygen. These effects should be borne in mind when interpreting phototoxicity mechanisms from in vitro cell studies. The excellent correlation achieved between laser flash photolysis data and measured phototoxicity gives credence to the direct use of photophysical techniques to elucidate photochemical mechanisms in biological media.

Animals↗
PubMed2006

Clinical pharmacokinetics of the PDT photosensitizers porfimer sodium (Photofrin), 2-[1-hexyloxyethyl]-2-devinyl pyropheophorbide-a (Photochlor) and 5-ALA-induced protoporphyrin IX.

BACKGROUND AND OBJECTIVES: Photodynamic therapy (PDT) uses a photosensitizer activated by light, in an oxygen-rich environment, to destroy malignant tumors. Clinical trials of PDT at Roswell Park Cancer Institute (RPCI) use the photosensitizers Photofrin, Photochlor, and 5-ALA-induced protoporphyrin IX (PpIX). In some studies the concentrations of photosensitizer in blood, and occasionally in tumor tissue, were obtained. Pharmacokinetic (PK) data from these individual studies were pooled and analyzed. This is the first published review to compare head-to-head the PK of Photofrin and Photochlor. STUDY DESIGN/MATERIALS AND METHODS: Blood and tissue specimens were obtained from patients undergoing PDT at RPCI. Concentrations of Photofrin, Photochlor, and PpIX were measured using fluorescence analysis. A non-linear mixed effects modeling approach was used to analyze the PK data for Photochlor (up to 4 days post-infusion; two-compartment model) and a simpler multipatient-data-pooling approach was used to model PK data for both Photofrin and Photochlor (at least 150 days post-infusion; three-compartment models). Physiological parameters were standardized to correspond to a standard (70 kg; 1.818 m2 surface area) man to facilitate comparisons between Photofrin and Photochlor. RESULTS: Serum concentration-time profiles obtained for Photofrin and Photochlor showed long circulating half-lives, where both sensitizers could be found more than 3 months after intravenous infusion; however, estimated plasma clearances (standard man) were markedly smaller for Photofrin (25.8 ml/hour) than for Photochlor (84.2 ml/hour). Volumes of distribution of the central compartment (standard man) for both Photofrin and Photochlor were about the size (3.14 L, 4.29 L, respectively) of plasma volume, implying that both photosensitizers are almost 100% bound to serum components. Circulating levels of PpIX were generally quite low, falling below the level of instrument sensitivity within a few days after topical application of 5-ALA. CONCLUSION: We have modeled the PK of Photochlor and Photofrin. PK parameter estimates may, in part, explain the relatively long skin photosensitivity attributed to Photofrin but not Photochlor. Due to the potential impact and limited experimental PK data in the PDT field further clinical studies of photosensitizer kinetics in tumor and normal tissues are warranted.

Administration, Topical↗
PubMed1994

Influence of dye and protein location on photosensitization of the plasma membrane.

Two membrane-photosensitizing dyes were used to investigate whether selected sites in the plasma membrane vary in their sensitivity to damage by singlet oxygen (1O2*) and, if so, what factors are responsible for the variation. The relative ability of Rose bengal (RB) and merocyanine 540 (MC540), both of which localize in the plasma membrane and produce 1O2*, to photosensitize five plasma membrane functions in P388D1 cells was evaluated. The five membrane functions assessed were: plasma membrane potential, proline transport, facilitated glucose diffusion, 5'-nucleotidase activity, and dye exclusion. Photosensitization efficiency by RB varied by a factor of 188 for these membrane functions, whereas for MC540 a range of only 24 was found. RB was a more efficient photosensitizer than MC540 but the relative efficiencies varied with the membrane function. The wide range of P50 values for RB suggests that it binds selectively to membrane sites where it causes damage with high efficiency; possibly a non-1O2* mechanism is involved. In contrast, MC540 photosensitized the three membrane functions involving integral membrane proteins about equally suggesting that differences are due to small variations in the distribution of MC540 in the plasma membrane and/or variations in the inherent reactivity of the membrane targets with 1O2*. The results indicate that the lability of membrane sites to photosensitization depends both on their inherent reactivity with 1O2* and the relative location of specific protein and dye molecules.

5'-Nucleotidase↗
PubMed1993

The role of lipoproteins in the delivery of tumour-targeting photosensitizers.

1. Serum lipoproteins play an important role in the in vivo transport of several porphyrinoid derivatives having a moderate or high degree of hydrophobicity. 2. There appears to exist a correlation between the extent of photosensitizer association with low-density lipoproteins (LDL) and the efficiency of tumour targeting by some classes of photosensitizers, such as differently sulphonated porphyrins and phthalocyanines, haematoporphyrin dialkylethers and unsubstituted phthalocyanines and naphthalocyanines. 3. In all cases, LDL-carried photosensitizers are preferentially released to malignant cells; hence, direct cell damage appears to be the major determinant of tumour damage consequent to photodynamic therapy. 4. Present evidence suggests that the LDL-associated photosensitizer is accumulated by tumour cells largely via a receptor-mediated endocytotic process. 5. Thus, the use of delivery systems for orientating a systemically injected photosensitizer towards lipoproteins has been explored; promising results have been obtained by incorporation of the dye into liposomal vesicles, oil emulsions or inclusion complexes, as well as by precomplexation of the dye with LDL. 6. Moreover, a suitable choice of the chemical constituents of the delivery system and the experimental conditions allows one to modulate the photosensitizer distribution among the different lipoproteins. 7. The occurrence of tumour-targeting strategies other than the LDL pathway is briefly discussed.

Animals↗
PubMed1996

The effects of electric fields on photosensitized erythrocytes: possible enhancement of photodynamic activation.

In this study it has been found that exposure of photosensitized erythrocytes to short, intense electric pulses, resulted in cell lysis. When erythrocytes were photosensitized with increasing concentrations of the photosensitizer, hematoporphyrin derivative (HPD), and subjected to electric pulses in the absence of light, cell lysis increased with increasing photosensitizer concentration. In addition, it has been shown that exposure of photosensitized erythrocytes to electric field pulses of increasing field strength resulted in increased cell lysis. Light activation of photosensitized erythrocytes, pre-treated with electric pulses, also resulted in increased cell lysis. The results presented here suggest that HPD may be activated in the absence of light using electric pulses. We suggest that enhancement of activation by electric field stimulation may find application in increasing the overall efficiency of photodynamic therapy.

Electric Stimulation↗
PubMed2004

Dynamics of interactions of photosensitizers with lipoproteins and membrane-models: correlation with cellular incorporation and subcellular distribution.

The incorporation and subcellular localization of photosensitizers are critical determinants of their efficiency. Here, we correlate these properties with the interactions of photosensitizers with membrane-models and low density lipoproteins (LDL) in acellular systems. Focus was given on dynamics aspects. Two amphiphilic photosensitizers, deuteroporphyrin (DP) and aluminum phthalocyanine sulfonated on two adjacent isoindole units (AlPcS2a) were selected. The phthalocyanine was bound to LDL with an overall association constant around 5 x 10(7)M(-1). Biphasic association kinetics was indicative of two types of sites. The release of the phthalocyanine into the bulk aqueous medium occurred within less than a second. A similar behavior was found previously for deuteroporphyrin although its affinity was somewhat higher (5.5 x 10(8)M(-1)). Both compounds were previously characterized by high affinity for membrane-models and quick exchange with the bulk solution. However, they strongly differed by their rate of transfer through the lipid bilayer, in the range of seconds for the porphyrin, several hours for the phthalocyanine. In the case of the porphyrin, fluorescence microscopy on human fibroblasts showed diffuse labeling with no significant modification of the distribution upon vectorization by LDL. In contrast, the phthalocyanine was localized in intracellular vesicles. Vectorization by LDL favored lysosomal localization although little effect was found on the overall uptake as shown by extraction experiments. The role of lipoproteins in the cellular localization of photosensitizers is significantly more important for photosensitizers not freely diffusing through bilayers. The dynamics of the interactions of photosensitizers with membranes appears as an important determinant of their subcellular localization.

Animals↗
PubMed2006

Photosensitized reduction of DDT using visible light: the intermediates and pathways of dechlorination.

A reaction mixture containing DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane), methylene green (as the photosensitizer), and triethylamine (as the electron donor) in acetonitrile:water (1:1) was irradiated by an ordinary 150-W GE-Miser spotlight to facilitate visible-light photosensitized DDT dehalogenation. The intermediates and reaction products were identified by GC/MS (gas chromatography/mass spectrometer) and NMR (nuclear magnetic resonance). The photosensitized dehalogenation method partially degraded DDT via an electron transfer relay mechanism. Results indicate that DDT lost about three chlorines after a total of 19 days of irradiation. Aliphatic chlorines were found to be removed easier than aromatic chlorines. Various types of reductants were compared for electron donation efficiency, and photosensitizer concentration was optimized for our reaction system. In most cases, clean and simple dechlorinated products were observed. The proposed photosensitized reduction was coexisted with a thermal elimination effect for the first chlorine removal of DDT, and the photosensitized electron transfer reduction was shown to be the dominating mechanism responsible for further dechlorination after the initial stage. A sequential dechlorination pathway was proposed, with each successive dehalogenation, the reaction proceeds more slowly. The results have shown the feasibility of utilizing visible light, nontoxic dyes and electron donors to render a toxic compound less toxic and to enhance the natural carbon regeneration rates.

DDT↗
PubMed2005

Photodegradation and photosensitization of mycosporine-like amino acids.

The photodegradation and photosensitization of several mycosporine-like amino acids (MAAs) were investigated. The photodegradation of the MAA, palythine, was tested with three photosensitizers: riboflavin, rose bengal and natural seawater. For comparison of degradation rates, the riboflavin-mediated photosensitization of six other MAAs was also examined. When riboflavin was used as a photosensitizer in distilled water, MAAs were undetectable after 1.5h. Palythine showed little photodegradation when rose bengal was added as the photosensitizer (k=0.12x10(-3)m(2)kJ(-1)). Palythine dissolved in natural seawater containing high nitrate concentrations also showed slow photodegradation rate constants (k=0.26x10(-3)m(2)kJ(-1)) over a 24-h period of constant irradiation. Similar experiments in deep seawater with porphyra-334 and shinorine resulted in 75% of the initial MAA remaining after 4h of irradiation and rates of 0.018 and 0.026x10(-3) m(2) kJ(-1), respectively. Experiments conducted in deep seawater with riboflavin additions resulted in photodegradation rate constants between 0.77x10(-3) and 1.19x10(-3)m(2)kJ(-1) for shinorine and porphyra-334, respectively. Photoproduct formation appeared to be minimal with the presence of a dehydration product of the cycloheximine ring structure indicated as well as the presence of amino acids. Evidence continues to build for the role of MAAs as potent and stable UV absorbers. This study further highlights the photostability of several MAAs in both distilled and seawater in the presence of photosensitizers.

Amino Acids↗