Solar light mediated anthracene abatement in aerated aqueous media using a thermoplastic nanocomposite photocatalyst.

Polycyclic aromatic hydrocarbons (PAHs) are the most widespread xenobiotic pollutants in water and their abatement usually involves expensive and energy-consuming treatments. In this work, anthracene (AN) was selected as the recalcitrant model of PAHs and its solar light-stimulated heterogeneous photocatalytic abatement in aerated aqueous media was investigated using a new TiO2 derived thermoplastic nanocomposite in thin film form. The results were also compared with the benchmark TiO2 photocatalyst in slurry form. Finally, the possible contribution of reactive intermediates such as hydroxyl radical, AN radical cation and singlet oxygen, was investigated by using a hydroxyl radical trap and laser flash photolysis. Based on the obtained results, a feasible mechanism for AN photodegradation, which involves hydroxyl radical as the key oxidizing species is proposed.

Photosensitized Thermoplastic Nano-Photocatalysts Active in the Visible Light Range for Potential Applications Inside Extraterrestrial Facilities.

Among different depollution methods, photocatalysis activated by solar light is promising for terrestrial outdoor applications. However, its use in underground structures and/or microgravity environments (e.g., extraterrestrial structures) is forbidden. In these cases, there are issues related to the energy emitted from the indoor lighting system because it is not high enough to promote the photocatalytic mechanism. Moreover, microgravity does not allow the recovery of the photocatalytic slurry from the depolluted solution. In this work, the synthesis of a filmable nanocomposite based on semiconductor nanoparticles supported by photosensitized copolyacrylates was performed through a bulk in situ radical copolymerization involving a photosensitizer macromonomer. The macromonomer and the nanocomposites were characterized through UV-Vis, fluorescence and NMR spectroscopies, gel permeation chromatography and thermogravimetric analysis. The photocatalytic activity of the sensitized nanocomposites was studied through photodegradation tests of common dyes and recalcitrant xenobiotic pollutants, employing UV-Vis and visible range (λ > 390 nm) light radiations. The sensitized nanocomposite photocatalytic performances increased about two times that of the unsensitized nanocomposite and that of visible range light radiation alone (>390 nm). The experimental data have shown that these new systems, applied as thin films, have the potential for use in indoor deep underground and extraterrestrial structures.

Microwave based regenerating permeable reactive barriers (MW-PRBs): Proof of concept and application for Cs removal.

The present study evaluates the concept of permeable reactive barrier (PRB) coupled with microwaves (MWs) as in situ-regenerating technology with focus on Cs-contaminated water. Experimental and modelling results data from batch and column tests were carried out, evaluating several chemical-physical and environmental parameters. Main results showed a very rapid increase in GAC temperature during MW irradiation up to ∼680 °C. This highlights the GAC strong ability to transform MW power into heat due to GAC excellent dielectric properties (ε' = 13.8). Physical characterization revealed that GAC pore volume and specific surface area change with the number of regeneration cycles. GAC regeneration efficiency variation reflects this behaviour with a maximum value of ∼112% (5th cycle). The final GAC weight loss of ∼7% further demonstrates GAC life span preservation during MW irradiation. Results from column tests confirms that GAC can be regenerated by MW also in dynamic condition, due to sublimation/vaporization and vapour stripping Cs removal mechanisms and that the regeneration effectiveness is time-dependent. The breakthrough curve shape confirms significant benefits from MW irradiation. Overall, obtained finding demonstrated the feasibility of the proposed concept, also providing essential data to guide its scaling-up application.

Field technical applicability and cost analysis for microwave based regenerating permeable reactive barriers (MW-PRBs) operating in Cs-contaminated groundwater treatment.

The present study tests the potentiality of a novel microwave based regenerating permeable reactive barrier (MW-PRB) system as combined treatment for Cs-contaminated groundwater. Granular activated carbon (GAC) was selected as adsorptive materials in batch and column MW-regeneration experiments. Experimental and modeling data were elaborated for technical and economic considerations in order to assess the MW-PRB feasibility jointly with essential information regarding its real field applicability. Batch experiments investigated the effects of 10 adsorption-MW regeneration cycles under different MW irradiation conditions (applied electric field = 200-460 V m-1; irradiation times = 1-15 min) by assessing GAC variation properties in term of regeneration yield (δ), specific area and weight loss (WL) variation. Column tests were carried using a dedicated setup essentially including a column filled with GAC implanted in a MW oven cavity (MW electric field of 385 V m-1, irradiation times 5-15 min). Lab-scale results shown the ability of MW in Cs removal from GAC as demonstrated by regeneration yield (δ = 79-110%) and WL (6.78% for 10 cycles) values. This was confirmed in dynamic conditions by data from MW-column tests highlighting the highest Cs removal of ~80% when the maximum regeneration time was applied. Residual Cs concentration in breakthrough curves fitted well with the proposed Yoon and Nelson model (R2 = ~0.97). Results from techno-economic analysis revealed the MW-PRB viability and its advantages also in comparison with conventional PRB systems, demonstrating the concept of combined MW-PRB treatment. Saved cost obtained demonstrated in fact the potential cost effectiveness of MW-PRB system and, consequently, the implementation of novel approach is encouraged. Calculated PRB longevity vs groundwater velocity curves are useful in order to predict long-term PRB performance and the response of the remediation activities, as well as for guiding the design and the scaling-up of MW-PRB treatment.

Antioxidant activity and photostability assessment of trans-resveratrol acrylate microspheres.

Trans-resveratrol (RSV) was microencapsulated in Eudragit® RS100 and RL100 resin blends. Lyophilized microspheres were characterized in the solid state for their micromeritic properties and drug loading. FT-IR, PXRD, and DSC analyzes suggested that RSV formed an intimate microcrystalline dispersion within the polymer network, also confirmed by SEM analysis. This produced a reduced degradation of RSV after storage at 40 °C, compared to the neat drug, and a protection of the drug from UV light-induced trans-cis isomerization (60% intact drug was found after 60 s irradiation at 350 nm, compared to 37% for the pure drug). Solubility and in vitro dissolution studies indicated that microencapsulation did not improve the dissolution pattern of RSV in simulated gastric and intestinal aqueous fluids. Evaluation of the in vitro antioxidant activity showed that, compared to the neat drug in aqueous solution, RSV loaded in the microspheres retained for a longer time, up to 22 days of incubation, the initial ORAC capacity. The present study thus demonstrated that Eudragit® Retard resins can be used to easily produce micro-sized solid dispersions with RSV, for potential oral administration, contributing to ameliorate the physico-chemical stability and antioxidant activity of this compound.

Mediterranean Diet and Particulate Matter Exposure Are Associated With LINE-1 Methylation: Results From a Cross-Sectional Study in Women.

Emerging evidence suggests that air pollution increases the risk of cardiovascular disease (CVD) and metabolic disorders, adding to the global burden of disease attributable to lifestyle and behavioral factors. Although long interspersed nucleotide elements 1 (LINE-1) methylation has been associated with these disorders, no studies have simultaneously examined the effects of diet and air pollution exposure on DNA methylation. Herein, we evaluated the association of particulate matter (PM with aerodynamic diameters of less than 10 mm) exposure and adherence to Mediterranean Diet (MD) with LINE-1 methylation. Healthy women (n = 299), aged 15 to 80 years, were enrolled in a cross-sectional study. Dietary data and adherence to MD were assessed by a Food Frequency Questionnaire (FFQ) and Mediterranean Diet Score (MDS). PM10 levels during 1-month before recruitment were recorded by monitoring stations and assigned to each woman based on their residential address and day of recruitment. LINE-1 methylation in blood samples was assessed by pyrosequencing and reported as percentage of 5-methylcytosine (5mC). The Mann-Whitney U test, Spearman's rank correlation test and linear regression models were applied. Our results demonstrated, for the first time, an inverse association between adherence to MD and exposure to PM10 with LINE-1 methylation: while higher monthly PM10 exposure decreases LINE-1 methylation level (ß = -0.121; p = 0.037), the adherence to MD increases it (ß = 0.691; p < 0.001). MDS seemed to interact with PM10 levels (p = 0.002) on LINE-1 methylation, as such we confirmed that the effect of MD decreased with increasing PM10 levels (ß = 0.657; p < 0.001 in the first tertile; ß = 0.573; p < 0.001 in the second tertile; ß = 0.551; p < 0.001 in the third tertile). Thus, we suggest that LINE-1 methylation is a possible mechanism underpinning environment-related health effects, and encourage further research to evaluate whether the adherence to the MD could counteract the negative effect of PM10 exposure.

Environmental Life Cycle Assessment of marine sediment decontamination by citric acid enhanced-microwave heating.

The potential ability of microwave heating (MWH) for the remediation of marine sediments affected by severe hydrocarbon (HC) contamination was investigated. Decontamination effectiveness and environmental sustainability through a comparative Life Cycle Assessment (LCA) were addressed. Main results revealed that the application of a 650-W MWH treatment resulted in a rapid (15min) HC removal. A citric acid (CA) dose of 0.1M led to enhanced-HC removals of 76.9, 96.5 and 99.7% after 5, 10 and 15min of MW irradiation, respectively. The increase in CA dose to 0.2M resulted in a shorter successful remediation time of 10min. The exponential kinetic model adopted showed a good correlation with the experimental data with R2 values in the 0.913-0.987 range. The nature of the MW treatment was shown to differently influence the HC fraction concentration after the irradiation process. Achieved HC removals in such a short remediation time are hardly possible by other clean-up techniques, making the studied treatment a potential excellent choice. Removal mechanisms, which allowed the enhanced-MWH to operate as a highly effective multi-step technique (pure thermal desorption+chemical washing), undoubtedly represent a key factor in the whole remediation process. The LCA highlighted that the MW technology is the most environmentally sustainable alternative for sediment decontamination applications, with a total damage, which was 75.74% lower than that associated with the EK (0.0503pt).

Integrated approach of nutritional and molecular epidemiology, mineralogical and chemical pollutant characterisation: the protocol of a cross-sectional study in women.

INTRODUCTION: Environmentally-related health and disease are the result of the exposome, the totality of a person's environmental exposures, from all sources and routes, across their lifespan. Epigenetic phenomena, including DNA methylation, can be potentially modified by environmental and lifestyle factors, and result in environmental reprogramming of the genome for exposed individuals and for future generations of offspring. OBJECTIVE: The objective of the project is to evaluate the risk of DNA hypomethylation due to air pollution, Mediterranean diet adherence, folate intake, and demographic and socioeconomic factors, in healthy women living in the metropolitan area of Catania, Italy. METHODS AND ANALYSIS: Non-pregnant healthy women will be enrolled in a cross-sectional study. Sociodemographic, lifestyle and dietary intake information will be collected. LINE-1 methylation will be measured by pyrosequencing. The participants' home addresses will be geocoded and each woman will be assigned to the closest monitoring station for particulate matter (PM) exposure assessment. Mineralogical-chemical characterisation of PM and cellular model assays will be performed. An integrated approach will be designed to estimate the combined possible effect of air pollution, Mediterranean diet adherence, folate intake and other lifestyle characteristics on LINE-1 methylation levels. ETHICS AND DISSEMINATION: The project has been approved by the ethics committees of the involved institution and funded by the University of Catania (Finanziamento della Ricerca, FIR 2014). All participants will be fully informed of the purpose and procedures of the study, and signed written consents will be obtained. All the data collected will be treated confidentially and analysed in an aggregate and anonymous way. The results will be published in peer-reviewed journals and communicated to local public health agencies, in order to provide essential information for timely and effective public health action.

Antioxidant capability and phytochemicals content of Sicilian prickly fruits.

The aim of the present study is to compare three cultivars of prickly pear fruits ("Sanguigna" red, "Sulfarina" yellow and "Muscaredda" white) regarding the quality parameters of antioxidant activity, phenolic compounds, betalains and ascorbic acid (vitamin C). Depending on the crop operation, these cultivars are represented by "Agostane" and "Bastardoni" and are located at an altitude between 150 and 750 m, above sea level. Their antioxidant activity was evaluated by ORAC assay. Total phenolic compounds, betalains and ascorbic acid recovered from pulp juice, were determined by a spectrophotometric analysis. The results indicate that the different cultivars of prickly pear possess antioxidant activity in function of the type of the adopted practice. These fruits were derived from the practice of scozzolatura, by dropping the berries to encourage a second bloom of the plant. Among the "Bastardoni", the "Sulfarina" possesses the highest antioxidant activity.

Molecular docking and fluorescence characterization of benzothieno[3,2-d]pyrimidin-4-one sulphonamide thio-derivatives, a novel class of selective cyclooxygenase-2 inhibitors.

The aims of this study were: (i) to explore the structure-activity relationship of some new anti-inflammatory benzothieno[3,2-d]pyrimidin-4-one sulphonamide thio-derivatives 1-11; and (ii) to evaluate the possibility of using the most active compounds as fluorescent probes to determine tumours or their progression. Therefore, to know the precise mechanism by which these compounds interact with cyclooxygenase (COX)-2 enzyme, a molecular docking study was carried out; to assess spectroscopic characteristics, their absorption and emission properties were determined. The results demonstrated that some derivatives of benzothieno[3,2-d] pyrimidine exhibit interesting anti-inflammatory properties related to interactions with active sites of COX-2 and are fluorescent. The antipyrine-bearing compound 4 displayed high COX-2 affinity (ΔG = -9.4) and good fluorescent properties (Φfl = 0.032). Thus, some members of this new class of anti-inflammatory may be promising for fluorescence imaging of cancer cells that express the COX-2 enzyme. Further in vitro and in vivo studies are needed to confirm this hypothesis.

UVA photoinduced yeast protein modifications by methylene blue and naproxen.

UVA photosensitization by methylene blue (MB) or by naproxen (NAP) towards cell proteins in yeast Saccharomyces cerevisiae was investigated in order to compare this system with two simpler models, such as free Trp in solution and as a component of bovine and human serum albumin. The process was studied by monitoring protein tryptophan (Trp) residue integrity. The sensitized photodegradation of proteins resulted in different degrees of Trp damage with different Trp (photo)-products. Indeed, many of these Trp derivatives are diagnostic for the photosensitization mechanism and some of them were obtained from cells by UVA photosensitization for the first time in this work. The analysis of quantum yields of photoproduct distribution allowed us to weigh up the type I/II contribution on a UVA photosensitization mechanism. The UVA mediated generation of these Trp derivatives is consistent with the occurrence of singlet oxygen formation (almost dominant in MB), and photoionization (significant in NAP) within the protein matrix. The results obtained in the case of this more complex system (cell) are in agreement with the two simpler models recently studied in our lab. The quantum yields of Trp photoinduced degradation, as well as of its photoproducts formation, decrease with increasing the complexity of the investigated target.

Photoinduced protein modifications by methylene blue and naproxen.

HPLC and emission spectroscopy were used to investigate UVA photosensitization of methylene blue (MB) or naproxen (NAP) towards bovine serum albumin (BSA). In addition, time resolved singlet oxygen measurements were carried out. The most stable drug : protein adducts stoichiometry of MB-BSA (1 : 1) and NAP-BSA (9 : 1) were verified by means of binding constant determination. UVA photosensitization of MB or NAP on BSA was studied by monitoring tryptophan (Trp) residue integrity. The sensitized photodegradation of the BSA resulted in different degrees of Trp damage. Thus, protein damage was determined by quantitative measurements of the different Trp (photo)-products. Indeed, many of these Trp derivatives are diagnostic for the photosensitization mechanism and some of them, for the first time in this work, were obtained by UVA photosensitization in proteins. The analysis of quantum yields of the photoproduct distribution allowed to weigh up the type I/II contribution to the UVA photosensitization mechanism. As expected, additional experiments in deuterated solvent resulted in an increase of the photodegradation quantum yields for those species where a singlet oxygen mechanism was involved. The UVA mediated generation of these Trp derivatives is consistent with the occurrence of singlet oxygen formation (almost dominant in MB), and photoionization (significant in NAP) within the protein matrix. Additional experiments at lower NAP concentration, as well as with human serum albumin (which differs for Trp content and, partially, localization), support further the molecular mechanism of photosensitization proposed. The results obtained in the case of this more complex system are in agreement with the free Trp model, even if, in almost all cases, the Trp photoproduct formation quantum yields are lower, due to the higher number of sensitization targets in the proteins.

Photosensitization reactions of fluoroquinolones and their biological consequences.

This review focuses on damage photosensitized by the fluoroquinolone (FQ) antibacterial drugs. Different models are employed to study biosubstrate photodamage mediated by FQs (organisms, cells, isolated biomolecules and super molecules). Being that the effect of environment (polarity of the medium, ions, pH, binding with bio-molecules, etc.) is crucial in FQ photochemistry, photobiological reactions can be consequently dramatically influenced. Thus, the photosensitization processes induced by FQs are here discussed taking into account that such extensive and cross-targeted pathological implications request an excursus covering photosensitization in systems of increasing molecular complexity. In vivo and in vitro evidences for photoallergy, phototoxicity, photomutagenesis and photocarcinogenesis mediated by FQs are discussed.

Photosensitization induced by the antibacterial fluoroquinolone Rufloxacin leads to mutagenesis in yeast.

Rufloxacin (RFX) is an antibacterial fluoroquinolone that exhibits UVA photosensitization properties. Photosensitization reactions lead to the formation of oxidative damage, mainly via singlet oxygen. Here we explore the phototoxic and photomutagenic potency of RFX using a panel of yeast (Saccharomyces cerevisiae) mutants affected in different DNA repair pathways. Yeast mutants provide a sensitive tool to identify the photodamage and the DNA repair pathways that cope with it. Cell viability test at increasing dose of UVA shows that both the DNA repair deficient and wild type cells are equally sensitive to RFX-induced photosensitization, demonstrating that phototoxic effect is not due to DNA injury. Photomutagenicity of RFX is evaluated by measuring the frequency of forward Can(R) mutations. The mutation induction is low in wild type cells. A high increase in mutation frequency is observed in strains affected in Ogg1 gene, compared to wild type and other base excision repair deficient strains. The mutation spectrum photomediated by RFX in wild type cells reveals a bias in favour of GC>TA transversions, whereas transition and frameshift mutations are less represented. Altogether data demonstrates that 8-oxo-7,8-dihydroguanine (8-oxoGua) is by far the major DNA damage produced by RFX photosensitization, leading to mutagenesis. We also explore the role played by DNA mismatch repair, translesion synthesis and post-replication repair in the prevention of mutagenic effects due to RFX exposure. In addition, we show that most of RFX photodegradation products are not mutagenic. This study defines the phototoxic and photomutagenic properties of antibacterial RFX and point out possible unwanted side effects in skin under sunlight.

Effects of bio-compatible metal ions on rufloxacin photochemistry, photophysics and photosensitization: copper(II).

The presence of copper(II) in the micromolar range modulates the photodegradation rate of the fluoroquinolone Rufloxacin (RFX), both under air and in nitrogen saturated aqueous solution. The photodegradation rate of RFX under aerobic conditions decreases in the presence of metal ions, and no change in the nature of the photoproducts is observed. In anaerobic media, RFX photodegradation rate increases with increasing copper(II) concentration and the photoproducts distribution changes. Copper(II) inhibits formation of type II products of 2'-deoxyguanosine diagnostic of photosensitization mediated by singlet oxygen. The overall results provide a clear example demonstrating how a bio-compatible trace element influences efficiently not only the bioavailability of a drug but also its molecular mechanism of photodegradation and photosensitization.

Role of aromatic amino acid tryptophan UVA-photoproducts in the determination of drug photosensitization mechanism: a comparison between methylene blue and naproxen.

The aromatic amino acid tryptophan is the most susceptible protein residue involved in various photosensitized adverse effects. Of these processes, the tryptophan photosensitization induced by methylene blue has been well studied. A predominant type II photosensitizing activity, mediated by singlet oxygen, has been already demonstrated on various models. The purpose of this study is to compare this photosensitization system with that induced by naproxen, belonging to the class of non-steroidal anti-inflammatory drugs. For this compound, a type I (radical) and type II (singlet oxygen) cooperative mechanism of photoinduced damage was previously proposed. This study represents an example of testing drugs on the simple experimental model of amino acid residues in proteins. Particular emphasis is dedicated to modifications caused by the formation of drug photomediated toxic species, such as reactive oxygen species (ROS). This is achieved following the kinetics of photodegradation of the sensitizers and of the amino acid, as well as the formation of their photoproducts and by evaluation of quantum yields of the various processes. Tryptophan photoproducts represent biomarkers of oxidative damage indicative for protein photooxidation and for the molecular mechanism of photosensitization; some of these have been identified for the first time as UVA photosensitization products. The pattern of Trp photoproducts formed by the two compounds differs and is specific for each type of sensitization process. These observations support extending the investigation to systems of increasing molecular complexity, that is Trp in isolated proteins and in cells and represent an effort to provide a simplified rationale of the complex picture coming out from literature data and our experimental results.

Spectroscopic properties of some derivatives of polycyclic aromatic hydrocarbons.

The aim of this paper is to provide a general picture of the spectral characteristics of some polycyclic aromatic hydrocarbon (PAH) derivatives. A great deal of data concerning PAHs has been reported in the literature, but there is lack of comprehensiveness about important parameters in the same experimental conditions for their nitro (NO(2)) and amino (NH(2)) derivatives such as absorption and emission characteristics. Thus, important parameters such as the molar extinction coefficient, absorption maxima, fluorescence maxima, and fluorescence quantum yield are reported here. The efficiencies of the reduction of NO(2)-PAHs to their corresponding amino compounds were also verified by means of high-performance liquid chromatography (HPLC). This class of derivatives represents one of the most toxic groups of carcinogenic substances and therefore the data reported here should be useful for toxicological research.

Rufloxacin-induced photosensitization in yeast.

The fluoroquinolone Rufloxacin (RFX) is active as specific inhibitor of bacterial gyrase. The adverse effects of the photosensitization induced by fluoroquinolones are well known. A predominant type II photosensitizing activity of Rufloxacin has already been demonstrated on simpler models (free nucleosides, calf thymus DNA), whereas a cooperative mechanism was corroborated on more complex ones (plasmid and fibroblast). The purpose of this study is to examine the drug photocytoxicity in another complex cellular model, a wild-type eukaryotic fast-growing microorganism whose cultivation is cheap and easily managed, Saccharomyces cerevisiae. This work represents the first report of the potential photogenotoxicity of Rufloxacin. Particular emphasis was given to DNA modifications caused in yeast by the formation of Rufloxacin photomediated toxic species, such as hydrogen peroxide and formaldehyde. Drug phototoxicity on yeast was evaluated by measuring DNA fragmentation (single/double strand breaks) using single cell gel electrophoresis assay and 8-OH-dGuo, a DNA photooxidation biomarker, by HPLC-ECD. Cellular sensitivity was also assessed by cell viability test. The extra- and intracellular RFX concentration (as well as its main photoproduct) was verified by HPLC-MS, whereas the cytotoxic species were evaluated by colorimetric assays. The results confirm the phototoxicity of Rufloxacin on yeast cell and are in agreement with those previously obtained with human fibroblast and with simpler models used recently, and provide a clear link between DNA photosensitization and overall phototoxicity.

Rufloxacin induced photosensitization in bio-models of increasing complexity.

Rufloxacin belongs to the class of fluoroquinolones that act mainly as specific inhibitors of bacterial Topoisomerase II. These drugs are widely known to be involved in various diseases ranging from cutaneous reactions to aging. The type II photosensitizing activity of Rufloxacin has been already demonstrated on calf thymus DNA and free nucleosides. The aim of this study is to examine in control untreated and UVA irradiated human fibroblasts the modifications on DNA status induced by Rufloxacin added in the culture medium. This allows to investigate the photosensitizing activity of Rufloxacin in a more complex cell model. Fibroblasts, either in the presence or in the absence of Rufloxacin, were exposed to UVA irradiation for different times. An experimental protocol was followed in order to evaluate the amount of single-strand breaks (SSB) and double-strand breaks (DSB) DNA fragmentation by comet assay, and plasmid photocleavage. The presence of oxidized bases was also evaluated using the 8-OH-dGuo test. The comet assay test was also employed to assess cellular repair capacity. The intracellular drug concentration was verified by HPLC-MS. The results confirming the role of Rufloxacin as photosensitizer were: (i) a time-dependent increase in DNA fragmentation when fibroblasts were irradiated in the presence of Rufloxacin; (ii) the efficiency of the cellular repair machinery to be exhaustive after 2 h (whereas no correlation between irradiation time and DNA damage repair was observed with a higher level of DNA fragmentation after shorter irradiation times); (iii) the increased number of cells exhibiting high DNA fragmentation, seen as comets with long tails, was not accompanied by a similar large extent of oxidised DNA base formation, as measured by 8-OH-dGuo analysis; (iv) the double helix SSB, formed in plasmid photosensitization, agreed with the comet assay results, pointing out a good correlation among the cell system and the simpler models used.

Photosensitizing effect of some nonsteroidal antiinflammatory drugs on natural and artificial membranes: dependence on phospholipid composition.

Previous studies have clarified the molecular mechanism of photosensitization on red blood cell membranes induced by some drugs belonging to the class of nonsteroidal antiinflammatory drugs: ketoprofen, naproxen, and diflunisal. This process involves the participation of photodegradation products, free radicals, and reactive oxygen species. The aim of the present paper is to investigate the photohemolytic process using red blood cells of mammalian species, with different membrane phospholipid compositions. Human and bovine red blood cell membranes were selectively enriched with phosphatidylcholine and sphingomyelin. For this purpose, a new approach for phospholipid investigation was undertaken. Moreover, the phototoxic effect was tested with liposomes at different phospholipid compositions. A structure-function relationship between the erythrocyte membrane phospholipid composition and the photohemolytic process induced by the sensitizers can be proposed. Indeed, the different contents of the photoperoxidable double bond and the variable architecture of the membrane bilayer, due to the different phosphatidylcholine and sphingomyelin contents, strongly influence the resistance of the cell to an osmotic shock induced by photogenerated transient species or by the lytic activity of drug photoproducts. The higher content of sphingomyelin, its asymmetric disposition at the outer surface of membrane bilayers, the high level of saturated acyl fatty chains, and the presence of photoperoxidable trans double bonds in the hydrophilic region greatly decrease the fluidity of bilayers and enhance the resistance of the membrane to phototoxic damage. On the other hand, an increase in the content of phosphatidylcholine, which is rich in species with unsaturated acyl fatty chains, decreases the membrane resistance, because these latter can be easily oxidized by drug-photogenerated reactive oxygen species.