VUV-photolysis of aqueous solutions of hydroxylamine and nitric oxide. Effect of organic matter: phenol.

VUV-irradiation of aqueous solutions containing hydroxylamine (NH2OH) in its acid form (NH3OH+) and phenol (C6H5OH) results in the simultaneous mineralization of the organic substrate and the almost quantitative reduction of NH3OH+ to ammonium ions (NH4+). Irradiation of aqueous solutions of NH3OH+ in the absence of organic substrates showed the formation of nitrate (NO3-) and nitrite (NO2-) and minor quantities of NH4+. In line with these experiments, VUV-irradiation of aqueous solutions of nitrogen monoxide (NO˙) yields NH4+ only when C6H5OH is simultaneously mineralized. A possible reaction mechanism is discussed, where reactions of NO˙ and NH3OH+ with hydrogen atoms (H˙), hydroxyl radicals (HO˙) and hydrated electrons (e-aq), all generated by the VUV-photochemically initiated homolysis of water, are of great importance to the observed results. In the presence of phenol, competition between phenol and either NO˙ or NH3OH+ for these reactive intermediates in the primary volume of reactions strongly determines the oxidation state and nature of the N-containing products. C-Centered radicals and intermediate products of reactions may also have an important effect on the overall mechanism. The present results are discussed in relation to the actual state of knowledge presented in the literature.

Continuous process of the vacuum ultraviolet- (VUV-) photochemical oxidation of thiophene in the gas phase.

Thiophene was taken as a model compound for investigations on the efficiency of a continuous process of the vacuum-ultraviolet- (VUV-) photochemically initiated oxidation and mineralization of sulfur containing organic compounds in the gas phase. In the presence of molecular oxygen, atomic oxygen and ozone were photochemically generated and are assumed to initiate or participate in the (thermal) oxidation network. Addition of water vapor for an additional initiation of the oxidation by hydroxyl radicals did not accelerate the process. For comparison, thiophene was exposed to ozone and oxidized under otherwise the same experimental conditions, but complete mineralization was only found in the photochemical process and for relatively small concentrations of the substrate. The result may be explained by low rates of secondary thermal reactions of a number of identified intermediate products. Combining already published results and mechanistic hypotheses with the results of the present work, pathways of oxidative degradation are proposed. The photolysis of thiophene in molecular nitrogen confirmed earlier findings.

The use of chemical actinometry for the evaluation of the light absorption efficiency in scattering photopolymerizable miniemulsions.

Oil-in-water miniemulsions containing a mixture of monomers as the dispersed organic phase have been shown recently to be promising media for the development of photoinitiated polymerization processes. Albeit a crucial factor for a successful application, the efficiency of light absorption by the photoinitiator in these highly scattering systems is difficult to evaluate. In this work, a well-characterized water insoluble chemical actinometer (DFIS) replaced the oil-soluble photoinitiator, and was used as a probe and a model for UV light absorption in miniemulsions of variable droplet sizes and organic phase compositions (i.e. at different levels of scattered light). In the first step, the photon flux absorbed by the actinometer was determined in model miniemulsions based on an inert solvent (ethyl acetate), at a low oil phase content (3.0-6.0 wt%). For these low to moderately scattering systems, the photon flux absorbed by the actinometer in the miniemulsions was comparable to that in a homogeneous solution of ethyl acetate. In the second step, the absorbed photon flux was investigated in photopolymerizable miniemulsions (a mixture of acrylate monomers as oil phase). Surprisingly, in spite of much higher scattering coefficients than those found for ethyl acetate based miniemulsions of otherwise the same composition, the photon flux absorbed by the actinometer in photopolymerizable miniemulsions showed only a small decreasing trend. Such a result may be considered favorable for the further development of applications of photopolymerizations in miniemulsions.

Micellar control of the photooxidation pathways of 10-methyl phenothiazine: electron versus energy transfer mechanisms.

10-Methyl phenothiazine (MPS) was chosen as a model compound to investigate the effects of compartmentalisation and of charged interfaces on the primary mechanisms involved in the phototoxic reactions related to phenothiazine drugs. Two most important pathways resulting from the interaction of the triplet excited state of MPS ((3)MPS*) with molecular oxygen ((3)O2) have to be considered: (i) energy transfer producing singlet oxygen ((1)O2) and (ii) electron transfer generating the superoxide anion (O2˙(-)) and the radical cation (MPS˙(+)). The quantum yields of (1)O2 production by MPS solubilized in the dispersed pseudo-phase of aqueous micellar systems were found to be similar to those determined in solvents of various polarities, regardless of the anionic or cationic nature of the surfactant (SDS or CTAC). However, micellar compartmentalisation and surfactant charge affect considerably both the sensitized and the self-sensitized photooxidation of MPS. The formation of 10-methyl phenothiazine sulfoxide (MPSO), produced by the reaction of MPS with (1)O2, proceeds at a higher rate in SDS micelles than in neat polar solvents. This result may be explained by the protonation of the zwitterionic intermediate Z (MPS(+)OO(-)) at the micellar interface to yield the corresponding cation C (MPS(+)OOH) that is stabilized in the negatively charged micelles and reacts much faster with MPS than Z to yield MPSO. The electron transfer reaction from (3)MPS* to O2 yielding MPS˙(+) and O2˙(-) is also enhanced in SDS micelles, as back electron transfer (BET) is prevented by ejection of O2˙(-) to the aqueous bulk phase and stabilization of MPS˙(+) in the anionic micelles. The size of the SDS micelles modulates the relative contribution of each pathway (formation of MPSO or MPS˙(+)) to the overall conversion of MPS to its oxidation products. Photooxidation of MPS in cationic micelles is a very slow process, as the formation of neither C nor MPS˙(+) is favoured in positively charged micelles.

Self sensitized photooxidation of N-methyl phenothiazine: acidity control of the competition between electron and energy transfer mechanisms.

The reaction pathways following electronic excitation of 10-methyl phenothiazine (MPS) in the presence of oxygen have been investigated as a contribution to establish the mechanisms involved in the phototoxic reactions related to phenothiazine drugs. In the context of previously published results, the pathways of oxidation via the radical cation and/or by reactive oxygen species, such as singlet oxygen and superoxide anion, are of particular interest. The effects of polarity of the medium as well as of proton donors on the different reaction pathways, in particular on the formation of reactive oxygen species and the intermediates of the oxidation of 10-methyl phenothiazine, have been investigated. No reaction was observed in non-polar solvents. In polar solvents, both self-sensitized and sensitized singlet oxygen generation lead to the oxidation of MPS and the production of 10-methyl phenothiazine sulfoxide (MPSO) most probably via a zwitterionic persulfoxide. During self-sensitized photooxidation of MPS in the presence of proton donors, such as carboxylic acids, the zwitterionic intermediate is protonated to the corresponding cation that in turn facilitates the reaction with a second molecule of MPS. In the presence of strong acids however, the formation of the radical cation of MPS and of the superoxide anion, by electron transfer from the triplet excited state of MPS to molecular oxygen, competes efficiently with singlet oxygen formation. In this case, the scavenging of the superoxide anion by protons to yield its conjugated acid (hydroperoxyl radical) and the subsequent disproportionation of the latter prevents back electron transfer.

Formation of hydrogen peroxide by VUV-photolysis of water and aqueous solutions with methanol.

The hydrogen peroxide production upon vacuum ultraviolet (VUV) irradiation of water is reviewed, because published results from the last 10 years lead to conflicting mechanistic interpretations. This work confirms that in pure water, hydrogen peroxide is only produced in the presence of molecular oxygen. Mechanistic schemes explain these findings and confirm earlier statements that recombination of hydroxyl radicals is kinetically disfavoured. In agreement with other recent publications, this work confirms that enhanced hydrogen peroxide production takes place upon VUV irradiation of aqueous solutions of organic compounds. For these investigations, methanol was chosen as an organic model compound. During photolyses, hydrogen peroxide, dissolved molecular oxygen, pH-value of the reaction system, methanol and its products of oxidative degradation were analyzed, and kinetic studies were undertaken to explain the evolution of the concentrations of these components.

Oxidation of polystyrene aerosols by VUV-photolysis and/or ozone.

Aerosols of submicron polystyrene particles were oxidized by either vacuum-ultraviolet (VUV) irradiation in the presence of molecular oxygen (O(2)) and/or by ozone (O(3)). Different degrees of oxidation and oxidative degradation were reached by VUV-photolysis depending on radiant energy, O(2) and H(2)O concentrations in the bulk gas mixture as well as on particle diameter. The same functionalization was obtained by exposing the aerosol to O(3), however, oxidation, in particular oxidative degradation, was less efficient. The evolution of hydroxyl and carbonyl functions introduced was quantified by ATR-FTIR spectroscopy of filtered particles, and oxidative degradation of the polymer particles was confirmed by determining size and number of aerosol particles before and after oxidation. Efficiency analyses are based on the results of an O(3) actinometry and on an evaluation of the rate of absorbed photons by the aerosol particles in function of their size.

Quenching of the fluorescence of aromatic pterins by deoxynucleotides.

Steady-state and time-resolved studies of the fluorescence of four aromatic unconjugated pterins (pterin (Ptr), 6-(hydroxymethyl)pterin (Hmp), 6-methylpterin (Mep), and 6,7-dimethylpterin (Dmp)) in aqueous solutions in the presence of different nucleotides (2'-deoxyguanosine 5'-monophosphate (dGMP), 2'-deoxyadenosine 5'-monophosphate (dAMP), and 2'-deoxycytosine 5'-monophosphate (dCMP)) have been performed using the single-photon counting technique. The singlet excited states of acid forms of pterins are deactivated by purine nucleotides (dGMP and dAMP) via a combination of dynamic and static processes. The efficiency of the dynamic quenching is high, independently of the nature of the purine base of the nucleotide and of the chemical structure of the substituents linked to the pterin moiety. Analysis of the static quenching indicates that ground-state association between pterins and purine nucleotides takes place, but the formation of the corresponding complexes is significant only at relatively high reactant concentrations. The quenching of the fluorescence of acid forms of pterin derivatives by dCMP, a pyrimidine nucleotide, is slightly less efficient than the quenching by purine nucleotides and is purely dynamic. In alkaline media, the fluorescence quenching is much less efficient than in acidic media, the deactivation by purine nucleotides being purely dynamic, whereas quenching by dCMP is negligible. Possible mechanisms for the quenching of fluorescence of pterin derivatives by the different nucleotides are discussed.

Photosensitization of 2'-deoxyadenosine-5'-monophosphate by pterin.

UV-A radiation (320-400 nm) induces damages to the DNA molecule and its components through photosensitized reactions. Pterins, heterocyclic compounds widespread in biological systems, participate in relevant biological processes and are able to act as photosensitizers. We have investigated the photosensitization of 2'-deoxyadenosine-5'-monophosphate (dAMP) by pterin (PT) in aqueous solution under UV-A radiation. The effect of pH was evaluated, the participation of oxygen was investigated and the products analyzed. Kinetic studies revealed that the reactivity of dAMP towards singlet oxygen (1O2) is very low and that this reactive oxygen species does not participate in the mechanism of photosensitization, although it is produced by PT upon UV-A excitation. In contrast, analysis of irradiated solutions by means of electrospray ionization mass spectrometry strongly suggested that 8-oxo-7,8-dihydro-2'-deoxyadenosine-5'-monophosphate (8-oxo-dAMP) was produced, indicating that the photosensitized oxidation takes place via a type I mechanism (electron transfer).

Mineralization of CCl4 by the UVC-photolysis of hydrogen peroxide in the presence of methanol.

A method for a photochemically induced mineralization of CCl4 is described in which use is made of reductive radicals. The UVC-photolysis (254 nm) of H2O2 added to aqueous solutions of CCl4 is leading to the homolysis of the oxidant yielding hydroxyl radicals (HO) that subsequently react with added methanol to generate hydroxymethyl radicals (CH2OH). The latter radicals initiate mineralization of CCl4 by reductive C-Cl bond splitting. CHCl3, C2Cl4 and C2Cl6 were found as reaction intermediates, but are quantitatively depleted in a parallel oxidative reaction manifold leading to mineralization. Carbon dioxide radical anion, CO2(-), an intermediate in the mineralization pathway of methanol, is also shown to initiate the mineralization of CCl4 by reductive dechlorination. A reaction mechanism is proposed and validated with computer simulations of all the experimental results.

Singlet oxygen (O2(1Deltag)) quenching by dihydropterins.

Pterins belong to a class of heterocyclic compounds present in a wide range of living systems. They participate in relevant biological functions and are involved in different photobiological processes. Dihydropterins are one of the biologically active forms of pterins. The photoinduced production and quenching of singlet oxygen (1O2) by a series of dihydropterins (7,8-dihydrobiopterin (DHBPT), 7,8-dihydroneopterin (DHNPT), 6-formyl-7,8-dihydropterin (FDHPT), sepiapterin (SPT), 7,8-dihydrofolic acid (DHFA), and 7,8-dihydroxanthopterin (DHXPT)) in aqueous solution at physiological pH ( approximately 7) were investigated, and the quantum yields of 1O2 production (PhiDelta) and rate constants of total quenching (kt) of 1O2 were determined. Studied compounds do not produce 1O2 under UV-A irradiation and are very efficient 1O2 quenchers. The chemical reactions between 1O2 and dihydropterin derivatives were investigated, and the corresponding rate constants (kr) were found to be particularly high. The oxidized pterin derivatives, biopterin (BPT), neopterin (NPT), 6-formylpterin (FPT), and folic acid (FA), were identified and quantified during the reaction of 1O2 with DHBPT, DHNPT, FDHPT, and DHFA, respectively. Besides the oxidation of the dihydropyrazine ring to yield the corresponding oxidized pterins, a second oxidation pathway, leading to fragmentation of the dihydropterin and formation of non-pterinic products, was identified. Mechanisms and biological implications are discussed.

Characterization of nanostructured surfaces generated by reconstitution of the porin MspA from Mycobacterium smegmatis.

Nanostructures with long-term stability at the surface of gold electrodes are generated by reconstituting the porin MspA from Mycobacterium smegmatis into a specially designed monolayer of long-chain lipid surfactant on gold. Tailored surface coverage of gold electrodes with long-chain surfactants is achieved by electrochemically assisted deposition of organic thiosulfates (Bunte salts). The subsequent reconstitution of the octameric-pore MspA is guided by its extraordinary self-assembling properties. Importantly, electrochemical reduction of copper(II) yields copper nanoparticles within the MspA nanopores. Electrochemical impedance spectroscopy, reflection electron microscopy, and atomic force microscopy (AFM) show that: 1) the MspA pores within the self-assembled monolayer (SAM) are monodisperse and electrochemically active, 2) MspA reconstitutes in SAMs and with a 10-nm thickness, 3) AFM is a suitable method to detect pores within SAMs, and 4) the electrochemical reduction of Cu2+ to Cu0 under overpotential conditions starts within the MspA pores.

Reactivity of conjugated and unconjugated pterins with singlet oxygen (O2(1Deltag)): physical quenching and chemical reaction.

Pterins (PTs) belong to a class of heterocyclic compounds present in a wide range of living systems. They participate in relevant biological functions and are involved in different photobiological processes. We have investigated the reactivity of conjugated PTs (folic acid [FA], 10-methylfolic acid [MFA], pteroic acid [PA]) and unconjugated PTs (PT, 6-hydroxymethylpterin [HPT], 6-methylpterin [MPT], 6,7-dimethylpterin [DPT], rhamnopterin [RPT]) with singlet oxygen (1O2) in aqueous solutions, and compared the efficiencies of chemical reaction and physical quenching. The chemical reactions between 1O2, produced by photosensitization, and PT derivatives were followed by UV-visible spectrophotometry and high-performance liquid chromatography, and corresponding rate constants (k(r)) were evaluated. Whenever possible, products were identified and quantified. Rate constants of 1O2 total quenching by the PT derivatives investigated were obtained from steady-state 1O2 luminescence measurements. Results show that the behavior of conjugated PTs differs considerably from that of unconjugated derivatives, and the mechanisms of 1O2 physical quenching by these compounds and of their chemical reaction with 1O2 are discussed in relation to their structural features.

Myoglobin modified electrodes as anchors for d metal cationic complexes.

The capability of adsorption of different electroactive cationic Re(V)-amine complexes onto myoglobin-containing electrodes has been investigated. The goal of this work was the development of an Au/thiol/myo electrode and, after incubation of such ensemble in the presence of three different Re(V)-amine complexes, the evaluation of the extent of surface coverage by the complexes (as a way to evaluate the interaction complex-protein) using electrochemical techniques. Our results showed that a protein-containing electrode could therefore be used for the detection of the interaction of small electroactive cationic complexes and the biomolecule. The extent of the coverage of the myoglobin electrode by the complex depends on the number of free tails from the ligands and the total charge of the complex.

Vacuum-ultraviolet photochemically initiated modification of polystyrene surfaces: morphological changes and mechanistic investigations.

Vacuum-ultraviolet (VUV) irradiation (lambda(exc): 172 +/- 12 nm) of polystyrene films in the presence of oxygen produced not only oxidatively functionalized surfaces, but generated also morphological changes. Whereas OH- and C=O-functionalized surfaces might be used for e.g. secondary functionalization, enhanced aggregation or printing, processes leading to morphological changes open new possibilities of microstructurization. Series of experiments made under different experimental conditions brought evidence of two different reaction pathways: introduction of OH- and C=O-groups at the polystyrene pathways is mainly due to the reaction of reactive oxygen species (hydroxyl radicals, atomic oxygen, ozone) produced in the gas phase between the VUV-radiation source and the substrate. However, oxidative fragmentation leading to morphological changes, oxidation products of low molecular weight and eventually to mineralization of the organic substrate is initiated by electronic excitation of the polymer leading to C-C-bond homolysis and to a complex oxidation manifold after trapping of the C-centred radicals by molecular oxygen. The pathways of oxidative functionalization or fragmentation could be differentiated by FTIR-ATR analysis of irradiated polystyrene surfaces before and after washing with acetonitrile and microscopic fluorescence analysis of the surfaces secondarily functionalized with the N,N,N-tridodecyl-triaza-triangulenium (TATA) cation. Ozonization of the polystyrene leads to oxidative functionalization of the polymer surface but cannot initiate the fragmentation of the polymer backbone. Oxidative fragmentation is initiated by electronic excitation of the polymer (contact-mode AFM analysis), and evidence of the generation of intermediate C-centred radicals is given e.g. by experiments in the absence of oxygen leading to cross-linking (solubility effects, optical microscopy, friction-mode AFM) and disproportionation (fluorescence).

Substituent effects on the photophysical properties of pterin derivatives in acidic and alkaline aqueous solutions.

Pterins are heterocyclic compounds with important biological functions, and most of them may exist in two acid-base forms in the pH range between 3 and 13 in aqueous solution. In this work, the photophysical properties of acid and basic forms of six compounds of the pterin family (6-hydroxymethylpterin [HPT], 6-methylpterin [MPT], 6,7-dimethylpterin [DPT], rhamnopterin [RPT], N-methylfolic acid [MFA], and pteroic acid [PA]) have been studied. The effects of the chemical nature of the substituents at position 6 of the pterin moiety and the effects of the pH on the absorption and emission properties are analyzed. The fluorescence characteristics (spectra, quantum yields, lifetimes) of these compounds have been investigated using the single-photon-counting technique. Results obtained for pterin derivatives containing small substituents with 1 carbon atom (HPT, MPT, DPT) and short hydrocarbon chain (4 carbon atoms) (RPT) are different from those found for pterin derivatives containing a p-aminobenzoic acid (PABA) moiety in the substituent (MFA and PA). Fluorescence quantum yields (Phi(F)) of the first group of compounds are relatively high (>/=0.4), whereas MFA and PA exhibit very small Phi(F) values (

157 nm pellicles (thin films) for photolithography: mechanistic investigation of the VUV and UV-C photolysis of fluorocarbons.

The use of 157 nm as the next lower wavelength for photolithography for the production of semiconductors has created a need for transparent and radiation-durable polymers for use in soft pellicles, the polymer films which protect the chip from particle deposition. The most promising materials for pellicles are fluorinated polymers, but currently available fluorinated polymers undergo photodegradation and/or photodarkening upon long term exposure to 157 nm irradiation. To understand the mechanism of the photodegradation and photodarkening of fluorinated polymers, mechanistic studies on the photolysis of liquid model fluorocarbons, including perfluorobutylethyl ether and perfluoro-2H-3-oxa-heptane, were performed employing UV, NMR, FTIR, GC, and GC/MS analyses. All hydrogen-containing compounds showed decreased photostability compared to the fully perfluorinated compounds. Irradiation in the presence of atmospheric oxygen showed reduced photostability compared to deoxygenated samples. Photolysis of the samples was performed at 157, 172, 185, and 254 nm and showed only minor wavelength dependence. Mechanisms for photodegradation of the fluorocarbons are proposed, which involve Rydberg excited states. Time-dependent density functional theory has been used to predict the excitation spectra of model compounds.

Vacuum-ultraviolet photochemically initiated modification of polystyrene surfaces: chemical changes.

Fourier-Transform infrared (FTIR) spectroscopy and surface energy analysis (contact angle measurements) have been performed as a means of identification and quantification of the functionalization of polystyrene surfaces upon vacuum ultraviolet- (VUV-) photochemically initiated oxidation. Photochemical oxidation was performed in the presence of water vapor and molecular oxygen using a pulsed Xe2-excimer radiation source (lambda(exc): 172 nm). Surface oxidation was studied as a function of two parameters: irradiation time and distance between sample and radiation source. During the first 1-2 min of irradiation, an increase of the concentrations of hydroxyl (OH) and carbonyl (C=O) groups on the surface was observed, both reaching limiting values. As expected, the rate of oxidation diminished exponentially with increasing distance between the radiation source and the surface of the polystyrene film. Changes in the surface energy due to the introduction of these polar (i.e. OH and C=O) groups were also determined. The densities of the functional groups decreased upon washing with acetonitrile, and analysis of the washing solution by means of gas chromatography-mass spectrometry (GC-MS) revealed the presence of a large number of products. The application of pulsed Xe2-excimer radiation sources as a valuable alternative to conventional means (i.e. laser and plasma) for the photochemical oxidation and surface modification of polystyrene is discussed.

Oxidative degradation of 2,4-xylidine by photosensitization with 2,4,6-triphenylpyrylium: homogeneous and heterogeneous catalysis.

The possibility of using zeolites containing the 2,4,6-triphenylpyrylium cation as photocatalysts for the degradation of pollutants has been tested on aqueous xylidine (2,4-dimethylaniline) solutions as models for contaminated wastewaters. The influence of the photocatalyst and substrate concentrations on xylidine oxidation has been investigated in homogeneous solution, by performing a series of experiments chosen according to the experimental design methodology (Doehlert uniform array). The empirical models and the corresponding response surfaces obtained from data analysis have been used for simulating and predicting degradation efficiency. The results have shown that conversion increases with increasing amounts of photocatalyst and decreasing concentration of the model pollutant. The fluorescence of 2,4,6-triphenylpyrylium was quenched by xylidine with a rate constant k(q) of 3.1x10(9)M(-1)s(-1). This result suggests a direct electron transfer between the excited pyrylium salt and xylidine. Because of the limited stability of the photocatalyst in homogeneous media, a pyrylium containing Y-zeolite has been tested for the photocatalytic oxidation of xylidine under heterogeneous conditions. The results suggest that the supported catalyst has a much improved stability and that xylidine oxidation rates remain nearly constant during the whole reaction time. An additional advantage of the pyrylium containing zeolite photocatalyst is that it can be recycled and used for further experiments.

Quenching of the fluorescence of pterin derivatives by anions.

Steady-state and time-resolved studies of the fluorescence of pterins in aqueous solutions in the presence of different anions have been performed using the single-photon counting technique. In the pH range between 3 and 13, most pterins exist in a protonated and a deprotonated form. Results obtained for both acid and basic forms of five compounds belonging to the pterin family (pterin, 6-carboxypterin, 6-formylpterin, biopterin and neopterin) show that the fluorescence of the acid forms is dynamically quenched by phosphate and acetate, and the corresponding bimolecular rate constants of fluorescence quenching (k(q)) are reported. These results are of importance from the technical and analytical points of view because measurements of the fluorescence of pterin derivatives for a variety of purposes are often performed in the presence of salts, especially buffers, and significant quenching of the pterin fluorescence by the buffer might lead to errors in interpretation and erroneous conclusions. No quenching of the fluorescence of the acid forms by chloride, sulfate or nitrate was detected. The fluorescence of the basic forms was either not quenched by anions or any such quenching was negligible in comparison with that observed for the acid forms.