Exploring the effects of dietary inulin in rainbow trout fed a high-starch, 100% plant-based diet.

BACKGROUND: High dietary carbohydrates can spare protein in rainbow trout (Oncorhynchus mykiss) but may affect growth and health. Inulin, a prebiotic, could have nutritional and metabolic effects, along with anti-inflammatory properties in teleosts, improving growth and welfare. We tested this hypothesis in rainbow trout by feeding them a 100% plant-based diet, which is a viable alternative to fishmeal and fish oil in aquaculture feeds. In a two-factor design, we examined the impact of inulin (2%) as well as the variation in the carbohydrates (CHO)/plant protein ratio on rainbow trout. We assessed the influence of these factors on zootechnical parameters, plasma metabolites, gut microbiota, production of short-chain fatty acids and lactic acid, as well as the expression of free-fatty acid receptor genes in the mid-intestine, intermediary liver metabolism, and immune markers in a 12-week feeding trial. RESULTS: The use of 2% inulin did not significantly change the fish intestinal microbiota, but interestingly, the high CHO/protein ratio group showed a change in intestinal microbiota and in particular the beta diversity, with 21 bacterial genera affected, including Ralstonia, Bacillus, and 11 lactic-acid producing bacteria. There were higher levels of butyric, and valeric acid in groups fed with high CHO/protein diet but not with inulin. The high CHO/protein group showed a decrease in the expression of pro-inflammatory cytokines (il1b, il8, and tnfa) in liver and a lower expression of the genes coding for tight-junction proteins in mid-intestine (tjp1a and tjp3). However, the 2% inulin did not modify the expression of plasma immune markers. Finally, inulin induced a negative effect on rainbow trout growth performance irrespective of the dietary carbohydrates. CONCLUSIONS: With a 100% plant-based diet, inclusion of high levels of carbohydrates could be a promising way for fish nutrition in aquaculture through a protein sparing effect whereas the supplementation of 2% inulin does not appear to improve the use of CHO when combined with a 100% plant-based diet.

Authenticating teas using multielement signatures, strontium isotope ratios, and volatile compound profiling.

High value food products are subject to adulterations and frauds. This study aimed to combine, in our knowledge for the first time, inorganic chemical tracers (multi-elements and Sr isotopy) with volatile organic compound (VOCs) to discriminate the geographic origin, the varieties and transformation processes to authenticate 26 tea samples. By measuring Sr isotope ratio using the multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), 6 out of 11 regions were successfully discriminated. The combination with the ICP-MS inorganic pattern allowed to discriminate 4 more regions with a significance level of 0.05. VOCs fingerprints, obtained with selected ion flow tube mass spectrometer (SIFT-MS), were not correlated with origin but with the cultivar and transformation processes. Green, oolong, and dark teas were clearly differentiated, with hexanal and hexanol contributing to the discrimination of oxidation levels. With this multi-instrumental approach, it is possible to certify the geographical origin and the tea conformity.

Influence of oxygen, UV light and reactive dissolved organic matter on the photodemethylation and photoreduction of monomethylmercury in model freshwater.

The key factors which affect the abiotic photodemethylation process of monomethylmercury (MMHg) in the freshwaters has remained unclear. Hence, this work aimed to better elucidate the abiotic photodemethylation pathway in a model freshwater. Anoxic and oxic conditions were implemented to investigate the simultaneous photodemethylation to Hg(II) and photoreduction to Hg(0). MMHg freshwater solution was irradiated through exposure to three wavelength ranges of full light (280-800 nm), without short UVB (305-800 nm), and visible light (400-800 nm). The kinetic experiments were performed following dissolved and gaseous Hg species concentrations (i.e., MMHg, iHg(II), Hg(0)). A comparison between two methods of post-irradiation purging and continuous-irradiation purging confirmed MMHg photodecomposition to Hg(0) is mainly induced by a first photodemethylation step to iHg(II) followed by a photoreduction step to Hg(0). Photodemethylation under full light extent normalized to absorbed radiation energy showed a higher rate constant in anoxic conditions at 18.0 ± 2.2 kJ-1 compared to oxic conditions at 4.5 ± 0.4 kJ-1. Moreover, photoreduction also increased up to four-fold under anoxic conditions. Normalized and wavelength-specific photodemethylation (Kpd) and photoreduction (Kpr) rate constants were also calculated for natural sunlight conditions to evaluate the role of each wavelength range. The relative ratio in wavelength-specific KPAR: Klong UVB+ UVA: K short UVB showed higher dependence on UV light for photoreduction at least ten-fold compared to photodemethylation, regardless of redox conditions. Both results using Reactive Oxygen Species (ROS) scavenging methods and Volatile Organic Compounds (VOC) measurements revealed the occurrence and production of low molecular weight (LMW) organic compounds that are as photoreactive intermediates responsible for MMHg photodemethylation and iHg(II) photoreduction in the dominant pathway. This study also supports the role of dissolved oxygen as an inhibitor for the photodemethylation pathways driven by LMW photosensitizers.

TiO2-SiO2 Self-Standing Materials bearing Hierarchical Porosity: MUB-200(x) Series toward 3D-Efficient VOC Photoabatement Properties.

Three-dimensional photoactive self-standing porous materials have been synthesized through the integration of soft chemistry and colloids (emulsions, lyotrope mesophases, and P25 titania nanoparticles). Final multiscale porous ceramics bear 700-1000 m2 g-1 of micromesoporosity depending on the P25 nanoparticle contents. The applied thermal treatment does not affect the P25 anatase/rutile allotropic phase ratio. Photonic investigations correlated with the foams' morphologies suggest that the larger amount of TiO2 that is introduced, the larger the walls' density and the smaller the mean size of the void macroscopic diameters, with both effects inducing a reduction of the photon transport mean free path (lt) with the P25 content increase. A light penetration depth in the range of 6 mm is reached, thus depicting real 3D photonic scavenger behavior. The 3D photocatalytic properties of the MUB-200(x) series, studied in a dynamic "flow-through" configuration, show that the highest photoactivity (concentration of acetone ablated and concentration of CO2 formed) is obtained with the highest monolith height (volume) while providing an average of 75% mineralization. These experimental results validate the fact that these materials, bearing 3D photoactivity, are paving the path for air purification operating with self-standing porous monolith-type materials, which are much easier to handle than powders. As such, the photocatalytic systems can now be advantageously miniaturized, thereby offering indoor air treatment within vehicles/homes while drastically limiting the associated encumbrance. This volumetric counterintuitive acting mode for light-induced reactions may find other relevant advanced applications for photoinduced water splitting, solar fuel, and dye-sensitized solar cells while both optimizing photon scavenging and opening the path for the miniaturization of the processes where encumbrance or a foot-print penalty would be advantageously circumvented.

Interaction between genetics and inulin affects host metabolism in rainbow trout fed a sustainable all plant-based diet.

Inulin affects nutrition and metabolism in many animals. Although inulin is widely used in the diet of teleosts, its mechanism of action is unknown. Here, we investigated the effect of inulin (2 %) on the intestinal microbiome and metabolism in rainbow trout (Oncorhynchus mykiss) selected for growth and survival when fed a 100 % plant-based diet (suave) and a control line (temoin). Metabolic responses to the two factors (line and inulin) in liver, intestine, muscle and adipose were tissue-specific, with line and interaction between the two factors influencing overall expression in liver. In the intestine, inulin and line and in muscle, line influenced the expression of metabolic genes. Microbiota between the mucus and digestive contents was significantly different, with genera from Proteobacteria being more abundant in the mucus, whereas genera from the Firmicutes and Planctomycetes being more abundant in contents. Effect of inulin and interaction between factors on the microbiome was evident in contents. The significant taxa of control and inulin-fed groups differed greatly with Streptococcus and Weissella being significantly abundant in the inulin-fed group. There was a general trend showing higher levels of all SCFA in temoin group with propionic acid levels being significantly higher. An operational taxonomic unit (OTU) belonging to the Ruminococcaceae was significantly abundant in suave. The tissue-specific correlations between OTU and gene expression may indicate the link between microbiome and metabolism. Together, these results suggest that line and inulin impact the gene expression in a tissue-specific manner, possibly driven by specific OTUs enriched in inulin-fed groups and suave.

Study of the Chemical Ionization of Organophosphate Esters in Air Using Selected Ion Flow Tube-Mass Spectrometry for Direct Analysis.

Organophosphate esters are an emerging environmental concern since they spread persistently across all environmental compartments (air, soil, water, etc.). Measurements of semivolatile organic compounds are important but not without challenges due to their physicochemical properties. Selected ion flow tube-mass spectrometry (SIFT-MS) can be relevant for their analysis in air because it is a direct analytical method without separation that requires little preparation and no external calibration. SIFT-MS is based on the chemical reactivity of analytes with reactant ions. For volatile and semivolatile organic compound analysis in the gas phase, knowledge of ion-molecule reactions and kinetic parameters is essential for the utilization of this technology. In the present work, we focused on organophosphate esters, semivolatile compounds that are now ubiquitous in the environment. The ion-molecule reactions of eight precursor ions that are available in SIFT-MS (H3O+, NO+, O2•+, OH-, O•-, O2•-, NO2-, and NO3-) with six organophosphate esters were investigated. The modeling of ion-molecule reaction pathways by calculations supported and complemented the experimental work. Organophosphate esters reacted with six of the eight precursor ions with characteristic reaction mechanisms, such as protonation with hydronium precursor ions and association with NO+ ions, while nucleophilic substitution occurred with OH-, O•-, and O2•-. No reaction was observed with NO2- and NO3- ions. This work shows that the direct analysis of semivolatile organic compounds is feasible using SIFT-MS with both positive and negative ionization modes.

Volatile fingerprint of food products with untargeted SIFT-MS data coupled with mixOmics methods for profile discrimination: Application case on cheese.

Volatile organic compounds (VOCs) emitted by food products are decisive for the perception of aroma and taste. The analysis of gaseous matrices is traditionally done by detection and quantification of few dozens of characteristic markers. Emerging direct injection mass spectrometry technologies offer rapid analysis based on a soft ionisation of VOCs without previous separation. The recent increase of selectivity offered by the use of several precursor ions coupled with untargeted analysis increases the potential power of these instruments. However, the analysis of complex gaseous matrix results in a large number of ion conflicts, making the quantification of markers difficult, and in a large volume of data. In this work, we present the exploitation of untargeted SIFT-MS volatile fingerprints of ewe PDO cheeses in a real farm model, using mixOmics methods allowing us to illustrate the typicality, the manufacturing processes reproducibility and the impact of the animals' diet on the final product.

FerrateVI oxidation of polycyclic aromatic compounds (PAHs and polar PACs) on DNAPL-spiked sand: degradation efficiency and oxygenated by-product formation compared to conventional oxidants.

In situ chemical oxidations are known to remediate PAH contaminations in groundwater and soils. In this study, batch-scale oxidations aim to compare the PAC (polycyclic aromatic compound) degradation of three oxidation processes traditionally applied for soil treatment: permanganate, heat-activated persulfate (60 °C) and Fenton-like activated by magnetite, to results obtained with ferrates (FeVI). Widely studied for water treatments, ferrates are efficient on a wide range of pollutants with the advantage of producing nontoxic ferric sludge after reaction. However, fewer works focus on their action on soil, especially on semi-industrial grade ferrates (compatible with field application). Oxidations were carried out on sand spiked with dense non-aqueous phase liquid (DNAPL) sampled in the groundwater of a former coking plant. Conventional 16 US-EPA PAHs and polar PACs were monitored, especially potential oxygenated by-products that can be more harmful than parent-PAHs. After seven reaction days, only the Fenton-like showed limited degradation. Highest efficiencies were obtained for heat-activated persulfate with no O-PAC ketones formed. Permanganate gave important degradation, but ketones were generated in large amount. The tested ferrates not only gave slightly lower yields due to their auto-decomposition but also induced O-PAC ketone production, suggesting a reactional pathway dominated by oxidoreductive electron transfer, rather than a radical one.

Direct analysis of aldehydes and carboxylic acids in the gas phase by negative ionization selected ion flow tube mass spectrometry: Quantification and modelling of ion-molecule reactions.

RATIONALE: The concentrations of aldehydes and volatile fatty acids have to be controlled because of their potential harmfulness in indoor air or relationship with the organoleptic properties of agri-food products. Although several specific analytical methods are currently used, the simultaneous analysis of these compounds in a complex matrix remains a challenge. The combination of positive and negative ionization selected ion flow tube mass spectrometry (SIFT-MS) allows the accurate, sensitive and high-frequency analysis of complex gas mixtures of these compounds. METHODS: The ion-molecule reactions of negative precursor ions (OH- , O•- , O2 •- , NO2 - and NO3 - ) with five aldehydes and four carboxylic acids were investigated in order to provide product ions and rate constants for the quantification of these compounds by negative ion SIFT-MS. The results were compared with those obtained by conventional analysis methods and/or with already implemented SIFT-MS positive ionization methods. The modelling of hydroxide ion (OH- )/molecule reaction paths by ab-initio calculation allowed a better understanding of these gas-phase reactions. RESULTS: Deprotonation systematically occurs by reaction between negative ions and aldehydes or acids, leading to the formation of [M - H]- primary ions. Ab-initio calculations demonstrated the α-CH deprotonation of aldehydes and the acidic proton abstraction for fatty acids. For aldehydes, the presence of water in the flow tube leads to the formation of hydrated ions, [M - H]- .H2 O. With the NO2 - precursor ion, a second reaction channel results in ion-molecule association with the formation of M.NO2 - ions. CONCLUSIONS: Except for formaldehyde, all the studied compounds can be quantified by negative ion SIFT-MS with significant rate constants. In addition to positive ion SIFT-MS with H3 O+ , O2 + and NO+ precursor ions, negative ionization with O•- , O2 •- , OH- , NO2 - and NO3 - extends the range of analysis of aldehydes and carboxylic acids in air without a preparation or separation step. This methodology was illustrated by the simultaneous quantification in single-scan experiments of seven aldehydes and six carboxylic acids released by building materials.

Mechanism for the oxidation of phenol by sulfatoferrate(VI): Comparison with various oxidants.

The oxidative action of a solid and stable potassium sulfatoferrate(VI) material on phenol was studied in aqueous solution under different stoichiometries. The performance towards phenol and the total organic carbon is compared to that of potassium permanganate and calcium hypochlorite. The total mineralization of phenol is not completely achieved by the studied chemical oxidants, and some oxidation products have been identified by gas chromatography-mass spectrometry and gas chromatography-flame ionization detector analysis. A radical reaction pathway, involving the formation of oxidation intermediates or by-products such as benzoquinone, phenoxyphenol and ring opening products, is proposed for the decomposition of phenol by ferrate(VI). Phenoxyphenol is also involved in the oxidation mechanism for permanganate whereas chlorinated phenols are produced by hypochlorite. The role of the chloride anion impurity of the potassium sulfatoferrate(VI) material has been highlighted in this study; no negative impact on the removal of phenol and its mineralization is observed compared to the use of a pure commercial ferrate(VI). The efficiency of sulfatoferrate(VI) for the oxidative removal of phenol from industrial wastewater is also confirmed.

Immobilized organic photosensitizers with versatile reactivity for various visible-light applications.

Various photosensitizers were grafted by conventional peptide coupling methods to functionalized silica with several macroscopic shapes (powders, films) or embedded in highly transparent and microporous silica xerogel monoliths. Owing to the transparency and free-standing shape of the monoliths, the transient species arising from irradiation of the PSs could be analyzed and were not strikingly different from those observed in solutions. The observed reactivity for either liquid-solid (α-terpinene oxygenation vs dehydrogenation) or gas-solid (dimethylsulfide, DMS, solvent-free oxidation) reactions was consistent with the properties of the excited states of the PSs under consideration. Immobilized anthraquinone-derived materials preferentially react in both cases by electron transfer from the substrate to the triplet state of the sensitizer, in spite of an efficient singlet oxygen production. The recently developed 9,14-dicyanobenzo[b]triphenylene-3-carboxylic acid, DBTP-COOH, efficiently reacts via energy transfer to yield singlet oxygen from its triplet state. It was shown to perform better than 9,10-dicyanoanthracene and rose bengal for DMS oxidation and α-terpinene photooxygenation to ascaridole, respectively. Thus, by a proper choice of the organic immobilized photocatalyst, it is possible to develop efficient and reusable materials, activated under visible light, for various applications and to tune the reaction pathway, opening the way to green oxidation processes.

Transparent organosilica photocatalysts activated by visible light: photophysical and oxidative properties at the gas-solid interface.

The photophysical properties of several photosensitizers (PSs) included or grafted in silica monoliths were compared to their properties in solution. The effects of the solid support on their steady-state and transient absorption spectra, on their quantum yields of singlet oxygen ((1)O2) production, and on their ability to photoinduce the oxidation of dimethylsulfide (DMS) were investigated. Two cyanoanthracene derivatives (9,14-dicyanobenzo[b]triphenylene, DBTP, and 9,10-dicyanoanthracene, DCA), as well as three phenothiazine dyes (methylene blue, MB(+), new methylene blue, NMB(+), methylene violet, MV), were encapsulated in silica, analyzed and compared to two reference PSs (perinaphthenone, PN and rose bengal, RB). A DBTP derivative (3-[N-(N″-triethoxysilylpropyl-N'-hexylurea)]carboxamido-9,14-dicyanobenzo[b]triphenylene, 3) was also prepared and grafted onto silica. Thanks to the transparency and the free-standing shape of the monoliths, the complete spectroscopic characterization of the supported PSs was carried out directly at the gas-solid interface. The influence of the silica network, the PS, and the adsorption/grafting link between the PS and silica was investigated. The effects of PS concentration, gaseous atmosphere, humidity, and hydrophobicity on the production of (1)O2 were analyzed. With all PSs, (1)O2 production was very efficient (quantum yields of (1)O2 production, relative to PN, between 0.6 and 1), and this species was the only one involved in the pollutant photooxidation. The influence of the matrix on the PSs' photophysics could be considered as negligible. In contrast, the matrix effect on DMS photooxidation was extremely important: the gas diffusion inside the porous structure, and thus, the photoactivity of the materials, strictly depended on silica's surface area and porosity. Our results highlight the suitability of these silica structures as inert supports for the study of the photosensitizing properties at the gas-solid interface. Moreover, thanks to the adsorption properties of the matrix, the synthesized materials can be used as microphotoreactor for the (1)O2-mediated oxidation of volatile pollutants.

Efficient cyanoaromatic photosensitizers for singlet oxygen production: synthesis and characterization of the transient reactive species.

In order to graft cyanoaromatic molecules onto various inert supports, we designed two new cyanoanthracene derivatives of benzo[b]triphenylene-9,14-dicarbonitrile (DBTP, 1), which already demonstrated good photosensitizing properties. We synthesized 3-(N-hydroxypropyl)carboxamido-9,14-dicyanobenzo[b]triphenylene, 3 and 3-(N-N0-Boc-aminohexyl)carboxamido-9,14-dicyanobenzo[b]triphenylene, 4 and compared their photophysical properties in acetonitrile relative to those of the parent compound 1 and its carboxylic derivative 9,14-dicyanobenzo[b]triphenylene-3-carboxylic acid, 2. The transient species were analysed and the quantum yields of singlet oxygen production (ΦΔ) determined in acetonitrile. The effect of chemical functionalization can be considered negligible, since absorption spectra, fluorescence emission spectra and fluorescence lifetimes do not significantly change with the substituent. The triplet-triplet absorption spectra and the triplet excited state lifetimes are similar for the whole series. For compounds 1-4 high values of ΦΔ, close to that of the standard sensitizer 1H-phenalen-1-one (PN, ΦΔ ≈ 1), and higher than that of the well-known photosensitizer 9,10-dicyanoanthracene (DCA), are due to very efficient intersystem crossing from the singlet to the triplet excited state and subsequent energy transfer to ground state oxygen ((3)O2). They belong to a class of very efficient photosensitizers, absorbing visible light and stable under irradiation, they may be functionalized without significant changes to their photophysical behaviour, and grafted onto various supports.

Selective oxidation with nanoporous silica supported sensitizers: an environment friendly process using air and visible light.

Transparent and porous silica xerogels containing various grafted photosensitizers (PSs) such as anthraquinone derivatives, Neutral Red, Acridine Yellow and a laboratory-made dicyano aromatics (DBTP) were prepared. In most cases, the xerogels were shown to be mainly microporous by porosimetry. The PSs were characterized in the powdered monoliths (form, aggregation, concentration) by electronic spectroscopy which also proved to be a useful tool for monitoring the material evolution after irradiation. These nanoporous xerogels were used as microreactors for gas/solid solvent-free photo-oxygenation of dimethylsulfide (DMS) using visible light and air as the sole reactant. All these PSs containing monoliths were efficient for gas-solid DMS oxidation, leading to sulfoxide and sulfone in varying ratios. As these polar oxidation products remained strongly adsorbed on the silica matrix, the gaseous flow at the outlet of the reactor was totally free of sulfide and odorless. The best results in term of yield and initial rate of degradation of DMS were obtained with DBTP containing xerogels. Moreover, as these materials were reusable without loss of efficiency and sensitizer photobleaching after a washing regeneration step, the concept of recyclable sensitizing materials was approved, opening the way to green process.

A new cyanoaromatic photosensitizer vs. 9,10-dicyanoanthracene: systematic comparison of the photophysical properties.

The cyanoanthracene derivative, benzo[b]triphenylene-9,14-dicarbonitrile (1) can be prepared readily with a graftable function while maintaining (1)O(2) photosensitizing properties comparable to those of the standard compound 9,10-dicyanoanthracene (DCA). In view of the high potential of the derivatives of 1 for photooxidation reactions under heterogeneous conditions, we compared the photophysical properties of 1 in solution with those of DCA. In pursuing the comparison of 1 and DCA, we observed small but significant changes of the vibronic bands in the electronic absorption spectra of DCA in different solvents, which were well correlated with solvent polarity, similar to the pyrene polarity scale. The main difference between 1 and DCA is in the emission properties: we observed a much stronger sensitivity of the fluorescence emission spectrum to the electron-donating ability of the solvent than for DCA. The emission spectrum of 1 is in general structureless with a large Stokes shift. The ability of the singlet state of 1 to participate in charge transfer interactions with electron-donating solvents is proposed to account for these results. It makes 1 a highly sensitive probe to the surrounding medium. Reversible reduction was observed for both photosensitizers, with a small shift to more negative potentials for 1 compared to DCA. The reduction potential of the first singlet excited state is of the same order of magnitude in both cases. Several photo-oxidation reactions sensitized by 1 and DCA are compared in homogeneous solution and at the gas-solid interface by embedding 1 and DCA in silica monoliths. Our results confirmed the dual character of both cyanoanthracene derivatives as electron transfer and energy transfer sensitizers, highly efficient for singlet oxygen production.

Solvent-free production of singlet oxygen at the gas-solid interface: visible light activated organic-inorganic hybrid microreactors including new cyanoaromatic photosensitizers.

We synthesized new cyanoaromatics, benzo[b]triphenylene-9,14-dicarbonitrile (DBTP) 1a and a graftable derivative, 9,14-dicyanobenzo[b]triphenylene-3-carboxylic acid (DBTP-COOH) 1b, easily prepared from commercial reagents. Their photosensitizing properties were investigated. Hybrid porous silica monoliths loaded with encapsulated 1a or grafted 1b were prepared, and their adsorption, spectroscopic and photosensitizing properties, as well as stability, were compared. Solvent-free, efficient oxidation of dimethylsulfide (DMS) was observed at the gas-solid interface under visible light irradiation. Quantum yields of formation of 1O2 inside the porous monoliths are comparable to those of phenalenone. Singlet oxygen lifetimes (approximately 25 micros) were found to be longer in silica monoliths than in usual polar solvents such as methanol or ethanol. This new class of hybrid materials work as porous, transparent, and highly efficient microreactors for oxidation reactions under visible light.

Hybrid functional mesostructured thin films with photo-oxidative properties in the visible range.

Hybrid mesostructured thin films functionalised with organic photosensitiser molecules demonstrated high efficiency for the decontamination of polluted atmosphere via singlet oxygen production.

Singlet oxygen in microporous silica xerogel: quantum yield and oxidation at the gas-solid interface.

The quantum yields of singlet oxygen ((1)O(2)) production (Phi(Delta)) and (1)O(2) lifetimes (tau(Delta)) at the gas-solid interface in silica gel material are determined. Different photosensitizers (PS) are encapsulated in parallelepipedic xerogel monoliths (PS-SG). PS were chosen according to their known photooxidation properties: 9,10-dicyanoanthracene (DCA), 9,10-anthraquinone (ANT), and a benzophenone derivative, 4-benzoyl benzoic acid (4BB). These experiments are mainly based on time-resolved (1)O(2) phosphorescence detection, and the obtained Phi(Delta) and tau(Delta) values are compared with those of a reference sensitizer for (1)O(2) production, 1H-phenalen-1-one (PN), included in the same xerogel. The trend between their ability to oxidize organic pollutants in the gas phase and their efficiency for (1)O(2) production is investigated through photooxidation experiments of a test pollutant dimethylsulfide (DMS). The Phi(Delta) value is high for DCA-SG relative to the PN reference, whereas it is slightly lower for 4BB-SG and for ANT-SG. Phi(Delta) is related to the production of sulfoxide and sulfone as the main oxidation products for DMS photosensitized oxidation. Additional mechanisms, leading to C--S bond cleaveage, appear to mainly occur for the less efficient singlet oxygen sensitizers 4BB-SG and ANT-SG.

Photo-oxidation of di-n-butylsulfide by various electron transfer sensitizers in oxygenated acetonitrile.

The selective activation of different photosensitizers has been carried out under comparable conditions and their efficiency towards di-n-butylsulfide oxidation in oxygenated acetonitrile compared from the product distribution after 150 minutes of irradiation. As expected, the best selectivity towards sulfoxide is obtained with a conventional energy transfer sensitizer such as Rose Bengal (RB), but also with a quinone with a low-lying triplet state, 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil or CHLO) and with 9,10-dicyanoanthracene (DCA). More significant yields in sulfonic and sulfuric acids are obtained under sensitization with 9,10-anthraquinone (ANT) or a derivative of benzophenone, 4-benzoyl benzoic acid (4-BB), with which additional experiments were carried out in order to discuss the involvement of either singlet oxygen or superoxide radical anion. Triphenyl pyrylium tetrafluoroborate (TPT+) is inefficient under the selected conditions and sulfide photo-oxidation can only be achieved with higher TPT+ concentrations with simultaneous total TPT+ bleaching. With TPT+, 1,2,4,5-tetracyanobenzene (TCNB) and TiO2, the product distribution and the low selectivity as well as the formation of numerous common by-products are indicative of radical mechanisms. All these results are discussed according to the possible formation of activated oxygen species, such as singlet oxygen, superoxide radical anion or alkylperoxy radicals.