Christian Mertz

Light- induced electron transfer and ATP synthesis in a carotene synthesizing insect

A singular adaptive phenotype of a parthenogenetic insect species (Acyrthosiphon pisum) was selected in cold conditions and is characterized by a remarkable apparition of a greenish colour. The aphid pigments involve carotenoid genes well defined in chloroplasts and cyanobacteria and amazingly present in the aphid genome, likely by lateral transfer during evolution. The abundant carotenoid synthesis in aphids suggests strongly that a major and unknown physiological role is related to these compounds beyond their canonical anti-oxidant properties. We report here that the capture of light energy in living aphids results in the photo induced electron transfer from excited chromophores to acceptor molecules. The redox potentials of molecules involved in this process would be compatible with the reduction of the NAD+ coenzyme. This appears as an archaic photosynthetic system consisting of photo-emitted electrons that are in fine funnelled into the mitochondrial reducing power in order to synthesize ATP molecules.

Degradation kinetic modelling of ascorbic acid and colour intensity in pasteurised blood orange juice during storage.

The stability of ascorbic acid and colour intensity in pasteurised blood orange juice (Citrus sinensis [L.] Osbeck) during one month of storage was investigated at 4-37 °C. The effects of ascorbic acid fortification (at 100, 200 mg L(-1)) and deaeration, temperature/time storage on the kinetic behaviour were determined. Ascorbic acid was monitored by HPLC-DAD and colour intensity by spectrophotometric measurements. Degradation kinetics were best fitted by first-order reaction models for both ascorbic acid and colour intensity. Three models (Arrhenius, Eyring and Ball) were used to assess the temperature-dependent degradation. Following the Arrhenius model, activation energies were ranged from 51 to 135 kJ mol(-1) for ascorbic acid and from 49 to 99 kJ mol(-1) for colour intensity. The effect of storage temperature and deaeration are the most influent factors on kinetics degradation, while the fortification revealed no significant effect on ascorbic acid content and colour intensity.

Anthocyanins degradation during storage of Hibiscus sabdariffa extract and evolution of its degradation products

Degradation parameters of two main anthocyanins from roselle extract (Hibiscus sabdariffa L.) stored at different temperatures (4-37°C) over 60days were determined. Anthocyanins and some of their degradation products were monitored and quantified using HPLC-MS and DAD. Degradation of anthocyanins followed first-order kinetics and reaction rate constants (k values), which were obtained by non-linear regression, showed that the degradation rate of delphinidin 3-O-sambubioside was higher than that of cyanidin 3-O-sambubioside with k values of 9.2·10(-7)s(-1) and 8.4·10(-7)s(-1) at 37°C respectively. The temperature dependence of the rate of anthocyanin degradation was modeled by the Arrhenius equation. Degradation of delphinidin 3-O-sambubioside (Ea=90kJmol(-1)) tended to be significantly more sensitive to an increase in temperature than cyanidin 3-O-sambubioside (Ea=80kJmol(-1)). Degradation of these anthocyanins formed scission products (gallic and protocatechuic acids respectively) and was accompanied by an increase in polymeric color index.

Fate of phytochemicals during malting and fermentation of type III tannin sorghum and impact on product biofunctionality.

The aim of the present study was to assess the effects of sorghum bioprocessing into Gowé on iron bioavailability and antioxidant properties of the final products. Gowé is an African sour beverage, whose process combines malting and fermenting of sorghum grains. The effects of the durations of germination and fermentation on the phytochemicals were evaluated using a central composite design. The antioxidant capacity and iron bioavailability of the derived flour were also evaluated. During the germination process, the tannin content of the grain decreased from 429.5 to 174.1 mg/100 g DM, while the total phenolic content increased from 300.3 to 371.5 mg GAE/100 g DM. The phenolic acid contents of the flour were significantly modified as a result of the durations of germination and fermentation. Both germination and fermentation enhanced the antioxidant capacity of sorghum flour, and antioxidant characteristics were significantly correlated with the levels of total phenolics, tannins, and phenolic acids. Phytate content of sorghum grain decreased drastically from 1003 to 369.1 mg/100 g DM when the duration of germination or fermentation increased. This was associated with an increase in the bioavailability of iron.

Effect of Temperature on Acidity and Hydration Equilibrium Constants of Delphinidin-3-O- and Cyanidin-3-O-sambubioside Calculated from Uni- and Multiwavelength Spectroscopic Data

Delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside are the main anthocyanins of Hibiscus sabdariffa calyces, traditionally used to make a bright red beverage by decoction in water. At natural pH, these anthocyanins are mainly in their flavylium form (red) in equilibrium with the quinonoid base (purple) and the hemiketal (colorless). For the first time, their acidity and hydration equilibrium constants were obtained from a pH-jump method followed by UV-vis spectroscopy as a function of temperature from 4 to 37 °C. Equilibrium constant determination was also performed by multivariate curve resolution (MCR). Acidity and hydration constants of cyanidin-3-O-sambubioside at 25 °C were 4.12 × 10(-5) and 7.74 × 10(-4), respectively, and were significantly higher for delphinidin-3-O-sambubioside (4.95 × 10(-5) and 1.21 × 10(-3), respectively). MCR enabled the obtaining of concentration and spectrum of each form but led to overestimated values for the equilibrium constants. However, both methods showed that formations of the quinonoid base and hemiketal were endothermic reactions. Equilibrium constants of anthocyanins in the hibiscus extract showed comparable values as for the isolated anthocyanins.

Exploration of reaction mechanisms of anthocyanin degradation in a roselle extract through kinetic studies on formulated model media

Effect of oxygen, polyphenols and metals was studied on degradation of delphinidin and cyanidin 3-O-sambubioside of Hibiscus sabdariffa L. Experiments were conducted on aqueous extracts degassed or not, an isolated polyphenolic fraction and extract-like model media, allowing the impact of the different constituents to be decoupled. All solutions were stored for 2months at 37°C. Anthocyanin and their degradation compounds were regularly HPLC-DAD-analyzed. Oxygen concentration did not impact the anthocyanin degradation rate. Degradation rate of delphinidin 3-O-sambubioside increased 6-fold when mixed with iron from 1 to 13mg.kg-1 but decreased with chlorogenic and gallic acids. Degradation rate of cyanidin 3-O-sambubioside was not affected by polyphenols but increased by 3-fold with increasing iron concentration with a concomitant yield decrease of scission product, protocatechuic acid. Two pathways of degradation of anthocyanins were identified: a major metal-catalyzed oxidation followed by condensation and a minor scission which represents about 10% of degraded anthocyanins.

Comparison of phenolic and volatile profiles of edible and toxic forms of Detarium senegalense J. F. GMEL

In Senegal, Detarium senegalense J.F. Gmel. (ditax in Wolof) is one of the most important forest fruit species. However, exploitation of the edible fruit is based on local people’s knowledge. Only trees whose fruits are consumed by animals are exploited. To identify them, a chemical comparison of edible and toxic forms was done in order to highlight differences between both forms. Dichloromethane leaf extracts from toxic and edible trees were analyzed by gas chromatography. Phenolic profile and volatile compounds from fruits extracts were studied respectively by High Performance Liquid Chromatography-mass spectrometry (HPLC-MS) and Gas Chromatography Mass Spectrometry (GCMS). Cytotoxicity effect of fruits extracts was evaluated on murine macrophage cells J774 A1. GC analysis of dichloromethane leaf extracts revealed the presence of lupenone and lupeol only in toxic extracts. 6’-O-galloyl-epiheterodendrin and isovaleronitrile were detected in toxic pulp. However, no cytotoxic effect was found in our conditions. This study has given the opportunity to identify within the same species, compounds which could differentiate both edible and toxic forms. Nevertheless further studies are needed to better understand which compounds are responsible for toxicity in the toxic form. Key words : Ditax, Detarium senegalense , toxicity, lupeol, lupenone, cyanogenic glycoside, isovaleronitrile