Valorization of raw materials from agricultural industry for astaxanthin and β-carotene production by Xanthophyllomyces dendrorhous

Waste deriving from food and agro-industries is a growing problem in our modern society. In order to reduce food waste and its associated impacts over the environment and public health, innovative strategies for the conversion of food wastes in added value products are studied. Whey is one of the prominent waste deriving from Sicilian diary industry. The growth and the carotenoid biosynthesis of the yeast Xanthophyllomyces dendrorhous by its cultivation in pre-treated whey were studied. The study showed the possibility of increasing the astaxanthin productivity from X. dendrorhous in a batch fermentative process under continuous illumination. Our work is focused on the importance of carotenogenesis by X. dendrorhous on whey for the economic and ecological aspect. The results obtained in the study provide useful information about the possible use of this waste material for carotenogenesis from X. dendrorhous.     

Theoretical and electrochemical analysis of dissociative electron transfers proceeding through formation of loose radical anion species: reduction of symmetrical and unsymmetrical disulfides

The dissociative reduction of a series of symmetrical (RSSR, R = H, Me, t-Bu, Ph) and unsymmetrical disulfides (RSSR', R = H, R' = Me and R = Ph, R' = Me, t-Bu) was studied theoretically, by MO ab initio calculations and, for five of them, also experimentally, by convolution voltammetry in N,N-dimethylformamide. The reduction is dissociative but proceeds by a stepwise mechanism entailing the formation of the radical anion species. The electrochemical data led to estimated large intrinsic barriers, in agreement with an unusually large structural modification undergone by the disulfide molecules upon electron transfer. The theoretical results refer to MP2/3-21G*//MP2/3-21G*, MP2/3-21*G*//MP2/3-21G*, CBS-4M, and G2(MP2), the latter approach being used only for the molecules of small molecular complexity. A loose radical-anion intermediate was localized and the dissociation pattern for the relevant bonds analyzed. For all compounds, the best fragmentation pathway in solution is cleavage of the S-S bond. In addition, S-S bond elongation is the major structural modification undergone by the disulfide molecule on its way to the radical anion and eventually to the fragmentation products. The calculated energy of activation for the initial electron transfer was estimated from the crossing of the energy profiles of the neutral molecule and its radical anion (in the form of Morse-like potentials) as a function of the S-S bond length coordinate. The inner intrinsic barrier obtained in this way is in good agreement with that determined by convolution voltammetry, once the solvent effect is taken into account.     

Understanding electron transfer across negatively-charged Aib oligopeptides

The physicochemical effects modulating the conformational behavior and the rate of intramolecular dissociative electron transfer in phthalimide-Aibn-peroxide peptides (n = 0-3) have been studied by an integrated density functional/continuum solvent model. We found that three different orientations of the phthalimide ring are possible, labeled Phihel, PhiC7, and PhipII. In the condensed phase, they are very close in energy when the system is neutral and short. When the peptide chain length increases and the system is negatively charged, Phihel becomes instead the most stable conformer. Our calculations confirm that the 3(10)-helix is the most stable secondary structure for the peptide bridge. However, upon charge injection in the phthalimide end of the phthalimide-Aib3-peroxide, the peptide bridge can adopt an alpha-helix conformation as well. The study of the dependence of the frontier orbitals on the length and on the conformation of the peptide bridge (in agreement with experimental indications) suggests that for n = 3 the process could be influenced by a 3(10) --> alpha-helix conformational transition of the peptide chain.     

Nitroxyl peptides as catalysts of enantioselective oxidations

The achiral, nitroxyl-containing alpha-amino acid TOAC (TOAC = 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid), in combination with the chiral alpha-amino acid C(alpha)-methyl valine [(alphaMe)Val], was used to prepare short peptides (from di- to hexa-) that induced the enantioselective oxidation of racemic 1-phenylethanol to acetophenone. The best catalyst was an N(alpha)-acylated dipeptide alkylamide with the -TOAC-(alphaMe)Val- sequence folded in a stable, intramolecularly hydrogen-bonded beta-turn conformation with large, lipophilic (hydrophobic) N- and C-terminal blocking groups. We rationalized our findings by proposing models for the diastereomeric intermediates between (R)-[and (S)]-1-phenylethanol and the catalyst Fmoc-TOAC-L-(alphaMe)Val-NHiPr, based on the X-ray diffraction structure of the latter.     

Alkyl capped carbonates ofβ-cyclodextrin

The synthesis is described of alkyl capped carbonates of-cyclodextrin, obtained from diols activated with carbonyldiimidazole. The reaction preferentially gave monocapped derivatives which were characterized by HPLC, TLC, FT-IR and¹³C-NMR. These compounds are stable at pH <7, and methyl orange was found to form stronger inclusion compounds with capped-cyclodextrin than with the parent-cyclodextrin. Paramagnetic Gd(III) complexes were also studied, but they were found to be included into capped-cyclodextrin as well as into-cyclodextrin.Part of this work was presented at the 7th International Symposium on Cyclodextrins, 1994, Tokyo, April 25–28, Book of Abstract, page 54.     

Anomalous distance dependence of electron transfer across peptide bridges

The first investigation on the distance dependence of a dissociative electron transfer process across peptide bridges is reported. This study was carried out by using a series of donor-peptide-acceptor systems in which the donor is a phthalimido moiety, the peptide bridges are provided by alpha-aminoisobutyric acid (Aib) homooligomers, and the acceptor is a peroxide functional group. The intramolecular electron transfer from the electrogenerated phthalimido radical anion to the peroxide was studied in comparison with the thermodynamic and kinetic information obtained with models of the acceptor and the donor. The intramolecular rate constants were determined in N,N-dimethylformamide by taking into account the corresponding intermolecular values. The experimental results point to an unusual non-exponential dependence of the intramolecular electron transfer rate on the number of bridge units. The same trend could be verified also by taking into account the actual donor-acceptor edge-to-edge distance. The peculiar distance dependence that was observed for the intramolecular electron transfer rate is attributed to the mediating effect of the intramolecular C=O...H-N hydrogen bonds.