Oxidative properties of the Iron - Thymine-1-acetic acid - Hydrogen peroxide catalytic system

The oxidation of alcohols and olefins is a pivotal reaction in organic synthesis. However, traditional oxidants are toxic and they often release a considerable amounts of by-products. Here, two IronIII-based systems are shown as oxidative catalyst, working in mild conditions with hydrogen peroxide as primary oxidant. An efficient catalytic system for the selective oxidation of several alcohols to their corresponding aldehydes and ketones was developed and characterized, [Fe(phen)2Cl2]NO3 (phen=1,10-Phenantroline). It was demonstrated that the adoption of a buffered aqueous solution is of crucial importance to ensure both considerable activity and selectivity.The Iron - Thymine-1-acetic acid in-situ complex was studied as catalyst in alcohol oxidations and C-H oxidative functionalization, involving hydrogen peroxide as primary oxidant in mild reaction conditions. The catalytic ability in alcohol oxidations was investigated by Density Functional Theory calculations, however the catalyst still has uncertain structure. The system shows satisfactory activity in alcohol oxidation and aliphatic rings functionalization. The Fe-THA system was studied in cyclohexene oxidation and oxidative halogenations. Halide salts such as NBu4X and NH4X were introduced in the catalytic system as halogens source to obtain cyclohexene derivatives such as halohydrins, important synthetic intermediates.The purpose of this dissertation is to contribute in testing new catalytic systems for alcohol oxidations and C-H functionalization. In particular, most of the efforts in this work focus on studying the Iron - Thymine-1-acetic acid (THA) systems as non-heme oxidative model, which present: •an iron metal centre(s) as a coordinative active site, •hydrogen peroxide as a primary oxidant, •THA as an eco-friendly, biocompatible, low cost coordinating ligand.

Assessing the impact of ammonia content in VFA-rich streams on the PHA-storing MMC acclimatization and the PHA production stage

The use of environmentally friendly products increased the interest in renewable resources as alternatives to petrochemical products. Polyhydroxyalkanoates (PHAs) are examples of such promising products, as they are biodegradable polymers with numerous potential applications. PHA production approach consists of using an open mixed microbial culture (MMC) and inexpensive feedstocks (waste or industry byproducts feedstock). The PHA process generally comprises three stages: (1) acidogenic fermentation (AF) stage (conversion of organic carbon into fermentation products); (2) culture selection stage (enrichment in PHA-storing organisms by applying Feast and Famine regime); and (3) PHA production stage (PHA accumulation up to the culture’s maximum capacity). AF of protein-rich residues results in ammonia-rich fermented streams, which can be presented as a challenge for the PHA production stage. The presence of ammonia during this stage may induce organisms to grow instead of producing PHAs. For this reason, the assessment of the effect of a high content of ammonia on PHA production it is the utmost importance. The main goal of the current project is to select a MMC enriched in PHA-accumulating organisms in conditions of high ammonia content and to evaluate the effects of ammonia presence during PHA accumulation. The culture was selected applying the Feast & Famine strategy, and fed, firstly, using a synthetic mixture of VFAs and later using a fermented stream obtained from the fermentation of protein-rich raw materials. The selected culture could accumulate up to 24% PHA per VSS with the synthetic mixture of VFAs and up to 29% for the real fermented stream. The PHA accumulation resulted in different production in the presence and absence of ammonia. Regarding to the synthetic feed, 59%wt. PHA (VSS basis) in the absence of ammonia, and 55%wt. (VSS basis) in the presence, were obtained. For the real feed, the PHA content was about 40%wt. (VSS basis) in both reactors.