Synthesis of heterocyclic compounds by radical electrochemical approach in environmentally friendly media

Radical cyclisation is rapidly becoming an important method for the formation of cyclic systems. Hence, some electrochemical results obtained in the study of electroreductive intramolecular cyclisation of ethyl 2-bromo-3-(3,4-methylenedioxophenyl)-3-(propargyloxy)propanoate (1a), [1-bromo-2-methoxy-2-(prop-2’-ynyloxy) ethyl] benzene (1b) and 1-[2-bromo-2-phenyl-1-(prop-2’-ynyloxy)ethyl]-4-methoxybenzene (1c) promoted by (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetra-decane)nickel(I), [Ni(tmc)]+, electrogenerated at glassy carbon cathodes in ethanol, ethanol / water and microemulsions made with cationic and anionic surfactants are presented. The results obtained indicate that the reaction proceeds via cleavage of the carbon–bromine bond to form a radical intermediate that undergoes cyclization on the unsaturated C-C bond to afford the substituted tetrahydrofurans.Fundação para a Ciência e a Tecnologia (FCT

Multi-level dynamic modeling in biological systems : application of hybrid Petri nets to network simulation

The recent progress in the high-throughput experimental technologies allows the reconstruction of many biological networks and to evaluate changes in proteins, genes and metabolites levels in different conditions. On the other hand, computational models, when complemented with regulatory information, can be used to predict the phenotype of an organism under different genetic and environmental conditions. These computational methods can be used for example to identify molecular targets capable of inactivating a bacterium and to understand its virulence factors. This work proposes a hybrid metabolic-regulatory Petri net approach that is based on the combination of approximate enzyme-kinetic rate laws and Petri nets. A prototypic network model is used as a test-case to illustrate the application of these concepts in Systems Biology.This work was partially supported by post-doctoral grant by Fundacao para a Ciencia e a Tecnologia (FCT) (SFRH/BPD/80784/2011), project PneumoSyS - A Systems Biology approach to the role of pneumococcal carbon metabolism in colonization and invasive disease (FCT contract: PTDC/SAU-MII/100964/2008) and by FCT (INESC-ID multiannual funding) through the PIDDAC program funds

Reactions radicalaires dans des milieux protiques et aprotiques : comparaisons entre les cyclisations reductives electrochimiques catalysees par des complexes du nickel

The electrochemical reductive cyclisation of unsaturated organic halides in the presence of Ni(II) complexes as catalysts was examined in aprotic solvents such as DMF and in protic solvents such as ethanol, butanol or ethanolewater mixtures. The presence of the alcohol media enhanced the rate of recycling of the catalytic species.La cyclisation réductive électrochimique d’halogénures insaturés en présence de complexes de Ni(II) comme catalyseurs a été examinée dans des solvants comme le DMF et dans des solvants protiques comme l’éthanol, le butanol ou des mélanges éthanol-eau. La présence du milieu alcoolique augmente la vitesse du recyclage des espèces catalytiques.Fundação para a Ciência e a Tecnologia (FCT

Electrosynthesis of nitrogen heterocycles using environmentally friendly methodologies

Cyclic voltammetry and constant-current electrolysis in a one-compartment cell with a sacrificial anode has been used to study the indirect electroreduction of N-allyl- -haloamides by electrogenerated Ni(I) complexes conducted inN,N-dimethylformamide (DMF) and acetonitrile (ACN) and the resultswere compared with those obtained in protic solvents such as EtOH and EtOH–H2O mixtures. It was observed that the indirect electrochemical reduction of N-allyl- -haloamides led to the corresponding lactams and the yields and selectivities obtained in EtOH and EtOH–H2O were much better than those obtained in DMF or ACN.Fundação para a Ciência e a Tecnologia (FCT

Intercalation of (η5-Pentamethylcyclopentadienyl)trioxomolybdenum(VI) in a Layered Double Hydroxide

A Zn,Al layered double hydroxide (LDH) with [Cp*MoO3]– (Cp* = η5‐C5Me5) anions in the interlayer has been prepared by a direct coprecipitation method. The intercalated LDH and the mixed metal oxide (MMO) obtained after its calcination were characterized by elemental and thermogravimetric analyses, powder X‐ray diffraction (PXRD), FT‐IR and FT‐Raman spectroscopy, 13C and 27Al MAS NMR, and scanning electron microscopy. The observed basal spacing of 17.1 Å for the LDH Zn,Al‐Cp*MoO3 (corresponding to a gallery height of 12.3 Å) suggests that the guest anions self‐assemble into dimers via offset face‐to‐face Cp*···Cp* interactions, which facilitates hydrogen‐bonding interactions between the oxido ligands of the complexes and the layer hydroxyl groups, while positioning the hydrophobic aromatic rings towards the center of the galleries. Calcination of Zn,Al‐Cp*MoO3 at 550 °C under air gave an MMO comprising well‐dispersed ZnO, α‐ZnMoO4 and ZnAl2O4 (spinel) oxides in a molar of ca. 1.4:1.6:1. The MMO exhibited catalytic activity for the epoxidation of cis‐cyclooctene with tert‐butylhydroperoxide (TBHP) as terminal oxidant, with quantitative yield of the epoxide being achieved within 24 h at 85 °C.publishe

Advances achieved by ionic-liquid-based materials as alternative supports and purification platforms for proteins and enzymes

Ionic liquids (ILs) have been applied in several fields in which enzymes and proteins play a noteworthy role, for instance in biorefinery, biotechnology, and pharmaceutical sciences, among others. Despite their use as solvents and co-solvents, their combination with materials for protein- and enzyme-based applications has raised significant attention in the past few years. Among them, significant advances were brought by supported ionic liquids (SILs), in which ILs are introduced to modify the surface and properties of materials, e.g., as ligands when covalently bond or when physiosorbed. SILs have been mainly investigated as alternative supports for enzymes in biocatalysis and as new supports in preparative liquid chromatography for the purification of high-value proteins and enzymes. In this manuscript, we provide an overview on the most relevant advances by using SILs as supports for enzymes and as purification platforms for a variety of proteins and enzymes. The interaction mechanisms occurring between proteins and SILs/ILs are highlighted, allowing the design of efficient processes involving SILs. The work developed is discussed in light of the respective development phase and innovation level of the applied technologies. Advantages and disadvantages are identified, as well as the missing links to pave their use in relevant applications.publishe

Influence of anion structure on thermal, mechanical and CO2 solubility properties of uv-cross-linked poly(Ethylene glycol) diacrylate iongels

PTDC/CTM-POL/2676/2014 UID/QUI/50006/2019 grant 471837 SFRH/BD/136963/2018 IF/00505/2014Iongel-based CO2 separation membranes were prepared by fast (< 1 min) UV-initiated polymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of different ionic liquids (ILs) with the [C2mim]+ cation and anions such as [TFSI]−, [FSI]−, [C(CN)3]− and [B(CN)4]−. The four ILs were completely miscible with the non-ionic PEGDA network. Transparent and freestanding iongels containing between 60 and 90 %wt of IL were obtained and characterized by diverse techniques (FTIR, TGA, DSC, DMTA, SEM, CO2 solubility and pure gas permeability). The thermal and mechanical stability of the iongels, as well as CO2 solubility, were found to be strictly dependent on the IL content and the anion’s nature. The TGA results indicated that the iongels mostly follow the thermal profile of the respective neat ILs. The DMTA analysis revealed that the iongels based on fluorinated anions have higher storage modulus than those of cyano-functionalized anions. Conversely, the PEGDA–C(CN)3 iongels presented the highest CO2 solubility values ranging from 72 to 80 mmol/g. Single CO2 permeabilities of 583 ± 29 Barrer and ideal CO2/N2 selectivities of 66 ± 3 were obtained with the PEGDA–70 C(CN)3 iongel membrane. This work demonstrates that the combination of PEGDA with high contents of the best performing ILs is a promising and simple strategy, opening up new possibilities in the design of high-performance iongel membranes for CO2 separation.publishersversionpublishe

Molybdenum(II) Diiodo-Tricarbonyl Complexes Containing Nitrogen Donor Ligands as Catalyst Precursors for the Epoxidation of Methyl Oleate

Resumo alargado de "Molybdenum(II) Diiodo-Tricarbonyl Complexes Containing Nitrogen Donor Ligands as Catalyst Precursors for the Epoxidation of Methyl Oleate"Com o apoio RAADRI

Effect of zeolite nanomaterials in methanogenic communities

Recently, the application of zeolite structures in methanogenic communities has attracted significant attention, since they may enhance the anaerobic digestion process, by affecting specifically the methanogenic activity of the sludges1. Zeolites are solid inorganic crystalline materials comprised of silicon, aluminum and oxygen in the three-dimensional structure. The building blocks become arranged in a periodic way to form channels and cages on a nano- and subnanometer scale of strictly regular dimensions, named micropores. The presence of the aluminum in the zeolite framework create a negative charge in the lattice, which can be balanced by the exchangeable cations, as sodium or metal ions.2 In this study, commercial zeolite structures (ZSM5, USY, NaX and NaY) with different particle sizes and different exchangeable cations (Co, Cu, Zn, Fe) were used in order to investigate their effect towards the specific methanogenic activity, both acetoclastic and hydrogenotrophic, of anaerobic sludge. In the acetoclastic methanogenic activity, NaY modified with Cobalt (CoY) decreased the activity in comparison with the control (without zeolite). The remaining zeolites (ZSM5, USY, NaX and NaY), even when modified with metal ions (Zn, Fe, Cu), seems to have no effect on this methanogenic pathway. On the other hand, the hydrogenotrophic methanogenesis was improved by the presence of NaY (109 %), which did not happen in the presence of ZSM5 and USY zeolites. Additionally, the effect of different zeolite concentration was accessed. Overall, the increase of zeolite concentration from 1 g/L to 5 g/L resulted in a higher inhibition towards the methanogenic activity. In addition, the application of these nanomaterials can be evaluated in pure cultures of methanogens, in order to understand and fine-tune the best zeolite nanomaterial concentration that may improve the specific methanogenic activity.We thank the Fundação para a Ciência e Tecnologia (FCT) for financial support through Centre of Chemistry (UID/QUI/00686/2013 and UID/QUI/0686/2016) and BioTecNorte (operation NORTE-01-0145-FEDER-000004), and through Centre of Biological -engineering (UIDB/04469/2020 unit). Cátia S. N. Braga holds a grant SFRH/BD/132003/2017 funded by FCT and European Union (EU), through the Portuguese State Budget and the European Social Fund under the scope of Programa Operacional Regional do Norte.info:eu-repo/semantics/publishedVersio

Simultaneous Separation of Antioxidants and Carbohydrates From Food Wastes Using Aqueous Biphasic Systems Formed by Cholinium-Derived Ionic Liquids

project CICECO-Aveiro Institute of Materials, UID/CTM/50011/2019. Associate Laboratory for Green Chemistry-LAQV, FCT Ref. UID/QUI/50006/2019. POCI-01-0145-FEDER-016403. Investigator FCT project IF/00621/2015. Programa Mais Centro under project CENTRO-07-ST24-FEDER-002008. COMPETE: PEst-C/SAU/UI0709/2011.The food industry produces significant amounts of waste, many of them rich in valuable compounds that could be recovered and reused in the framework of circular economy. The development of sustainable and cost-effective technologies to recover these value added compounds will contribute to a significant decrease of the environmental footprint and economic burden of this industry sector. Accordingly, in this work, aqueous biphasic systems (ABS) composed of cholinium-derived bistriflimide ionic liquids (ILs) and carbohydrates were investigated as an alternative process to simultaneously separate and recover antioxidants and carbohydrates from food waste. Aiming at improving the biocompatible character of the studied ILs and proposed process, cholinium-derived bistriflimide ILs were chosen, which were properly designed by playing with the cation alkyl side chain and the number of functional groups attached to the cation to be able to create ABS with carbohydrates. These ILs were characterized by cytotoxicity assays toward human intestinal epithelial cells (Caco-2 cell line), demonstrating to have a significantly lower toxicity than other well-known and commonly used fluorinated ILs. The capability of these ILs to form ABS with a series of carbohydrates, namely monosaccharides, disaccharides and polyols, was then appraised by the determination of the respective ternary liquid-liquid phase diagrams at 25 degrees C. The studied ABS were finally used to separate carbohydrates and antioxidants from real food waste samples, using an expired vanilla pudding as an example. With the studied systems, the separation of the two products occurs in one-step, where carbohydrates are enriched in the carbohydrate-rich phase and antioxidants are mainly present in the IL-rich phase. Extraction efficiencies of carbohydrates ranging between 89 and 92% to the carbohydrate-rich phase, and antioxidant relative activities ranging between 65 and 75% in the IL-rich phase were obtained. Furthermore, antioxidants from the IL-rich phase were recovered by solid-phase extraction, and the IL was recycled for two more times with no losses on the ABS separation performance. Overall, the obtained results show that the investigated ABS are promising platforms to simultaneously separate carbohydrates and antioxidants from real food waste samples, and could be used in further related applications foreseeing industrial food waste valorization.publishersversionpublishe