A Green Lipophilization Reaction of a Natural Antioxidant.

A natural antioxidant, widely spread in plants, chlorogenic acid (CGA), can be lipophilized through a heterogeneous, non-enzymatic, catalytic process. Thus, sulfonic resins under no solvent conditions allow to obtain a series of esters in up to 93% yield through reaction of CGA with fatty alcohols of different chain length. The reaction takes place in one single step under mild conditions with conversions up to 96% and selectivity up to 99%. Product recovery in high purity was very easy and the esters obtained were fully characterized with spectroscopic techniques and through the DPPH test to verify the preservation of antioxidant activity. According to this test, all of them showed increased activity with respect to the parent acid and anyway higher than butylated hydroxyanisole. An in-silico method also suggested their very low toxicity. The increased lipophilicity of the esters allows their formulation in cosmetic and nutraceutic lipid-based products.

Sustainable Extraction Methods Affect Metabolomics and Oxidative Stability of Myrtle Seed Oils Obtained from Myrtle Liqueur By-Products: An Electron Paramagnetic Resonance and Mass Spectrometry Approach.

Myrtle liqueur production generates high amounts of by-products that can be employed for the extraction of bioactive compounds. Bio-based, non-toxic and biodegradable solvents (ethyl acetate and 2-methyltetrahydrofuran), and a mechanical extraction were applied to myrtle seeds, by-products of the liqueur production, to extract oils rich in phenolic compounds. The oils obtained were characterized for yield, peroxide value (PV), lipid composition, and total phenolic concentration (TPC). The phenolic profile of the oils, determined by LC-MS, the antioxidant activity, and the oxidative stability were also analyzed. A validated UHPLC-ESI-QTRAP-MS/MS analytical method in multiple reaction monitoring (MRM) mode was applied to quantify myricetin and its main derivatives in myrtle oils. The results pointed out clear differences among extraction methods on myricetin concentration. The oxidative stability of myrtle oils was studied with electron paramagnetic resonance (EPR) spectroscopy highlighting the effect of the extraction method on the oxidation status of the oils and the role of phenolic compounds in the evolution of radical species over time. A principal component analysis applied to LC-MS data highlighted strong differences among phenolic profiles of the oils and highlighted the role of myricetin in the oxidative stability of myrtle oils. Myrtle oil, obtained from the by-products of myrtle liqueur processing industry, extracted with sustainable and green methods might have potential application in food or cosmetic industries.

Fishery waste valorization: Sulfated ZrO2 as a heterogeneous catalyst for chitin and chitosan depolymerization.

Chitin and chitosan are abundant unique sources of biologically-fixed nitrogen mainly derived from residues of the fishery productive chain. Their high potential as nitrogen-based highly added-value platform molecules is still largely unexploited and a catalytic way for their valorization would be strongly desirable within a biorefinery concept. Here we report our results obtained with a series of heterogeneous catalysts in the depolymerization of chitosan and chitin to acetylglucosamine. Copper catalysts supported on SiO2, SiO2-Al2O3, SiO2-ZrO2, ZrO2 and the corresponding bare oxides/mixed oxides were tested, together with a sulfated zirconia system (ZrO2-SO3H) that revealed to be extremely selective towards glucosamine, both for chitosan and chitin, thus giving pretty high yields with respect to the values reported so far (44% and 21%, respectively). The use of a heterogeneous catalyst alone, without the need of any additives or the combination with a mineral acid, makes these results remarkable.

Styrene-Free Bio-Based Thermosetting Resins with Tunable Properties Starting from Vegetable Oils and Terpenes.

The substitution of fossil-based monomers in the thermosetting formulations is a fundamental issue to face the environmental concerns related to the use of traditional resins. In this paper, styrene-free thermosetting resins were prepared to start from vegetable oils with different compositions and unsaturation degrees, namely soybean, hempseed, and linseed oils. Using terpenic comonomers such as limonene and ß-myrcene allows one to prepare thermosets avoiding the traditional fossil-based diluents such as styrene, thus obtaining an outstanding gain in terms of both environmental and safety concerns. Furthermore, the materials obtained reveal tunable physical properties upon the proper choice of the monomers, with glass transition temperature ranging from 40 to 80 °C and Young's modulus ranging from 200 to 1800 MPa. The possibility of preparing composite materials starting from the resins prepared in this way and natural fibres has also been explored due to the potential applications of bio-based composites in several industrial sectors.

Green pathway to a new fuel extender: continuous flow catalytic synthesis of butanol/butyl butyrate mixtures.

The preparation of a butanol/butyl butyrate mixture was performed in one-step under continuous flow conditions with a CuO/ZrO2 catalyst. The catalytic system allows one to directly obtain up to 40-42% of butyl butyrate starting from butanol via a dehydrogenative coupling reaction without using solvent or additives. The obtained mixture was tested in a direct injection spark ignition engine as a blend of 70%vol gasoline and 30%vol butanol/butyl butyrate mixture. One of the main goals was to evaluate overall performance and whether knock tendency increased compared to the reference condition that featured gasoline only fueling. Exhaust gas pollutants were evaluated as well, so as to give a more complete picture of environmental impact effects. Overall engine performance and emissions were found to be comparable to those obtained for the reference case, with negligible increase in knocking characteristics.

Selective synthesis of thioethers in the presence of a transition-metal-free solid Lewis acid.

The synthesis of thioethers starting from alcohols and thiols in the presence of amorphous solid acid catalysts is reported. A silica alumina catalyst with a very low content in alumina gave excellent results in terms of both activity and selectivity also under solvent-free conditions. The reaction rate follows the electron density of the carbinol atom in the substrate alcohol and yields up to 99% and can be obtained for a wide range of substrates under mild reaction conditions.

CuO/SiO2 as a simple, effective and recoverable catalyst for alkylation of indole derivatives with diazo compounds.

The purely inorganic copper oxide on silica catalyzes the reaction of methyl phenyldiazoacetate with N-methyl indole under mild reaction conditions, giving the alkylation (formally a C-H insertion) in position 3, and the catalyst can be recovered and reused at least in 5 consecutive runs with only minor loss in activity. The scope of the reaction includes various diazo compounds and indole or pyrrole derivatives leading to alkylation or cyclopropanation depending on the heterocycle structure. An alternative mechanism, without reduction of Cu(II) to Cu(I), is proposed on the basis of the obtained results.

Epoxidation of alkenes through oxygen activation over a bifunctional CuO/Al2O3 catalyst.

The epoxidation of alkenes was carried out over a CuO/Al(2)O(3) catalyst using cumene as an oxygen carrier, through a one-pot reaction, giving high conversion and selectivity with different substrates. Trans-ß-methylstyrene gave the corresponding epoxide in 95% yield after 3 h.

Unravelling the properties of supported copper oxide: can the particle size induce acidic behaviour?

There is a renewed interest in designing solid acid catalysts particularly due to the significance of Lewis acid catalyzed processes such as Friedel-Crafts acylation and alkylation and cellulose hydrolysis for the development of sustainable chemistry. This paper reports a new focus point on the properties of supported CuO on silica, a material that up to now has been considered only as the precursor of an effective hydrogenation catalyst. Thus, it deals with a re-interpretation of some of our results with supported copper oxide aimed to unveil the root of acidic activity exhibited by this material, e.g. in alcoholysis reactions. Several techniques were used to highlight the very high dispersion of the oxide phase on the support allowing us to ascribe the acidic behavior to coordinative unsaturation of the very small CuO particles. In turn this unsaturation makes the CuO particles prone to coordinate surrounding molecules present in the reaction mixture and to exchange them according to their nucleophilicity.

Esterification of acidic oils over a versatile amorphous solid catalyst.

An amorphous SiO(2)-ZrO(2) catalyst shows high activity in the esterification of free fatty acids contained in vegetable oils while at the same time promoting the transesterification of triglycerides. The catalyst is hence a good candidate for a low-waste deacidification pretreatment or for a one-pot biodiesel production process starting from oils with a high acid content.

Synthetic scope of alcohol transfer dehydrogenation catalyzed by Cu/Al2O3: a new metallic catalyst with unusual selectivity.

A method for the anaerobic oxidation of a wide series of alcohols including cyclohexanols and steroidal alcohols, has been set up. It relies on a transfer dehydrogenation reaction from the substrate alcohol to styrene catalyzed by a heterogeneous, reusable copper catalyst under very mild liquid-phase experimental conditions (90 degrees C, N(2)) and shows unusual selectivity. Thus, the method is selective for the oxidation of secondary and allylic alcohols even in the presence of unprotected primary and benzylic alcohols. Electronic effects and the choice of the hydrogen acceptor account for the selectivity observed.

Dependence of copper species on the nature of the support for dispersed CuO catalysts.

Copper catalysts prepared by chemisorption-hydrolysis technique over silica (Cu/Si) and silica-alumina (Cu/SiAl) supports were studied to understand the role of the support on the nature and surface properties of the copper species stabilized on their surfaces. The morphological and surface properties of the copper phases have been characterized by complementary techniques, such as HRTEM, EXAFS-XANES, EPR, XPS, and FTIR. For the FTIR investigation, molecular probes (CO and NO) were also adsorbed on the surfaces to test the reactivity of the copper species. Moreover, the catalytic performances of the two catalysts have been compared in the HC-SCR reaction (NO reduction by C(2)H(4)) performed in highly oxidant conditions. The superior activity and selectivity of the supported silica-alumina catalyst with respect to that supported on silica could be related with the different nature of the copper species stabilized on the two supports, as emerged from the results obtained from the spectroscopic investigations. Small and well-dispersed CuO particles were present on silica, whereas isolated copper ions predominated on silica-alumina, likely in regions rich in alumina that made some exchangeable sites available, as indicated by FTIR spectra of adsorbed CO. The less positive global charge of copper species on Cu/SiAl than in Cu/Si has been confirmed by EPR, XPS, and EXAFS-XANES analyses.

Anaerobic oxidation of non-activated secondary alcohols over Cu/Al2O3.

A liquid phase, transfer dehydrogenation reaction promoted by an 8% Cu/Al(2)O(3) catalyst allows complete conversion of secondary alcohols into ketones under very mild conditions and in short times without any additives.