Development of a green scalable route toward the synthesis of bio-based 2-pyrones

2-Pyrones are molecules that gained significant attention in the field of medicine and synthetic chemistry. They are broadly present in nature, where they play an important role in the defense mechanisms of the organisms in which they are present. Due to their unique structure, 2-pyrones hold immense potential both for the development of pharmacologically active compounds and as building blocks in synthetic chemistry; for these reasons those molecules have attracted researcher's attention during the past decade. In this work, we present the synthesis optimization of bio-based 2-pyrones starting from bio sourced galactaric acid by means of a statistical design of experiment, its scale up from 500 mg to 100 g, the solvent recycling to make the reaction greener as well as the synthesis of galactaric acid from galactose

Development of a flow process for an easy and fast access to 2-pyrone derivatives

2-Pyrones are compounds widely present in nature and they represent interesting building blocks both in medicinal and synthetic chemistry. Due to their peculiar pharmacological activity and structure, they have attracted much attention during the last decades and several protocols for their synthesis have been developed. In this work we propose the synthesis of bio-sourced 2-pyrones, exploiting continuous-flow conditions for an easy, sustainable and fast access to these important molecules

Biosourced Aromatic Derivatives in the Upcycling of Recycled PET: Mellophanic Dianhydride as a Chain Extender

The synthesis of mellophanic dianhydride (MEDA) from biosourced 1,2,3,4-benzene tetracarboxylic derivatives and its use as a chain extender for mechanically recycled PET (R-PET) as an alternative to traditional oil-based pyromellitic dianhydride (PMDA) is reported. The rheological tests performed on the R-PET extruded with MEDA have shown similar results to those obtained with PMDA, and dynamic mechanical thermal analysis (DMTA) showed that, in the 90–110 °C range (i.e., the temperature range commonly used for blow molding of bottles), Young’s modulus of R-PET containing MEDA is about 20% higher in comparison to that of pristine R-PET. The advantage of MEDA is that it can be prepared using building blocks obtained from agricultural waste via a sustainable protocol, whereas PMDA is a product of oil-based chemistr

Carbon nanotubes-based nanohybrids for multifunctional nanocomposites

In the present work, nano-hybrids based on carbon nanotubes (CNTs) bearing immobilized, either through covalent linkage and physical absorption, commercial anti-oxidant molecules have been formulated and used as nanofillers in Ultra High Molecular Weight Polyethylene (UHMWPE), aiming at preparing multifunctional nanocomposites. The effective immobilization of the anti-oxidant molecules has been probed by spectroscopic and thermogravimetric analyses. The study of the morphology and the rheological behaviour of the nanocomposites show that the immobilization of anti-oxidant molecules onto the CNTs surface is beneficial for the state of the polymer/nanoparticles interfacial region. Additionally, the study of the nanocomposites thermo-oxidative behaviour reveals that the nano-hybrids are able to exert a remarkable anti-oxidant action which is related to the strong interactions established between the anti-oxidant molecules and the CNTs, resulting in the formation of structural defects onto the CNTs surface and in the consequent amplification of the intrinsic CNTs radical scavenging activity

Sonication-induced modification of carbon nanotubes: Effect on the rheological and thermo-oxidative behaviour of polymer-based nanocomposites

The aim of this work is the investigation of the effect of ultrasound treatment on the structural characteristics of carbon nanotubes (CNTs) and the consequent influence that the shortening induced by sonication exerts on the morphology, rheological behaviour and thermo-oxidative resistance of ultra-high molecular weight polyethylene (UHMWPE)-based nanocomposites. First, CNTs have been subjected to sonication for different time intervals and the performed spectroscopic and morphological analyses reveal that a dramatic decrease of the CNT's original length occurs with increased sonication time. The reduction of the initial length of CNTs strongly affects the nanocomposite rheological behaviour, which progressively changes from solid-like to liquid-like as the CNT sonication time increases. The study of the thermo-oxidative behaviour of the investigated nanocomposites reveals that the CNT sonication has a detrimental effect on the thermo-oxidative stability of nanocomposites, especially for long exposure times. The worsening of the thermo-oxidative resistance of sonicated CNT-containing nanocomposites could be attributed to the lower thermal conductivity of low-aspect-ratio CNTs, which causes the increase of the local temperature at the polymer/nanofillers interphase, with the consequent acceleration of the degradative phenomena

Comparison of Branched and Linear Perfluoropolyether Chains Functionalization on Hydrophobic, Morphological and Conductive Properties of Multi-Walled Carbon Nanotubes

The functionalization of multi-walled carbon nanotubes (MW-CNTs) was obtained by generating reactive perfluoropolyether (PFPE) radicals that can covalently bond to MW-CNTs’ surface. Branched and linear PFPE peroxides with equivalent molecular weights of 1275 and 1200 amu, respectively, have been thermally decomposed for the production of PFPE radicals. The functionalization with PFPE chains has changed the wettability of MW-CNTs, which switched their behavior from hydrophilic to super-hydrophobic. The low surface energy properties of PFPEs have been transferred to MW-CNTs surface and branched units with trifluoromethyl groups, CF3, have conferred higher hydrophobicity than linear units. Porosimetry discriminated the effects of PFPE functionalization on meso-porosity and macro-porosity. It has been observed that reactive sites located in MW-CNTs mesopores have been intensively functionalized by branched PFPE peroxide due to its low average molecular weight. Conductivity measurements at different applied pressures have showed that the covalent linkage of PFPE chains, branched as well as linear, weakly modified the electrical conductivity of MW-CNTs. The decomposed portions of PFPE residues, the PFPE chains bonded on carbon nanotubes, and the PFPE fluids obtained by homo-coupling side-reactions were evaluated by mass balances. PFPE-modified MW-CNTs have been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), static contact angle (SCA), surface area, and porosity measurement

Amino-TEMPO grafted on magnetic multi walled nanotubes: An efficient and recyclable heterogeneous oxidation catalyst

An efficient and easy recyclable heterogeneous oxidation catalyst was prepared by grafting TEMPO–NH2 moieties on the surface of magnetic multi-walled carbon nanotubes (MWCNT), first by a radical reaction introducing butyric acid moieties on carbon nanotube surface. Subsequently, carboxylic acid moieties were submitted for amidation using TEMPO–NH2. The functionalized nanotubes [MWCNT-{(CH2)3-CO-NHTEMPO} n] were investigated as a (pre-)catalyst for the oxidation of primary and secondary alcohols for the production of aldehydes and ketones in a Montanari-type catalytic oxidation using the cheap and readily available 1,3-dichloro-5,5-dimethylhydantoin as the terminal oxidant

Proteomic fingerprinting of protein corona formed on PEGylated multi-walled carbon nanotubes

In Nanomedicine, carbon-based nanomaterials, like Carbon Nanotubes (CNT), are considered potential candidates as drug delivery systems. In vivo adsorption of physiological proteins onto carbon nanotubes, through noncovalent interactions, forms a protein corona or bio corona, able to influence biological properties and biocompatibility of CNT. This study aimed to explore the composition of protein corona formed onto PEGylated Multi-Walled Carbon Nanotubes (MWCNT-PEG5k), after their incubation in human plasma. Plasma proteins were sequentially eluted in different conditions by using both native and denaturant buffers, useful to characterize soft and hard corona. Proteomic methods and mass spectrometry analysis have identified proteins in soft corona, involved in the regulation of immune response and in the CNT transport, and biomolecules in hard corona with a role in the maintenance of host homeostasis. These promising results have demonstrated the potential of PEGylated Multi-Walled Carbon Nanotubes as future candidates for drug delivery

The Baeyer-Villiger oxidation versus aromatic ring hydroxylation: competing organic peracid oxidation mechanisms explored by multivariate modelling of designed multi-response experiments

Peroxy acids can be used as the terminal oxidant for the Baeyer–Villiger oxidation of acetophenones and for direct ring hydroxylation of methoxy-substituted benzenes. An oxidative system involving 3-chloroperbenzoic acid (mCPBA) and 2,6- dimethoxyacetophenone as model substrate was investigated by means of statistical experimental design, multivariate modelling and response surface methodology. The outcome of the organic peracid oxidation experiments was portrayed by a multi-response matrix consisting of the yields of three different compounds; 2,6-dimethoxyphenyl acetate, 1-(4-hydroxy-2,6-dimethoxy-phenyl)ethanone and 3-hydroxy-2,6-dimethoxy-phenyl acetate. The optimized reaction protocol was utilized to investigate a series of various substituted acetophenones. The overall investigation revealed that both the molecular structure of the acetophenone substrate and the experimental conditions exhibited a substantial impact on whether the oxidation reaction follows the oxygen insertion or direct ring hydroxylation mechanism. An improved protocol for the direct ring hydroxylation was also obtained from the experimental and modelling described herei