Rossella Arrigo

Hybrid supramolecular gels of Fmoc-F/halloysite nanotubes: systems for sustained release of camptothecin

Supramolecular gel hybrids obtained by self-assembly of Fmoc-l-phenylalanine (Fmoc-F) in the presence of functionalized halloysite nanotubes (f-HNT) were obtained in biocompatible solvents and employed as carriers for the delivery of camptothecin (CPT) molecules. The synthesis of the new f-HNT material as well as its characterization are described. The properties of the hybrid hydrogels and organogels were analyzed by several techniques. The presence of small amounts of f-HNT allows good dispersion of the tubes and the subsequent formation of homogeneous gels. The experimental results show that f-HNT functions only as an additive in the hybrid gels and does not demonstrate gelator behavior. The in vitro kinetic release from both f-HNT/CPT and Fmoc-F/f-HNT/CPT was studied in media that imitates physiological conditions, and the factors controlling the release process were determined and discussed. Furthermore, the antiproliferative in vitro activities of the gels were evaluated towards human cervical cancer HeLa cells. A comparison of data collected in both systems shows the synergistic action of f-HNT and the gel matrix in controlling the release of CPT in the media and maintaining the drug in its active form. Finally, a comparison with pristine HNT is also reported. This study suggests a suitable strategy to obtain two-component gel hybrids based on nanocarriers with controlled drug carrier capacity for biomedical applications.

Natural compounds as light stabilizer for a starch-based biodegradable polymer

Abstract The photooxidation behavior of a commercial starch-based biodegradable polymer, i.e., new generation Mater-Bi, loaded with natural stabilizers was investigated in consideration for outdoor agricultural applications. The photooxidation behavior of the biodegradable films was monitored mainly by mechanical tests and spectroscopic analysis. In order to formulate biodegradable films without any synthetic compounds, suitable for outdoor applications and with good photooxidation stability, antioxidants such as α-tocopherol and quercetin (Q) were considered. The results obtained using natural compounds were compared with those obtained by using a synthetic antioxidant and a light stabilizer. Among the investigated natural compounds, the flavonoid compound seemed to work better than the antioxidant and the improvement in the photooxidation behavior of the biodegradable film was very similar to that obtained using the synthetic light stabilizer. A flavonoid compound can be considered as an outstanding natural stabilizer to replace synthetic light stabilizers in the formulation of 100% natural compounds based films, suitable for outdoor applications.

Advanced nano-hybrids for thermo-oxidative-resistant nanocomposites

In the present work, trisilanol phenyl polyhedral olygomeric silsesquiosane (TSPh-POSS) has been physically immobilized onto carbon nanotubes (CNTs) bearing covalently linked Br-terminated long-alkyl chain (Br-alkyl-f-CNTs), and the so obtained hybrid nanoparticles (Br-alkyl-f-CNTs/TSPh-POSS) have been used to prepare ultra-high molecular weight polyethylene (UHMWPE)-based nanocomposites with enhanced thermo-oxidative resistance. The effective immobilization of the TSPh-POSS molecules has been confirmed by spectroscopic and thermo-gravimetric analyses. Besides, the influence of the hybrid nanoparticles on the rheological and mechanical behaviour and morphology of the nanocomposites have been fully investigated. The obtained results show that the rheological and thermo-mechanical behaviour of UHMWPE/Br-alkyl-f-CNTs/TSPh-POSS nanocomposite is affected by two different opposite contributions: reinforcement effect of CNTs and plasticizing action induced by TSPh-POSS molecules. The unexpected excellent thermo-oxidative resistance of the nanocomposite containing hybrid nanoparticles seems to be due to a synergistic effect of TSPh-POSS and CNTs. Moreover, TSPh-POSS molecules, upon thermo-oxidative treatment, are able to migrate toward film surface, forming a TSPh-POSS-rich protective layer that hinders the oxygen diffusion.

Immobilization of natural anti-oxidants on carbon nanotubes and aging behavior of ultra-high molecular weight polyethylene-based nanocomposites

The use of natural antioxidants is an attractive way to formulate nanocomposites with extended durability and with potential applications in bio-medical field. In this work, Vitamin E (VE) in the form of α-tocopherol and Quercetin (Q) are physically immobilized on the outer surface of multi-walled carbon nanotubes (CNTs). Afterward, the CNTs-VE and CNTs-Q are used to formulate thermally stable ultra high molecular weight polyethylene based nanocomposites. The obtained results in the study of the thermo-oxidation behavior suggest a beneficial effect of the natural anti-oxidant carbon nanotubes systems. The unexpected excellent thermo-resistance of the nanocomposites seems to be due to a synergistic effect of the natural anti-oxidant and carbon nanotubes, i.e. strong interaction between CNT surface and anti-oxidant molecules. Particularly, these interactions cause the formation of structural defects onto outer CNT surfaces, which, in turn, increase the CNT radical scavenging activity.

Rheological Percolation Threshold in High-Viscosity Polymer/CNTs Nanocomposites

AbstractPolystyrene (PS)/multi-walled carbon nanotubes (CNT) nanocomposites have been prepared through melt mixing processing aiming at obtaining a uniform and homogeneous dispersion of the used nanoparticles within the polymeric matrix. Optical and scanning electron microscopy has been employed to determine the dispersion and distribution of CNTs at different length scales. Furthermore, the linear viscoelastic behavior of formulated nanocomposites has been deeply investigated. As a result of CNTs added, the nanocomposites experience a transition from liquid-like to solid-like rheological behavior, and a disappearance of relaxation processes at low frequency can be noticed. By plotting G’ versus CNTs loading and fitting with a power-law function, the rheological threshold of PS-based nanocomposites has been calculated. Moreover, the mechanical behavior of nanocomposites has been investigated and related to the formed CNTs network within polymer matrix.

Biopolyester-based systems containing naturally occurring compounds with enhanced thermo-oxidative stability

Background This work presents a sustainable approach for the stabilization of polylactic acid (PLA) against thermo-oxidative aging. Methods Naturally occurring phenolic and polyphenolic compounds, such as ferulic acid (FerAc), vanillic acid (VanAc), quercetin (Querc) and vitamin E (VitE), were introduced into PLA. Results The preliminary characterization of the systems formulated containing different amounts of natural stabilizers showed that all compounds used acted as plasticizers, leading to a decrease in rheological functions with respect to neat PLA, without significantly modifying the crystallinity of the raw material. The study of the thermo-oxidative behavior of neat PLA and PLA/natural compound systems, performed by spectrometric and thermal analyses, indicated that all stabilizers considered were able to exert a remarkable antioxidant action against thermo-oxidative phenomena. Conclusions All natural compounds considered are thus proposed as ecofriendly stabilizers, to get fully bio-based polymer systems with enhanced thermo-oxidative stability, suitable for biomedical applications.

On the role of multi-functional polyhedral oligomeric silsesquioxane in polystyrene-zinc oxide nanocomposites

Abstract Multi-functional trisilanol phenyl (TSPH) and trisilanol isobutyl (TSIB) polyhedral oligomeric silsesquioxane (POSS) have been used in the formulation of advanced polystyrene (PS)-zinc oxide (ZnO) nanocomposites. The neat matrix and PS/ZnO-based nanocomposites have been characterized through rheological, morphological, mechanical, and dynamic thermo-mechanical analysis. Both TSPH and TSIB are able to improve the dispersion of ZnO into the polystyrene matrix; furthermore, adding TSIB leads to better results because it facilitates better solubility into the PS matrix and interaction/reaction with the ZnO nanopowder. Finally, the optical properties and photo-oxidative resistance of the nanocomposite films have been evaluated. The POSS molecules synergistically interact with ZnO nanopowder in the protection of PS matrix against photo-oxidative process. The nanocomposite films containing both ZnO and POSS molecules, particularly TSIB, exhibit better UV-shielding properties than the PS/ZnO one, without loss of optical transparency.

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.

Supramolecular Hydro- and Ionogels: A Study of Their Properties and Antibacterial Activity

Diimidazolium-based organic salts, bearing peptides or amino acids as anions have been synthesised and tested for their gelling ability in biocompatible solvents. These low molecular weight salts were successfully used as gelators in phosphate buffered saline (PBS) solution and ionic liquids. Then, the properties of the obtained soft materials were analysed in terms of melting temperature and gel strength as accounted for by rheological investigations. The gel-phase formation was studied by using UV/Vis and resonance light scattering measurements, whereas the morphology of the soft materials was analysed by using polarised optical microscopy and scanning electron microscopy. To get information about the organisation of the gelator in the gelatinous matrix, X-ray diffraction measurements were performed both on the neat gelators and their gels. The results collected show that the properties of the gel phases, like the thermal stability, the self-repairing ability, the resistance to flow as well as the morphology, are dependent on the nature of the anion. Furthermore, bioassays revealed that the obtained diimidazolium organic salts possessed antimicrobial activity, against gram-negative and gram-positive tester strains. In particular and noteworthy, the diimidazolium organic salts exert a bactericidal capability, which was retained even if they are included in the gel phase. Thus, a novel kind of bioactive soft material was obtained that could be fruitfully employed as a non-covalent coating exerting antibacterial capability.

Double bond-functionalized POSS: dispersion and crosslinking in polyethylene-based hybrid obtained by reactive processing

Polyethylene-based organic inorganic hybrids were prepared by one-step reactive melt mixing using a mono-functionalized nanofiller, i.e., allyl-heptaisobutyl-substituted polyhedral oligomeric silsesquioxane (1POSS) and a multi-functionalized octavinyl polyhedral oligomeric silsesquioxane (8POSS). The hybrids were also prepared in dicumyl peroxide (DCP) presence and morphological, spectroscopical and calorimetric analysis were carried out. Moreover, rheological measurement and Sohxlet extraction were performed on investigated samples. It was inferred that double bonds of POSS functional groups were triggered by radicals coming from the peroxide decomposition or from the degradation reactions occurring during preparation. The type of the functional groups (mono- or multi-reactive) of the POSS is a leading factor, along with radicals content in the systems, in the formation of a polymeric network. In particular, the presence of multi-reactive groups in 8POSS molecules results in a successful POSS grafting/crosslinking in the polymeric backbone: the covalent bonds formation between nanofillers and matrix during processing improves POSS dispersion within the polyolefin matrix and leads to a network structure formation.