Bottom-Up Strategy to Forecast the Drug Location and Release Kinetics in Antitumoral Electrospun Drug Delivery Systems.

Electrospun systems are becoming promising devices usable for topical treatments. They are eligible to deliver different therapies, from anti-inflammatory to antitumoral. In the current research, polycaprolactone electrospun membranes loaded with synthetic and commercial antitumoral active substances were produced, underlining how the matrix-filler affinity is a crucial parameter for designing drug delivery devices. Nanofibrous membranes loaded with different percentages of Dacarbazine (the drug of choice for melanoma) and a synthetic derivative of Dacarbazine were produced and compared to membranes loaded with AuM1, a highly active Au-complex with low affinity to the matrix. AFM morphologies showed that the surface profile of nanofibers loaded with affine substances is similar to one of the unloaded systems, thanks to the nature of the matrix-filler interaction. FTIR analyses proved the efficacy of the interaction between the amidic group of the Dacarbazine and the polycaprolactone. In AuM1-loaded membranes, because of the weak matrix-filler interaction, the complex is mainly aggregated in nanometric domains on the nanofiber surface, which manifests a nanometric roughness. Consequently, the release profiles follow a Fickian behavior for the Dacarbazine-based systems, whereas a two-step with a highly prominent burst effect was observed for AuM1 systems. The performed antitumoral tests evidence the high-cytotoxic activity of the electrospun systems against melanoma cell lines, proving that the synthetic substances are more active than the commercial dacarbazine.

Electrospun Membranes Designed for Burst Release of New Gold-Complexes Inducing Apoptosis of Melanoma Cells.

Two non-commercial metallic Au-based complexes were tested against one of the most aggressive malignant melanomas of the skin (MeWo cells), through cell viability and time-lapse live-cell imaging system assays. The tests with the complexes were carried out both in the form of free metallic complexes, directly in contact with the MeWo cell line culture, and embedded in fibers of Polycaprolactone (PCL) membranes produced by the electrospinning technique. Membranes functionalized with complexes were prepared to evaluate the efficiency of the membranes against the melanoma cells and therefore their feasibility in the application as an antitumoral patch for topical use. Both series of tests highlighted a very effective antitumoral activity, manifesting a very relevant cell viability inhibition after both 24 h and 48 h. In the case of the AuM1 complex at the concentration of 20 mM, melanoma cells completely died in this short period of time. A mortality of around 70% was detected from the tests performed using the membranes functionalized with AuM1 complex at a very low concentration (3 wt.%), even after 24 h of the contact period. The synthesized complexes also manifest high selectivity with respect to the MeWo cells. The peculiar structural and morphological organization of the nanofibers constituting the membranes allows for a very effective antitumoral activity in the first 3 h of treatment. Experimental points of the release profiles were perfectly fitted with theoretical curves, which easily allow interpretation of the kinetic phenomena occurring in the release of the synthesized complexes in the chosen medium.

Multifunctionality of structural nanohybrids: the crucial role of carbon nanotube covalent and non-covalent functionalization in enabling high thermal, mechanical and self-healing performance.

This study proposes new kinds of functionalization procedures able to preserve specific properties of carbon nanotubes (CNTs) and to improve compatibility with the epoxy matrix. Through a covalent approach, for the first time, CNTs are functionalized with the same hardener agent, 4,4'-diaminodiphenyl sulfone, employed to solidify the epoxy matrix and capable to fulfill mechanical requirements of industrial structural resins. The same CNTs are non-covalently modified through the polymer wrapping mechanism with benzoxazine (Bz) terminated polydimethylsiloxane (PDMS). The comparison between electrical and mechanical properties of the nanocomposites highlights the success of the non-covalent functionalization in determining an increase in the glass transition temperature (Tg) and in better preserving the unfunctionalized CNT electrical conductivity. Besides, tunneling atomic force microscopy (TUNA), powerful to catch ultra-low currents, has been used for revealing the morphology on nanoscale domains and detecting the conductivity on the same location of CNT/epoxy resins. No electrical contacts to the grounds have been used for the TUNA analysis; a procedure that does not alter the results on the interface domains which experience contact areas with strong differences in their properties. The effectiveness of performed CNT functionalizations as a route to impart self-healing efficiency to the resin formulations has also been proved.

Influence of carbon nanoparticles/epoxy matrix interaction on mechanical, electrical and transport properties of structural advanced materials.

The focus of this study is to design new nano-modified epoxy formulations using carbon nanofillers, such as carbon nanotubes, carbon nanofibers and graphene-based nanoparticles (CpEG), that reduce the moisture content and provide additional functional performance. The chemical structure of epoxy mixture, using a non-stoichiometric amount of hardener, exhibits unique properties in regard to the water sorption for which the equilibrium concentration of water (C eq) is reduced up to a maximum of 30%. This result, which is very relevant for several industrial applications (aeronautical, shipbuilding industries, wind turbine blades, etc), is due to a strong reduction of the polar groups and/or sites responsible to bond water molecules. All nanofillers are responsible of a second phase at lower glass transition temperature (Tg). Compared with other carbon nanofillers, functionalized graphene-based nanoparticles exhibit the best performance in the multifunctionality. The lowest moisture content, the high performance in the mechanical properties, the low electrical percolation threshold (EPT) have been all ascribed to particular arrangements of the functionalized graphene sheets embedded in the polymeric matrix. Exfoliation degree and edge carboxylated groups are responsible of self-assembled architectures which entrap part of the resin fraction hindering the interaction of water molecules with the polar sites of the resin, also favouring the EPT paths and the attractive/covalent interactions with the matrix.

The role of carbon nanofiber defects on the electrical and mechanical properties of CNF-based resins.

Heat treatment of carbon nanofibers has proven to be an effective method in removing defects from carbon nanofibers, causing a strong increase in their structural perfection and thermal stability. It affects the bonding states of carbon atoms in the nanofiber structure and causes a significant transformation in the hybridization state of the bonded carbon atoms.Nanofilled resins made of heat-treated CNF show significant increases in their electrical conductivity even at low concentrations. This confirms that enhancement in the perfection of the fiber structure with consequent change in the morphological features plays a prominent role in affecting the electrical properties. Indeed heat-treated CNFs display a stiff structure and a smooth surface which tends to lower the thickness of the unavoidable insulating epoxy layer formed around the CNF which, in turn, plays a fundamental role in the electrical transport properties along the conducting clusters. This might be very beneficial in terms of electrical conductivity but might have negligible effect on the mechanical properties.

Entrapment of Acridine Orange in Metakaolin-Based Geopolymer: A Feasibility Study.

Few studies have explored the immobilization of organic macromolecules within the geopolymer matrix, and some have found their chemical instability in the highly alkaline geopolymerization media. The present work reports on the feasibility of encapsulating the potentially toxic acridine orange (AO) dye in a metakaolin based geopolymer while maintaining its structural integrity. The proper structural, chemical, and mechanical stabilities of the final products were ascertained using Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric (TGA/DTG), and mechanical analyses, whereas the dye integrity and its stability inside the geopolymer were investigated by the UV-Vis analysis. In addition, the antimicrobial activity was investigated. The FT-IR and XRD analyses confirmed the geopolymerization occurrence, whereas the TGA/DTG and mechanical (compressive and flexural) strength revealed that the addition of 0.31% (AO mg/ sodium silicate L) of AO to the fresh paste did not affect the thermal stability and the mechanical properties (above 6 MPa in flexural strength and above 20 MPa for compressive strength) of the hardened product. UV-Vis spectroscopy revealed that the dye did not undergo chemical degradation nor was it released from the geopolymer matrix. The results reported herein provide a useful approach for the safe removal of toxic macromolecules by means of encapsulation within the geopolymer matrix.

Thermal and Electrical Characterization of Polyester Resins Suitable for Electric Motor Insulation.

This paper undertakes the thermal and electrical characterization of three commercial unsaturated polyester imide resins (UPIR) to identify which among them could better perform the insulation function of electric motors (high-power induction motors fed by pulse-wide modulation (PWM) inverters). The process foreseen for the motor insulation using these resins is Vacuum Pressure Impregnation (VPI). The resin formulations were specially selected because they are one-component systems; hence, before the VPI process, they do not require mixing steps with external hardeners to activate the curing process. Furthermore, they are characterized by low viscosity and a thermal class higher than 180 °C and are Volatile Organic Compound (VOC)-free. Thermal investigations using Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) techniques prove their excellent thermal resistance up to 320 °C. Moreover, impedance spectroscopy in the frequency range of 100 Hz-1 MHz was analyzed to compare the electromagnetic performance of the considered formulations. They manifest an electrical conductivity starting from 10-10 S/m, a relative permittivity around 3, and a loss tangent value lower than 0.02, which appears almost stable in the analyzed frequency range. These values confirm their usefulness as impregnating resins in secondary insulation material applications.

Nanometric Mechanical Behavior of Electrospun Membranes Loaded with Magnetic Nanoparticles.

This work analyzes on nanoscale spatial domains the mechanical features of electrospun membranes of Polycaprolactone (PCL) loaded with Functionalized Magnetite Nanoparticles (FMNs) produced via an electrospinning process. Thermal and structural analyses demonstrate that FMNs affect the PCL crystallinity and its melting temperature. HarmoniX-Atomic Force Microscopy (H-AFM), a modality suitable to map the elastic modulus on nanometric domains of the sample surface, evidences that the FMNs affect the local mechanical properties of the membranes. The mechanical modulus increases when the tip reveals the magnetite nanoparticles. That allows accurate mapping of the FMNs distribution along the nanofibers mat through the analysis of a mechanical parameter. Local mechanical modulus values are also affected by the crystallinity degree of PCL influenced by the filler content. The crystallinity increases for a low filler percentage (<5 wt.%), while, higher magnetite amounts tend to hinder the crystallization of the polymer, which manifests a lower crystallinity. H-AFM analysis confirms this trend, showing that the distribution of local mechanical values is a function of the filler amount and crystallinity of the fibers hosting the filler. The bulk mechanical properties of the membranes, evaluated through tensile tests, are strictly related to the nanometric features of the complex nanocomposite system.

Role of MWCNTs Loading in Designing Self-Sensing and Self-Heating Structural Elements.

This work proposes nanocomposites with carbon nanotubes characterized by self-sensing and self-heating properties. Recently, a growing interest in these two properties has been found in many industrial sectors, especially in the aerospace and automotive fields. While the self-sensing function allows diagnosing the presence of micro-damage in the material thanks to the detection of residual resistance, the self-heating function is exploited to properly tune the heating performance in terms of the heating rate and final temperature values. An electrical percolation value of around 0.5% by weight of carbon nanotubes was found by electrical characterization. The AC conductivity of the nanocomposites, in the range of 100 Hz to 1 MHz, evidences that beyond a CNTs amount of 0.5% wt/wt, they are characterized by a purely resistive behavior. The self-sensing analysis displayed a gauge factor value of 4.1. The solid thermal stability up to 300 °C makes the material suitable as a heating element at high temperatures. SEM investigations and temperature maps evidence a good dispersion of the conductive filler in the epoxy matrix and, consequently, good isotropy in heat distribution. As regards the trend of electrical resistance by varying the temperature, the electro-thermal investigation has shown the presence of both Positive Temperature Coefficient (PTC) and Negative Temperature Coefficient (NTC) behaviors with a predominance of NTC as soon as the temperature becomes closer to the glass transition temperature of the epoxy resin.

Rheological, Thermal and Mechanical Characterization of Toughened Self-Healing Supramolecular Resins, Based on Hydrogen Bonding.

This paper proposes the design of toughened self-healing supramolecular resins able to fulfill functional and structural requirements for industrial applications. These new nanocomposites are based on compounds acting as promotors of reversible self-healing interactions. Electrically conductive carbon nanotubes, selected among those allowing to reach the electrical percolation threshold (EPT) with a very low amount of nanofiller, were dispersed in the self-healing polymeric matrix to contrast the electrical insulating properties of epoxy matrices, as required for many applications. The formulated supramolecular systems are thermally stable, up to 360 °C. Depending on the chemical formulation, the self-healing efficiency η, assessed by the fracture test, can reach almost the complete self-repairing efficiency (η = 99%). Studies on the complex viscosity of smart nanocomposites highlight that the effect of the nanofiller dominates over those due to the healing agents. The presence of healing compounds anchored to the hosting epoxy matrix determines a relevant increase in the glass transition temperature (Tg), which results in values higher than 200 °C. Compared to the unfilled matrix, a rise from 189 °C to 223 °C is found for two of the proposed formulations.

Effective Practical Solutions for De-Icing of Automotive Component.

Carbon Nanotube (CNTs)-based masterbatches have been mixed with thermoplastic polymers currently used to manufacture automotive components. These mixtures have been tailored to integrate an effective heating function in the materials. The manufacturing method for composite compounding and processing conditions significantly affects the electrical resistivity of the developed materials. The resistivity of the material can be controlled within tight tolerances sufficient to meet automotive requirements. The optimal compounding parameters of the melt process technologies were defined to obtain uniform filler dispersion and distribution. Heating and de-icing tests were performed on sheet specimens with optimized CNT content and electrical conductivity suitable for effective electro-thermal behaviour with low input voltages (≤24 V DC), making them safe for users. Finally, a simplified analytical model of the Joule effect arising from an energy balance of the system under study (heat equation) was developed and validated by comparison with experimental data for use in future development for the purpose of the preliminary design of components in the automotive sector.

Resistive Response of Carbon Nanotube-Based Composites Subjected to Water Aging.

This work aimed to monitor, through the changes in electrical resistance, the evolution of the mechanical properties due to aging caused by water sorption in carbon nanotube-based epoxy composites. The epoxy/CNT nanocomposites were prepared by dispersing the filler in the precursor through the ultra-sonication process and mixing the hardener by mechanical stirring. After an evaluation of the electrical properties, detected through a two-probe electrical measurement method, of nanocomposites at different percentages by weight of the filler (0.025, 0.05, 0.1, 0.3, 0.5, and 1.0), a concentration (0.1% by weight), close to that of the electrical percolation threshold, was chosen to evaluate the resistive response. This specific concentration was selected in order to obtain maximized values of the variation detected for the changes in the electrical resistance resulting from phenomena of structural relaxations/rearrangements due to water absorption. In particular, the electrical conductivity value switched from 8.2 × 10-14 S/m for the unfilled epoxy resin to 6.3 × 10-2 S/m for carbon nanotube-based epoxy composite at 0.1% by weight of the nanofiller. The water sorption caused a reduction in the mechanical properties (storage modulus and tan δ) due to swelling and plasticization phenomena, which caused the structural reorganization of the conductive interparticle contacts in the matrix with a consequent variation in the electrical resistance of the material. The found 'non-Fickian' water diffusion behavior was very similar to the variation in the electrical resistance with time. This last correlation allows the association of the measurement of the electrical resistance with the quantity of absorbed water and, therefore, with the aging of the material to water absorption, through the sensitivity factor (ß). The resistive nature of the composite can be used to monitor the amount of water absorption and the changes in the structure of the material subject to water aging.

Self-Sensing Nanocomposites for Structural Applications: Choice Criteria.

Epoxy resins containing multi-wall carbon nanotubes (MWCNTs) have proven to be suitable for manufacturing promising self-sensing materials to be applied in the automotive and aeronautic sectors. Different parameters concerning morphological and mechanical properties of the hosting matrices have been analyzed to choose the most suitable system for targeted applications. Two different epoxy precursors, the tetrafunctional tetraglycidyl methylene dianiline (TGMDA) and the bifunctional bisphenol A diglycidyl ether (DGEBA) have been considered. Both precursors have been hardened using the same hardener in stoichiometric conditions. The different functionality of the precursor strongly affects the crosslinking density and, as a direct consequence, the electrical and mechanical behavior. The properties exhibited by the two different formulations can be taken into account in order to make the most appropriate choice with respect to the sensing performance. For practical applications, the choice of one formulation rather than another can be performed on the basis of costs, sensitivity, processing conditions, and most of all, mechanical requirements and in-service conditions of the final product. The performed characterization shows that the nanocomposite based on the TGMDA precursor manifests better performance in applications where high values in the glass transition temperature and storage modulus are required.

Ice-Prevention and De-Icing Capacity of Epoxy Resin Filled with Hybrid Carbon-Nanostructured Forms: Self-Heating by Joule Effect.

In this study, CNTs and graphite have been incorporated to provide electrical conductivity and self-heating capacity by Joule effect to an epoxy matrix. Additionally, both types of fillers, with different morphology, surface area and aspect ratio, were simultaneously incorporated (hybrid CNTs and graphite addition) into the same epoxy matrix to evaluate the effect of the self-heating capacity of carbon materials-based resins on de-icing and ice-prevention capacity. The self-heating capacity by Joule effect and the thermal conductivity of the differently filled epoxy resin were evaluated for heating applications at room temperature and at low temperatures for de-icing and ice-prevention applications. The results show that the higher aspect ratio of the CNTs determined the higher electrical conductivity of the epoxy resin compared to that of the epoxy resin filled with graphite, but the 2D morphology of graphite produced the higher thermal conductivity of the filled epoxy resin. The presence of graphite enhanced the thermal stability of the filled epoxy resin, helping avoid its deformation produced by the softening of the epoxy resin (the higher the thermal conductivity, the higher the heat dissipation), but did not contribute to the self-heating by Joule effect. On the other hand, the feasibility of electrically conductive epoxy resins for de-icing and ice-prevention applications by Joule effect was demonstrated.

Cure behavior and physical properties of epoxy resin-filled with multiwalled carbon nanotubes.

Different experimental procedures were investigated for incorporating Multi walled Carbon nanotubes (MWCNT) into epoxy diglycidil-ether bisphenol-A (DGEBA), cured with 4,4' diamine-dibenzyl-sulfone (DDS): (i) mechanical mixing for either 60 or 120 minutes; (ii) high energy ball milling for 30 minutes; (iii) ultrasonication for 20 minutes. The mechanical properties of the obtained samples were monitored and used in order to guide the selection of the most promising composite system. The best results were obtained by using, as method of incorporation of carbon nanotubes in the resin, sonication for 20 minutes. Moreover it was found that the presence of an accelerating agent, BF3, commonly used for the cure reaction, is ineffective in the presence of carbon nanotubes, besides leading to composites with a lower glass transition. Afterwards resins with increasing MWCNT concentration were prepared and the thermal properties analyzed, showing a slight improvement in either the glass transition or the degradation temperature. The electrical conductivity of the selected composite system is characterised by a percolation threshold (lower than 0.1%) comparable to that found for similar systems, but beyond threshold it assumes greater values. The conductivity is characterised by only a slight increase with temperature in the range 30-90 degrees C. The positive temperature coefficient can be related to a decrease of the small gaps separating the CNTs clusters. A simple power law describes the relation between the composite conductivity and CNT concentration near the percolation threshold. A dependence of all the parameters of the power law on the temperature has also been evidenced, and it should be properly considered and indicated when using such a model in describing the behaviour of composites near the percolation threshold.

Design of Multifunctional Composites: New Strategy to Save Energy and Improve Mechanical Performance.

In this paper, an alternative curing strategy, based on the application of an electric field, is proposed to harden nano-filled multifunctional resins. The resin is obtained through the dispersion of carbon nanotubes, which act as nanometric heater elements in the epoxy matrix. The electro-curing is activated by applying an external electric voltage, which allows tunable cross-linking within the epoxy matrix entrapped between the nanotubes. The electro-curing method allows reaching higher curing degrees with respect to the conventional ones and, consequently, higher glass transition temperatures. This is a direct consequence of the fact that the curing reactions start directly in the regions at the interphase between carbon nanotubes, acting as heater nano-filaments, and the polymeric matrix. The proposed method is able to give composites better properties, making the curing process fast and energy-saving.

Damage Monitoring of Structural Resins Loaded with Carbon Fillers: Experimental and Theoretical Study.

In the present study, nanocomposite materials for structural applications with self-sensing properties are proposed. In particular, suitable processing of epoxy resins filled with carbon nanotubes and expanded graphite characterized by very different aspect ratio leads to nanocomposite systems with high glass transition temperatures and remarkable values of the gauge factor. In particular, this notable property ranges between four, for composites filled with one-dimensional nanofiller, and 39 for composites with two-dimensional (2D) graphite derivatives. The greater sensitivity of the 2D system against permanent deformations is interpreted on the basis of an empirical mathematical model and morphological descriptions. The larger inter-contact area among the graphite layers determines a larger contact resistance change than that occurring among carbon nanotubes. The proposed systems turn out to be very advantageous in strain-sensor applications where damage detection is a key requirement to guarantee the reliability of the structures and the safety of the end-users.

Low-Voltage Icing Protection Film for Automotive and Aeronautical Industries.

High-performance heater films are here proposed. They manifest great applicative potentiality in the de-icing technology of aircraft and motor vehicles. The films are suitable to be integrated into composite structures for the de/anti-icing function, which can be activated if the need arises. The heating is based on the joule effect of the current flowing through the electrically conductive films. Voltage and current parameters have been set based on the generators' capacities on-board an aircraft and a car, as well as on the energy consumption during the operating conditions and the autonomy in the time. Green processes have been employed through all preparative steps of the films, which are composed of expanded graphite (60% wt/wt) and polyvinyl alcohol (PVA) (40% wt/wt). The results reveal a very significant influence of the aspect ratio of the filler on the heating and de-icing performance and suggest how to enhance the de-icing efficiency saving energy and adapting the current on-board aircraft/car generators for de-icing operations.

Simulation of self-heating process on the nanoscale: a multiscale approach for molecular models of nanocomposite materials.

A theoretical-computational protocol to model the Joule heating process in nanocomposite materials is presented. The proposed modeling strategy is based on post processing of trajectories obtained from large scale molecular simulations. This protocol, based on molecular models, is the first one to be applied to organic nanocomposites based on carbon nanotubes (CNT). This strategy allows to keep a microscopic explicit picture of the systems, to directly catch the molecular structure underlying the process under study and, at the same time, to include macroscopic boundary conditions fixed in the experiments. As validation and first application of the proposed strategy, a detailed investigation on CNT based organic composites is reported. The effect of CNT morphologies, concentration and working conditions on Joule heating has been modelled and compared with available experiments. Further experiments are performed also in this work to increase the number of comparisons especially in specific voltage ranges where available references from literature were missing. Simulations are in both qualitative and quantitative agreement with several experiments and trends reported in the recent literature, as well as with experiments performed in this work. The proposed approach combined with large scale hybrid particle-field molecular simulations can give insights and opens to way to a rational design of self-heating nanocomposites.

Multifunctional Performance of a Nano-Modified Fiber Reinforced Composite Aeronautical Panel.

The adoption of multifunctional flame-resistant composites is becoming increasingly attractive for many components of aircrafts and competition cars. Compared to conventional alloy solutions, the reduced weight and corrosion resistance are only a couple of the relevant advantages they can offer. In this paper, a carbon fiber reinforced panel (CFRP) was impregnated with an epoxy resin enhanced using a combination of 0.5 wt% of carbon nanotubes (CNTs) and 5 wt% of Glycidyl-Polyhedral Oligomeric Silsesquioxanes (GPOSS). This formulation, which is peculiar to resins with increased electrical conductivity and flame-resistance properties, has been employed for manufacturing a carbon fiber reinforced panel (CFRP) composed of eight plies through a liquid infusion technique. Vibro-acoustic tests have been performed on the panel for the characterization of the damping performance, as well the transmission loss properties related to micro-handling treatments. The spectral excitation has been provided by an acoustic source simulating the aerodynamic pressure load agent on the structure. The incorporation of multi-walled carbon nanotubes MWCNTs in the epoxy matrix determines a non-trivial improvement in the dynamic performance of the laminate. An increased damping loss factor with reference to standard CFRP laminate and also an improvement of the sound insulation parameter was found for the specific test article.