Self-Standing 3D-Printed PEGDA-PANIs Electroconductive Hydrogel Composites for pH Monitoring.

Additive manufacturing (AM), or 3D printing processes, is introducing new possibilities in electronic, biomedical, sensor-designing, and wearable technologies. In this context, the present work focuses on the development of flexible 3D-printed polyethylene glycol diacrylate (PEGDA)- sulfonated polyaniline (PANIs) electrically conductive hydrogels (ECHs) for pH-monitoring applications. PEGDA platforms are 3D printed by a stereolithography (SLA) approach. Here, we report the successful realization of PEGDA-PANIs electroconductive hydrogel (ECH) composites produced by an in situ chemical oxidative co-polymerization of aniline (ANI) and aniline 2-sulfonic acid (ANIs) monomers at a 1:1 equimolar ratio in acidic medium. The morphological and functional properties of PEGDA-PANIs are compared to those of PEGDA-PANI composites by coupling SEM, swelling degree, I-V, and electro-chemo-mechanical analyses. The differences are discussed as a function of morphological, structural, and charge transfer/transport properties of the respective PANIs and PANI filler. Our investigation showed that the electrochemical activity of PANIs allows for the exploitation of the PEGDA-PANIs composite as an electrode material for pH monitoring in a linear range compatible with that of most biofluids. This feature, combined with the superior electromechanical behavior, swelling capacity, and water retention properties, makes PEGDA-PANIs hydrogel a promising active material for developing advanced biomedical, soft tissue, and biocompatible electronic applications.

A New Strong-Acid Free Route to Produce Xanthan Gum-PANI Composite Scaffold Supporting Bioelectricity.

Conductive hybrid xanthan gum (XG)-polyaniline (PANI) biocomposites forming 3D structures able to mimic electrical biological functions are synthesized by a strong-acid free medium. In situ aniline oxidative chemical polymerizations are performed in XG water dispersions to produce stable XG-PANI pseudoplastic fluids. XG-PANI composites with 3D architectures are obtained by subsequent freeze-drying processes. The morphological investigation highlights the formation of porous structures; UV-vis and Raman spectroscopy characterizations assess the chemical structure of the produced composites. I-V measurements evidence electrical conductivity of the samples, while electrochemical analyses point out their capability to respond to electric stimuli with electron and ion exchanges in physiological-like environment. Trial tests on prostate cancer cells evaluate biocompatibility of the XG-PANI composite. Obtained results demonstrate that a strong acid-free route produces an electrically conductive and electrochemically active XG-PANI polymer composite. The investigation of charge transport and transfer, as well as of biocompatibility properties of composite materials produced in aqueous environments, brings new perspective for exploitation of such materials in biomedical applications. In particular, the developed strategy can be used to realize biomaterials working as scaffolds that require electrical stimulations for inducing cell growth and communication or for biosignals monitoring and analysis.

Electrically conductive scaffolds mimicking the hierarchical structure of cardiac myofibers.

Electrically conductive scaffolds, mimicking the unique directional alignment of muscle fibers in the myocardium, are fabricated using the 3D printing micro-stereolithography technique. Polyethylene glycol diacrylate (photo-sensitive polymer), Irgacure 819 (photo-initiator), curcumin (dye) and polyaniline (conductive polymer) are blended to make the conductive ink that is crosslinked using free radical photo-polymerization reaction. Curcumin acts as a liquid filter and prevents light from penetrating deep into the photo-sensitive solution and plays a central role in the 3D printing process. The obtained scaffolds demonstrate well defined morphology with an average pore size of 300 ± 15 µm and semi-conducting properties with a conductivity of ~ 10-6 S/m. Cyclic voltammetry analyses detect the electroactivity and highlight how the electron transfer also involve an ionic diffusion between the polymer and the electrolyte solution. Scaffolds reach their maximum swelling extent 30 min after immersing in the PBS at 37 °C and after 4 weeks they demonstrate a slow hydrolytic degradation rate typical of polyethylene glycol network. Conductive scaffolds display tunable conductivity and provide an optimal environment to the cultured mouse cardiac progenitor cells.

A Sustainable Hydroxypropyl Cellulose-Nanodiamond Composite for Flexible Electronic Applications.

Designing fully green materials for flexible electronics is an urgent need due to the growing awareness of an environmental crisis. With the aim of developing a sustainable, printable, and biocompatible material to be exploited in flexible electronics, the rheological, structural and charge transport properties of water-based hydroxypropyl cellulose (HPC)-detonation nanodiamond (DND) viscous dispersions are investigated. A rheological investigation disclosed that the presence of the DND affects the orientation and entanglement of cellulose chains in the aqueous medium. In line with rheological analyses, the NMR diffusion experiments pointed out that the presence of DND modifies the hydrodynamic behavior of the cellulose molecules. Despite the increased rigidity of the system, the presence of DND slightly enhances the ionic conductivity of the dispersion, suggesting a modification in the charge transport properties of the material. The electrochemical analyses, performed through Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS), revealed that the HPC-DND system is remarkably stable in the explored voltage range (-0.1 to +0.4 V) and characterized by a lowered bulk resistance with respect to HPC. Such features, coupled with the printability and filmability of the material, represent good requirements for the exploitation of such systems in flexible electronic applications.

From Soft to Hard Biomimetic Materials: Tuning Micro/Nano-Architecture of Scaffolds for Tissue Regeneration.

Failure of tissues and organs resulting from degenerative diseases or trauma has caused huge economic and health concerns around the world. Tissue engineering represents the only possibility to revert this scenario owing to its potential to regenerate or replace damaged tissues and organs. In a regeneration strategy, biomaterials play a key role promoting new tissue formation by providing adequate space for cell accommodation and appropriate biochemical and biophysical cues to support cell proliferation and differentiation. Among other physical cues, the architectural features of the biomaterial as a kind of instructive stimuli can influence cellular behaviors and guide cells towards a specific tissue organization. Thus, the optimization of biomaterial micro/nano architecture, through different manufacturing techniques, is a crucial strategy for a successful regenerative therapy. Over the last decades, many micro/nanostructured biomaterials have been developed to mimic the defined structure of ECM of various soft and hard tissues. This review intends to provide an overview of the relevant studies on micro/nanostructured scaffolds created for soft and hard tissue regeneration and highlights their biological effects, with a particular focus on striated muscle, cartilage, and bone tissue engineering applications.

Effect of Volatile Organic Compounds Adsorption on 3D-Printed PEGDA:PEDOT for Long-Term Monitoring Devices.

We report on the preparation and stereolithographic 3D printing of a resin based on the composite between a poly(ethylene glycol) diacrylate (PEGDA) host matrix and a poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) filler, and the related cumulative volatile organic compounds' (VOCs) adsorbent properties. The control of all the steps for resin preparation and printing through morphological (SEM), structural (Raman spectroscopy) and functional (I/V measurements) characterizations allowed us to obtain conductive 3D objects of complex and reproducible geometry. These systems can interact with chemical vapors in the long term by providing a consistent and detectable variation of their structural and conductive characteristics. The materials and the manufacture protocol here reported thus propose an innovative and versatile technology for VOCs monitoring systems based on cumulative adsorption effects.

Graphene platelets from shungite rock modulate electropolymerization and charge storage mechanisms of soft-template synthetized polypyrrole-based nanocomposites.

We report here on soft-template electropolymerizations of polypyrrole (Ppy)-based nanocomposites triggered by graphene platelets (GP) from shungite (SH) rocks. A properly designed procedure for an efficient extraction of graphene platelets from SH powders is established to produce remarkable graphene materials in a low oxidation state and with a high electrical conductivity (1490 S cm-1). By using positively and negatively charged templating surfactants the role played by the graphene units on the electropolymerization reactions is pointed out by SEM, EDX, TEM, SAED, XPS and Raman spectroscopy. The morphological/structural characterizations highlight that GP from SH have a surface chemistry suitable for selective and mutual interactions with the growing Ppy chains. CV and galvanostatic charge/discharge measurements evidence that GP improve the transport of both electrons and ions within the bulk material by means of a synergistic action with the polymer phase. This cooperative behavior induces an enhancement of the specific capacitance up to 250 F g-1 at 2 A g-1. The Ppy-GP materials produced following the settled protocols result to be appropriate for fabricating multifunctional charge transport and storage electroactive systems.

Shungite Carbon as Unexpected Natural Source of Few-Layer Graphene Platelets in a Low Oxidation State.

The paper reports on the feasibility of obtaining graphene nanomaterials with remarkable structural and chemical features from shungite rocks. The investigation of the composition and structural modifications induced in the pristine, natural C-containing mineraloid by a specifically designed physicochemical purification treatment is performed by a combined use of several techniques (scanning electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, Raman and X-ray photoelectron spectroscopies). The adopted material processing enables efficient extraction of the C phase in the form of thin polycrystalline platelets of a few hundred nanometers sizes, and formed by 6-10 graphene sheets. About 80% of such nanostructures are characterized by a regular sp2 C honeycomb lattice and an ordered stacking of graphene layers with a d-spacing of ∼0.34 nm. The low oxygen content (∼5%), mainly found in the form of hydroxyl functional groups, provides the graphene platelets (GP) with a chemistry strictly close to that of conventional rGO materials. Such a feature is supported by the high conductivity value of 1.041 × 103 S cm-1 found for pelletized GP, which can be considered a valuable active material for a wide spectrum of advanced applications.

Nanotechnology for Food Packaging and Food Quality Assessment.

Nanotechnology has paved the way to innovative food packaging materials and analytical methods to provide the consumers with healthier food and to reduce the ecological footprint of the whole food chain. Combining antimicrobial and antifouling properties, thermal and mechanical protection, oxygen and moisture barrier, as well as to verify the actual quality of food, e.g., sensors to detect spoilage, bacterial growth, and to monitor incorrect storage conditions, or anticounterfeiting devices in food packages may extend the products shelf life and ensure higher quality of foods. Also the ecological footprint of food chain can be reduced by developing new completely recyclable and/or biodegradable packages from natural and eco-friendly resources. The contribution of nanotechnologies to these goals is reviewed in this chapter, together with a description of portable devices ("lab-on-chip," sensors, nanobalances, etc.) which can be used to assess the quality of food and an overview of regulations in force on food contact materials.

Hydrogen Adsorption Properties of Carbon Nanotubes and Platinum Nanoparticles from a New Ammonium-Ethylimidazolium Chloroplatinate Salt.

Self-supporting membranes built entirely of carbon nanotubes have been prepared by wet methods and characterized by Raman spectroscopy. The membranes are used as supports for the electrodeposition of Pt nanoparticles without the use of additional additives and/or stabilizers. The Pt precursor is an ad hoc synthesized ammonium-ethylimidazolium chloroplatinate(IV) salt, [NH3 (CH2 )2 MIM)][PtCl6 ]. The Pt complex was characterized using NMR spectroscopy, XRD, ESI-MS, and FTIR spectroscopy. The interaction between the Pt-carbon nanotubes nanocomposites and hydrogen is analyzed using electrochemical and quartz microbalance measurements under near-ambient conditions. The contribution of the Pt phase to the hydrogen adsorption on nanotube is found and explained by a kinetic model that takes into account a spillover event. Such a phenomenon may be exploited conveniently for catalysis and electrocatalysis applications in which the hybrid systems could act as a hydrogen transfer agent in specific hydrogenation reactions.

Polyaniline-nanodiamond fibers resulting from the self-assembly of nano-fibrils: a nanomechanical study.

Based on atomic force microscopy (AFM), torsional harmonics atomic force microscopy (TH-AFM, also referred to with the commercial name HarmoniX™) allows one to perform a quantitative characterization of the mechanical properties of soft samples on the nanometer scale. In this work, such a technique has been employed to study the mechanical properties of self-assembled micrometric fibers of polyaniline (PANI) doped with nanodiamond (ND) particles and to investigate the role of ND in the assembly. In particular, besides PANI-ND fibers, other features, i.e., nano-fibrils and blobs, have also been observed on the sample, the mechanical properties of which have been determined and compared after correcting for the effect of the substrate and of the cylindrical geometry of nano-fibrils. Their similar mechanical properties suggest that PANI-ND micro-fibers are constituted by self-assembly of nano-fibrils. Finally, the combination of nanomechanical characterization with energy dispersive X-ray (EDX) and Raman analyses allowed us to determine that softer blobs are residuals of amorphous PANI not polymerized in nano-fibrils.

Nanodiamonds for field emission: state of the art.

The aim of this review is to highlight the recent advances and the main remaining challenges related to the issue of electron field emission (FE) from nanodiamonds. The roadmap for FE vacuum microelectronic devices envisages that nanodiamonds could become very important in a short time. The intrinsic properties of the nanodiamond materials indeed meet many of the requirements of cutting-edge technologies and further benefits can be obtained by tailored improvements of processing methodologies. The current strategies used to modulate the morphological and structural features of diamond to produce highly performing emitting systems are reported and discussed. The focus is on the current understanding of the FE process from nanodiamond-based materials and on the major concepts used to improve their performance. A short survey of non-conventional microsized cold cathodes based on nanodiamonds is also reported.

Nanocarbon surfaces for biomedicine.

The distinctive physicochemical, mechanical and electrical properties of carbon nanostructures are currently gaining the interest of researchers working in bioengineering and biomedical fields. Carbon nanotubes, carbon dendrimers, graphenic platelets and nanodiamonds are deeply studied aiming at their application in several areas of biology and medicine.   Here we provide a summary of the carbon nanomaterials prepared in our labs and of the fabrication techniques used to produce several biomedical utilities, from scaffolds for tissue growth to cargos for drug delivery and to biosensors.

Mechanical characterization of polymeric thin films by atomic force microscopy based techniques.

Polymeric thin films have been awakening continuous and growing interest for application in nanotechnology. For such applications, the assessment of their (nano)mechanical properties is a key issue, since they may dramatically vary between the bulk and the thin film state, even for the same polymer. Therefore, techniques are required for the in situ characterization of mechanical properties of thin films that must be nondestructive or only minimally destructive. Also, they must also be able to probe nanometer-thick ultrathin films and layers and capable of imaging the mechanical properties of the sample with nanometer lateral resolution, since, for instance, at these scales blends or copolymers are not uniform, their phases being separated. Atomic force microscopy (AFM) has been proposed as a tool for the development of a number of techniques that match such requirements. In this review, we describe the state of the art of the main AFM-based methods for qualitative and quantitative single-point measurements and imaging of mechanical properties of polymeric thin films, illustrating their specific merits and limitations.

Hybrid Au/CNT systems: a novel breakthrough for enhanced Raman sensing of nitrile-based organic solvents.

This work deals with the preparation of carbon nabotube (CNT) deposits decorated with gold nanoparticles, and the use of Surface Enhanced Raman Spectroscopy (SERS) related to the strong plasmon absorption of gold for the detection of cyanide groups. Au nanoparticles with controlled sizes are produced by electrochemical techniques onto ensambles of CNTs deposited from hexane in N2 atmosphere. The synthesis methodologies employed to produce these hybrid materials assure an excellent adhesion to the substrate, avoiding hazardous dispersion of the nanocomponents. The use of Raman spectroscopy in the 2150-2350 cm(-1) frequency range enables to detect the presence of nitrilebased organic solvents and to discriminate between different organic cyanides. The response of the Au/CNT systems contacting nitrile-based solvents is characterized by good sensitivity, selectivity, reversibility and stability. The proposed methodology can detect in real time low levels of organic solvents and of other chemicals able to interact with gold, also in flowing systems and without stringent sample-volume requirements.

Carbon nanotubes/polydimethylsiloxanes systems for thermal management of miniaturized electronic components.

The thermal performances of nanocomposite layers formed by Single-walled Carbon Nanotubes (SWCNT) dispersed in 2 different kind of polydimethyl-siloxane (PDMSO) matrices has been investigated by measuring the thermal resistance under conditions similar to the ones used for thermal management in microelectronics. A series of nanocomposite samples with thickness in the range 25 microm(-1) cm have been tested. The nanocomposites were prepared varying the amounts of nanotubes embedded in the matrix (from 0.1 to 5%w). In some cases also microsized graphites were mixed to the nanotube's fillers. For 25 micron thick layers, the thermal resistance of the neat silicone specimen can be reduced of 54% with the addition of 2%w carbon nanotubes. The variation of thermal conductivity as a function of the SWCNT's loading is reported and discussed. Furthermore the dispersion's effects of the nanotubes in the layers and the effects on the realization of a net-like system have been investigated.