Characterization of Conductive Carbon Nanotubes/Polymer Composites for Stretchable Sensors and Transducers.

The increasing interest in stretchable conductive composite materials, that can be versatile and suitable for wide-ranging application, has sparked a growing demand for studies of scalable fabrication techniques and specifically tailored geometries. Thanks to the combination of the conductivity and robustness of carbon nanotube (CNT) materials with the viscoelastic properties of polymer films, in particular their stretchability, "surface composites" made of a CNT on polymeric films are a promising way to obtain a low-cost, conductive, elastic, moldable, and patternable material. The use of polymers selected for specific applications, however, requires targeted studies to deeply understand the interface interactions between a CNT and the surface of such polymer films, and in particular the stability and durability of a CNT grafting onto the polymer itself. Here, we present an investigation of the interface properties for a selected group of polymer film substrates with different viscoelastic properties by means of a series of different and complementary experimental techniques. Specifically, we studied the interaction of a single-wall carbon nanotube (SWCNT) deposited on two couples of different polymeric substrates, each one chosen as representative of thermoplastic polymers (i.e., low-density polyethylene (LDPE) and polypropylene (PP)) and thermosetting elastomers (i.e., polyisoprene (PI) and polydimethylsiloxane (PDMS)), respectively. Our results demonstrate that the characteristics of the interface significantly differ for the two classes of polymers with a deeper penetration (up to about 100 µm) into the polymer bulk for the thermosetting substrates. Consequently, the resistance per unit length varies in different ranges, from 1-10 kΩ/cm for typical thermoplastic composite devices (30 µm thick and 2 mm wide) to 0.5-3 MΩ/cm for typical thermosetting elastomer devices (150 µm thick and 2 mm wide). For these reasons, the composites show the different mechanical and electrical responses, therefore suggesting different areas of application of the devices based on such materials.

Effects of IPR by mechanical oscillating strips system on biological structures: a quantitative and qualitative evaluation.

BACKGROUND: To evaluate by means of profilometric analysis and scanning electronic microscope (SEM) the effects on enamel surfaces of oscillating mechanical systems for interproximal enamel reduction (IPR). Fifteen complete (Group 1) oscillating IPR sequence and 15 single metallic strips (Group 2) for active IPR phase of 0.2 mm were selected and tested on 30 freshly extracted teeth by means of tribological tests with alternative dry-sliding motion (Linear Reciprocating Tribometer, C.S.M. Instruments, Peseaux, Switzerland). Enamel surface roughness and waviness measurements were assessed by contact probe surface profiler (TalySurf CLI 2000; Taylor Hobson, Leicester, UK) and a TayMap software for the 3D analysis. Statistical analysis was performed with independent samples t-test. Significance was established at the P < .05 level. SEM analysis of enamel surfaces was conducted with a FEI Quanta 200 (Hillsboro, USA) in high vacuum at 30.00 kV. Images were acquired at 30X, 100X, and 300X of magnification. RESULTS: Teeth undergone Group 1 showed lower values of surface roughness (Ra - 0.34 µm, Rt - 1.55 µm) and significant increase of waviness parameters (Wa 0.25 µm, Wt 4.02 µm) when compared with those treated with Group 2. SEM evaluation showed smoothers and more regular surfaces when IPR was performed by complete IPR sequence. Single metallic strip determined more irregular surfaces characterized by extended grooves, alternated with enamel ridges and irregular fragments. CONCLUSION: The adoption of a standardized oscillating IPR sequence determines more regular and harmonious enamel surfaces at the end of the procedure. An adequate polishing after IPR plays a crucial role to guarantee a good long-term prognosis and a good respect of biological structures.

Comparative study of different techniques for the sterilization of poly-L-lactide electrospun microfibers: effectiveness vs. material degradation.

Electrospinning of biopolymeric scaffolds is a new and effective approach for creating replacement tissues to repair defects and/or damaged tissues with direct clinical application. However, many hurdles and technical concerns regarding biological issues, such as cell retention and the ability to grow, still need to be overcome to gain full access to the clinical arena. Interaction with the host human tissues, immunogenicity, pathogen transmission as well as production costs, technical expertise, and good manufacturing and laboratory practice requirements call for careful consideration when aiming at the production of a material that is available off-the-shelf, to be used immediately in operative settings. The issue of sterilization is one of the most important steps for the clinical application of these scaffolds. Nevertheless, relatively few studies have been performed to systematically investigate how sterilization treatments may affect the properties of electrospun polymers for tissue engineering. This paper presents the results of a comparative study of different sterilization techniques applied to an electrospun poly-L-lactide scaffold: soaking in absolute ethanol, dry oven and autoclave treatments, UV irradiation, and hydrogen peroxide gas plasma treatment. Morphological and chemical characterization was coupled with microbiological sterility assay to validate the examined sterilization techniques in terms of effectiveness and modifications to the scaffold. The results of this study reveal that UV irradiation and hydrogen peroxide gas plasma are the most effective sterilization techniques, as they ensure sterility of the electrospun scaffolds without affecting their chemical and morphological features.

Enzymatic hydrolysis of poly(1,4-butylene 2,5-thiophenedicarboxylate) (PBTF) and poly(1,4-butylene 2,5-furandicarboxylate) (PBF) films: A comparison of mechanisms.

Enzymatic hydrolysis of poly(1,4-butylene 2,5-thiophenedicarboxylate) (PBTF) and poly(1,4-butylene 2,5-furandicarboxylate) (PBF) by Humicola insolens (HiC) and Thermobifida cellulosilytica (Cut) cutinases is investigated. For the first time, the different depolymerization mechanisms of PBTF (endo-wise scission) and PBF (exo-wise cleavage) has been unveiled and correlated to the chemical structure of the two polyesters.

Composition-Nanostructure Steered Performance Predictions in Steel Wires.

Neutron scattering in combination with scanning electron and atomic force microscopy were employed to quantitatively resolve elemental composition, nano- through meso- to metallurgical structures and surface characteristics of two commercial stainless steel orthodontic archwires-G&H and Azdent. The obtained bulk composition confirmed that both samples are made of metastable austenitic stainless steel type AISI 304. The neutron technique's higher detection sensitivity to alloying elements facilitated the quantitative determination of the composition factor (CF), and the pitting resistance equivalent number (PREN) for predicting austenite stability and pitting-corrosion resistance, respectively. Simultaneous neutron diffraction analyses revealed that both samples contained additional martensite phase due to strain-induced martensite transformation. The unexpectedly high martensite content (46.20 vol%) in G&H was caused by combination of lower austenite stability (CF = 17.37, p = .03), excessive cold working and inadequate thermal treatment during material processing. Together, those results assist in revealing alloying recipes and processing history, and relating these with corrosion resistance and mechanical properties. The present methodology has allowed access to unprecedented length-scale (µm to sub-nm) resolution, accessing nano- through meso-scopic properties. It is envisaged that such an approach can be extended to the study and design of other metallic (bio)materials used in medical sciences, dentistry and beyond.

Fabrication of bioactive glass-ceramic foams mimicking human bone portions for regenerative medicine.

A technique for the preparation of bioglass foams for bone tissue engineering is presented. The process is based on the in situ foaming of a bioglass-loaded polyurethane foam as the intermediate step for obtaining a bioglass porous monolith, starting from sol-gel synthesized bioglass powders. The obtained foams were characterized using X-ray diffraction analysis, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy observations. The material was assessed by soaking samples in simulated body fluid and observing apatite layer formation. Diagnostic imaging taken from human patients was used to reconstruct a human bone portion, which was used to mould a tailored scaffold fabricated using the in situ foaming technique. The results confirmed that the obtained bioactive materials prepared with three-dimensional processing are promising for applications in reconstructive surgery tailored to each single patient.

Mechanical properties of "two generations" of teeth aligners: Change analysis during oral permanence.

Aim of this in vitro study was to analyze structural properties of two different polymeric orthodontic aligners, Exceed30 (EX30) and Smart Track (LD30), before and after use. Forty patterns of aligners were randomly selected: 20 LD30 and 20 EX30, worn intra-orally for 14±3 days, 22 h/day. From each aligner, 10 specimens were prepared from buccal surfaces of the incisor region by the cutting of samples 5×5 mm under a stereomicroscope. All samples were subjected to Fourier transform infrared spectroscopy, micro-Raman spectroscopy, X-ray diffraction, tensile and indentation strength test. LD30 appeared more homogeneous, with a crystalline fraction lower than EX30 and exhibited a higher elastic behavior and a lower tendency to warp after use than EX30. LD30 demonstrated better adaptability to the dental arch and greater consistency of application of orthodontic forces than produced with EX30. However, both materials showed structural modifications that resulted in increased sample hardness and hyper-plasticity.

Orthodontic archwire composition and phase analyses by neutron spectroscopy.

Quantitative metallurgical and phase analyses employing neutron diffraction technique were conducted on two as-received commercial rectangular austenitic stainless steel orthodontic archwires, G&H and Azdent, 0.43×0.64 mm (0.017×0.025 inch). Results showed a bi-phase structure containing martensitic phase (45.67% for G&H and 6.62% for Azdent) in addition to the expected metastable austenite. The former may be a strain-induced phase-transformation arising during the cold working process of wire fabrication. Further neutron resonance capture analysis determinations provided atomic and isotopic compositions, including alloying elements in each sample, complementary to the results of traditional energy dispersive X-ray spectroscopy. Together, these results assist in relating commercial alloying recipes and processing histories with mechanical performance, strength and ductility in particular.

Omega-3 and Omega-6 Fatty Acids Act as Inhibitors of the Matrix Metalloproteinase-2 and Matrix Metalloproteinase-9 Activity.

Polyunsaturated fatty acids have been reported to play a protective role in a wide range of diseases characterized by an increased metalloproteinases (MMPs) activity. The recent finding that omega-3 and omega-6 fatty acids exert an anti-inflammatory effect in periodontal diseases has stimulated the present study, designed to determine whether such properties derive from a direct inhibitory action of these compounds on the activity of MMPs. To this issue, we investigated the effect exerted by omega-3 and omega-6 fatty acids on the activity of MMP-2 and MMP-9, two enzymes that actively participate to the destruction of the organic matrix of dentin following demineralization operated by bacteria acids. Data obtained (both in vitro and on ex-vivo teeth) reveal that omega-3 and omega-6 fatty acids inhibit the proteolytic activity of MMP-2 and MMP-9, two enzymes present in dentin. This observation is of interest since it assigns to these compounds a key role as MMPs inhibitors, and stimulates further study to better define their therapeutic potentialities in carious decay.

Nanocomposite polymeric electrolytes to record electrophysiological brain signals in prolonged, unconventional or extreme conditions.

Chemically stable nanocomposite iono-conducting polymeric membranes (based on lithium salts and nanocrystalline oxide powders dispersed in a polymethyl methacrylate matrix) performed successfully in the recording of human brain responses to visual stimulation. Impedance was higher than that of conventional electrodes. However, the electrophysiological signals recorded by acid Al(2)O(3) and neutral Al(2)O(3) 5 wt.% and 10 wt.% nanocomposite gel electrolytes were comparable to those obtained with standard electrodes, even without preliminary skin cleaning and in the absence of gel electrolytes allowing better contact with and skin-electrode ionic conductance. The electrochemical and mechanical characteristics of these membranes make them fit for human and animal research, for clinical application (specifically in emergencies, prolonged electrophysiological recordings), or in unconventional or extreme conditions when fluid electrolytes are unsuitable (e.g., biomedical space research).

A primer of statistical methods for correlating parameters and properties of electrospun poly(L-lactide) scaffolds for tissue engineering--PART 2: regression.

This two-articles series presents an in-depth discussion of electrospun poly-L-lactide scaffolds for tissue engineering by means of statistical methodologies that can be used, in general, to gain a quantitative and systematic insight about effects and interactions between a handful of key scaffold properties (Ys) and a set of process parameters (Xs) in electrospinning. While Part-1 dealt with the DOE methods to unveil the interactions between Xs in determining the morphomechanical properties (ref. Y1₋4), this Part-2 article continues and refocuses the discussion on the interdependence of scaffold properties investigated by standard regression methods. The discussion first explores the connection between mechanical properties (Y4) and morphological descriptors of the scaffolds (Y1₋3) in 32 types of scaffolds, finding that the mean fiber diameter (Y1) plays a predominant role which is nonetheless and crucially modulated by the molecular weight (MW) of PLLA. The second part examines the biological performance (Y5) (i.e. the cell proliferation of seeded bone marrow-derived mesenchymal stromal cells) on a random subset of eight scaffolds vs. the mechanomorphological properties (Y1₋4). In this case, the featured regression analysis on such an incomplete set was not conclusive, though, indirectly suggesting in quantitative terms that cell proliferation could not fully be explained as a function of considered mechanomorphological properties (Y1₋4), but in the early stage seeding, and that a randomization effects occurs over time such that the differences in initial cell proliferation performance (at day 1) is smeared over time. The findings may be the cornerstone of a novel route to accrue sufficient understanding and establish design rules for scaffold biofunctional vs. architecture, mechanical properties, and process parameters.

A primer of statistical methods for correlating parameters and properties of electrospun poly(L-lactide) scaffolds for tissue engineering--PART 1: design of experiments.

Tissue engineering scaffolds produced by electrospinning are of enormous interest, but still lack a true understanding about the fundamental connection between the outstanding functional properties, the architecture, the mechanical properties, and the process parameters. Fragmentary results from several parametric studies only render some partial insights that are hard to compare and generally miss the role of parameters interactions. To bridge this gap, this article (Part-1 of 2) features a case study on poly-L-lactide scaffolds to demonstrate how statistical methods such as design of experiments can quantitatively identify the correlations existing between key scaffold properties and control parameters, in a systematic, consistent, and comprehensive manner disentangling main effects from interactions. The morphological properties (i.e., fiber distribution and porosity) and mechanical properties (Young's modulus) are "charted" as a function of molecular weight (MW) and other electrospinning process parameters (the Xs), considering the single effect as well as interactions between Xs. For the first time, the major role of the MW emerges clearly in controlling all scaffold properties. The correlation between mechanical and morphological properties is also addressed.

The effect of post-mastectomy radiation therapy on breast implants: Unveiling biomaterial alterations with potential implications on capsular contracture.

Post-mastectomy breast reconstruction with expanders and implants is recognized as an integral part of breast cancer treatment. Its main complication is represented by capsular contracture, which leads to poor expansion, breast deformation, and pain, often requiring additional surgery. In such a scenario, the debate continues as to whether the second stage of breast reconstruction should be performed before or after post-mastectomy radiation therapy, in light of potential alterations induced by irradiation to silicone biomaterial. This work provides a novel, multi-technique approach to unveil the role of radiotherapy in biomaterial alterations, with potential involvement in capsular contracture. Following irradiation, implant shells underwent mechanical, chemical, and microstructural evaluation by means of tensile testing, Attenuated Total Reflectance Fourier Transform InfraRed spectroscopy (ATR/FTIR), Scanning Electron Microscopy (SEM), high resolution stylus profilometry, and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS). Our findings are consistent with radiation-induced modifications of silicone that, although not detectable at the microscale, can be evidenced by more sophisticated nanoscale surface analyses. In light of these results, biomaterial irradiation cannot be ruled out as one of the possible co-factors underlying capsular contracture.

Spider silk as a load bearing biomaterial: tailoring mechanical properties via structural modifications.

Spider silk shows great potential as a biomaterial: in addition to biocompatibility and biodegradability, its strength and toughness are greater than native biological fibres (e.g. collagen), with toughness exceeding that of synthetic fibres (e.g. nylon). Although the ultimate tensile strength and toughness at failure are unlikely to be limiting factors, its yield strain of 2% is insufficient, particularly for biomedical application because of the inability to mimic the complex ultrastructure of natural tissues with current tissue engineering approaches. To harness the full potential of spider silk as a biomaterial, it is therefore necessary to increase its yield strain. In this paper, we discuss the means by which the mechanical properties of spider silk, particularly the yield strain, can be optimized through structural modifications.

Multiscale three-dimensional scaffolds for soft tissue engineering via multimodal electrospinning.

A novel (scalable) electrospinning process was developed to fabricate bio-inspired multiscale three-dimensional scaffolds endowed with a controlled multimodal distribution of fiber diameters and geared towards soft tissue engineering. The resulting materials finely mingle nano- and microscale fibers together, rather than simply juxtaposing them, as is commonly found in the literature. A detailed proof of concept study was conducted on a simpler bimodal poly(epsilon-caprolactone) (PCL) scaffold with modes of fiber distribution at 600 nm and 3.3 microm. Three conventional unimodal scaffolds with mean diameters of 300 nm and 2.6 and 5.2 microm, respectively, were used as controls to evaluate the new materials. Characterization of the microstructure (i.e. porosity, fiber distribution and pore structure) and mechanical properties (i.e. stiffness, strength and failure mode) indicated that the multimodal scaffold had superior mechanical properties (Young's modulus approximately 40MPa and strength approximately 1MPa) in comparison with the controls, despite the large porosity ( approximately 90% on average). A biological assessment was conducted with bone marrow stromal cell type (mesenchymal stem cells, mTERT-MSCs). While the new material compared favorably with the controls with respect to cell viability (on the outer surface), it outperformed them in terms of cell colonization within the scaffold. The latter result, which could neither be practically achieved in the controls nor expected based on current models of pore size distribution, demonstrated the greater openness of the pore structure of the bimodal material, which remarkably did not come at the expense of its mechanical properties. Furthermore, nanofibers were seen to form a nanoweb bridging across neighboring microfibers, which boosted cell motility and survival. Lastly, standard adipogenic and osteogenic differentiation tests served to demonstrate that the new scaffold did not hinder the multilineage potential of stem cells.

Thick soft tissue reconstruction on highly perfusive biodegradable scaffolds.

The lack of a vascular network and poor perfusion is what mostly prevents three-dimensional (3D) scaffolds from being used in organ repair when reconstruction of thick tissues is needed. Highly-porous scaffolds made of poly(L-lactic acid) (PLLA) are prepared by directional thermally induced phase separation (dTIPS) starting from 1,4-dioxane/PLLA solutions. The influence of polymer concentration and temperature gradient, in terms of imposed intensity and direction, on pore size and distribution is studied by comparison with scaffolds prepared by isotropic TIPS. The processing parameters are optimized to achieve an overall porosity for the 3D scaffolds of about 93% with a degree of interconnectivity of 91%. The resulting pore network is characterized by the ordered repetition of closely packed dendrite-like cavities, each one showing stacks of 20 microm large side lamellar branches departing from 70 microm diameter vertical backbones, strongly resembling the vascular patterns. The in vitro biological responses after 1 and 2 weeks are evaluated from mesenchymal (bone marrow stromal) cells (MSC) static culturing. A novel vacuum-based deep-seeding method is set up to improve uniform cell penetration down to scaffold thicknesses of over 1 mm. Biological screenings show significant 3D scaffold colonization even after 18 h, while cellular retention is observed up to 14 d in vitro (DIV). Pore architecture-driven cellular growth is accompanied by cell tendency to preserve their multi-potency towards differentiation. Confluent tissues as thick as 1 mm were reconstructed taking advantage of the large perfusion enhanced by the highly porous microstructure of the engineered scaffolds, which could successfully serve for applications aimed at vascular nets and angiogenesis.