Mechanical writing of electrical polarization in poly (L-lactic) acid.

Stimuli responsive materials are found in a broad range of applications, from energy harvesters to biomolecular sensors. Here, we report the production of poly (L-lactic acid) (PLLA) thin films that exhibit a mechanical stress responsive behaviour. By simply applying a mechanical stress through an AFM tip, a local electrical polarization was generated and measured by Kelvin Probe Force Microscopy. We showed that the magnitude of the stress generated electrical polarization can be manipulated by varying the thickness or crystallization state of the PLLA thin films. Besides exhibiting a mechanical stress-response behaviour with potential for energy harvesting and sensor applications, we show by AFM that these platforms react to mechanical forces with physiological relevance: interaction forces as low as a cell sheet migrating over a substrate or larger ones as the fluid induced stresses in bone tissue. In living tissues, as most mechanical stimuli are transduced as strain gradients for the anatomical structures, these mechanically responsive substrates can be used as ex vivo platforms to study the protein and cells response over a large range of electrical stimuli amplitude. As a proof of concept, selective adsorption of a human fibronectin was demonstrated by local patterning of the stimuli responsive PLLA films. STATEMENT OF SIGNIFICANCE: Bioelectricity is inherent to the formation and repair of living tissues and electrical stimulation has been recognized for promoting regeneration. Given the proven beneficial effects of electric fields and the absence of a suitable method of stimulation, there is a clinical need for smart substrates, which can generate a polarization (charges) to promote tissue regeneration without the need of external devices. In this work, we report the fabrication of poly(L-lactic) acid platforms that exhibit a mechanical stress responsive behaviour when subjected to physiologically relevant forces. This behaviour can be tailored by varying the thickness or crystallization state of the PLLA films. We further demonstrate the biofunctionality of such platforms by exploiting the mechanically-induced charge for adhesion protein adsorption.

PDMS-SiO2-TiO2-CaO hybrid materials - Cytocompatibility and nanoscale surface features.

Two PDMS-SiO2-TiO2-CaO porous hybrid materials were prepared using the same base composition, precursors, and solvents, but following two different sol-gel procedures, based on the authors' previous works where for the first time, in this hybrid system, calcium acetate was used as calcium source. The two different procedures resulted in monolithic materials with different structures, microstructures, and surface wettability. Even though both are highly hydrophobic (contact angles of 127.2° and 150.6°), and present different filling regimes due to different surface topographies, they have demonstrated to be cytocompatible when tested with human osteoblastic cells, against the accepted idea that high-hydrophobic surfaces are not suitable to cell adhesion and proliferation. At the nanoscale, the existence of hydrophilic silica domains containing calcium, where water molecules are physisorbed, is assumed to support this capability, as discussed.

A biocompatible hybrid material with simultaneous calcium and strontium release capability for bone tissue repair.

The increasing interest in the effect of strontium in bone tissue repair has promoted the development of bioactive materials with strontium release capability. According to literature, hybrid materials based on the system PDMS-SiO2 have been considered a plausible alternative as they present a mechanical behavior similar to the one of the human bone. The main purpose of this study was to obtain a biocompatible hybrid material with simultaneous calcium and strontium release capability. A hybrid material, in the system PDMS-SiO2-CaO-SrO, was prepared with the incorporation of 0.05 mol of titanium per mol of SiO2. Calcium and strontium were added using the respective acetates as sources, following a sol-gel technique previously developed by the present authors. The obtained samples were characterized by FT-IR, solid-state NMR, and SAXS, and surface roughness was analyzed by 3D optical profilometry. In vitro studies were performed by immersion of the samples in Kokubo's SBF for different periods of time, in order to determine the bioactive potential of these hybrids. Surfaces of the immersed samples were observed by SEM, EDS and PIXE, showing the formation of calcium phosphate precipitates. Supernatants were analyzed by ICP, revealing the capability of the material to simultaneously fix phosphorus ions and to release calcium and strontium, in a concentration range within the values reported as suitable for the induction of the bone tissue repair. The material demonstrated to be cytocompatible when tested with MG63 osteoblastic cells, exhibiting an inductive effect on cell proliferation and alkaline phosphatase activity.

Three-dimensional printed PCL-hydroxyapatite scaffolds filled with CNTs for bone cell growth stimulation.

A three-phase [nanocrystalline hydroxyapatite (HA), carbon nanotubes (CNT), mixed in a polymeric matrix of polycaprolactone (PCL)] composite scaffold produced by 3D printing is presented. The CNT content varied between 0 and 10 wt % in a 50 wt % PCL matrix, with HA being the balance. With the combination of three well-known materials, these scaffolds aimed at bringing together the properties of all into a unique material to be used in tissue engineering as support for cell growth. The 3D printing technique allows producing composite scaffolds having an interconnected network of square pores in the range of 450-700 µm. The 2 wt % CNT scaffold offers the best combination of mechanical behaviour and electrical conductivity. Its compressive strength of ∼4 MPa is compatible with the trabecular bone. The composites show typical hydroxyapatite bioactivity, good cell adhesion and spreading at the scaffolds surface, this combination of properties indicating that the produced 3D, three-phase, scaffolds are promising materials in the field of bone regenerative medicine. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1210-1219, 2016.

Evaluating structural and microstructural changes of PDMS-SiO2 hybrid materials after sterilization by gamma irradiation.

PDMS-SiO2 hybrid materials obtained by sol-gel process have been extensively studied over the past years due to its promising biomedical applications namely as bone substitutes, catheters, and drug delivery devices. Regardless of the intended biomedical application, all these materials should go through a sterilization process before interfacing with a living structure. However, it is unclear whether they undergo structural and microstructural changes when subjected to sterilization by gamma irradiation. This paper addresses this issue by showing that a sol-gel processed biomaterial based on the PDMS-CaO-SiO2 hybrid system suffers only small structural changes when submitted to a radiation dose of 25kGy, the dose usually recommended to achieve a Sterility Assurance Level of 10(-6) when the natural contamination level and microorganism types cannot be calculated. The characterization was assessed by FT-IR, (29)Si-{(1)H} CP-MAS, thermal analysis (DTG), and SEM.

Contrasting light spectra constrain the macro and microstructures of scleractinian corals.

The morphological plasticity of scleractinian corals can be influenced by numerous factors in their natural environment. However, it is difficult to identify in situ the relative influence of a single biotic or abiotic factor, due to potential interactions between them. Light is considered as a major factor affecting coral skeleton morphology, due to their symbiotic relation with photosynthetic zooxanthellae. Nonetheless, most studies addressing the importance of light on coral morphological plasticity have focused on photosynthetically active radiation (PAR) intensity, with the effect of light spectra remaining largely unknown. The present study evaluated how different light spectra affect the skeleton macro- and microstructures in two coral species (Acropora formosa sensu Veron (2000) and Stylophora pistillata) maintained under controlled laboratory conditions. We tested the effect of three light treatments with the same PAR but with a distinct spectral emission: 1) T5 fluorescent lamps with blue emission; 2) Light Emitting Diodes (LED) with predominantly blue emission; and 3) Light Emitting Plasma (LEP) with full spectra emission. To exclude potential bias generated by genetic variability, the experiment was performed with clonal fragments for both species. After 6 months of experiment, it was possible to detect in coral fragments of both species exposed to different light spectra significant differences in morphometry (e.g., distance among corallites, corallite diameter, and theca thickness), as well as in the organization of their skeleton microstructure. The variability found in the skeleton macro- and microstructures of clonal organisms points to the potential pitfalls associated with the exclusive use of morphometry on coral taxonomy. Moreover, the identification of a single factor influencing the morphology of coral skeletons is relevant for coral aquaculture and can allow the optimization of reef restoration efforts.

Ash from a pulp mill boiler--characterisation and vitrification.

The physical, chemical and mineralogical characterisation of the ash resulting from a pulp mill boiler was performed in order to investigate the valorisation of this waste material through the production of added-value glassy materials. The ash had a particle size distribution in the range 0.06-53 microm, and a high amount of SiO(2) (approximately 82 wt%), which was present as quartz. To favour the vitrification of the ash and to obtain a melt with an adequate viscosity to cast into a mould, different amounts of Na(2)O were added to act as fluxing agent. A batch with 80 wt% waste load melted at 1350 degrees C resulting in a homogeneous transparent green-coloured glass with good workability. The characterisation of the produced glass by differential thermal analysis and dilatometry showed that this glass presents a stable thermal behaviour. Standard leaching tests revealed that the concentration of heavy metals in the leaching solution was lower than those allowed by the Normative. As a conclusion, by vitrification of batch compositions with adequate waste load and additive content it is possible to produce an ash-based glass that may be used in similar applications as a conventional silicate glass inclusively as a building ecomaterial.