Micro/nano-structured superhydrophobic surfaces in the biomedical field: part I: basic concepts and biomimetic approaches.

Inspired by natural structures, great attention has been devoted to the study and development of surfaces with extreme wettable properties. The meticulous study of natural systems revealed that the micro/nano-topography of the surface is critical to obtaining unique wettability features, including superhydrophobicity. However, the surface chemistry also has an important role in such surface characteristics. As the interaction of biomaterials with the biological milieu occurs at the surface of the materials, it is expected that synthetic substrates with extreme and controllable wettability ranging from superhydrophilic to superhydrophobic regimes could bring about the possibility of new investigations of cellâ material interactions on nonconventional surfaces and the development of alternative devices with biomedical utility. This first part of the review will describe in detail how proteins and cells interact with micro/nano-structured surfaces exhibiting extreme wettabilities.

A template-assembled synthetic protein surface mimetic of the von Willebrand factor A1 domain inhibits botrocetin-induced platelet aggregation.

Platelet adhesion, the initial step of platelet activation, is mediated by the interaction of von Willebrand factor (VWF) with its platelet receptor, the GPIb-IX complex. The binding of VWF to GPIb-IX is induced either by increased shear stress or by exogenous modulators, such as botrocetin. At a molecular level, this interaction takes place between the A1 domain of VWF and the GPIb alpha chain of the GPIb-IX complex. We report here the design and functional characteristics of a VWF template-assembled synthetic protein (TASP), a chimeric four-helix-bundle TASP scaffold mimicking the surface of the A1 domain. Twelve residues located on helices alpha 3 and alpha 4 in the native A1 domain were grafted onto a surface formed by two neighboring helices of the TASP. VWF TASP was found to inhibit specifically botrocetin-induced platelet aggregation and to bind both botrocetin and GPIb alpha. However, in contrast to the native A1 domain, VWF TASP did not bind simultaneously to both ligands. Modeling studies revealed that the relative orientation of the alpha helices in VWF TASP led to a clash of bound botrocetin and GPIb alpha. These results demonstrate that a chimeric four-helix-bundle TASP as a scaffold offers a suitable surface for presenting crucial residues of the VWF A1 domain; the potential of the TASP approach for de novo protein design and mimicry is thereby illustrated.

Development of biomimetic squid-inspired suckers

Biomechanical properties of squid suckers were studied to provide inspiration for the development of sucker artefacts for a robotic octopus. Mechanical support of the rings found inside squid suckers was studied by bending tests. Tensile tests were carried out to study the maximum possible sucking force produced by squid suckers based on the strength of sucker stalks, normalized by the sucking areas. The squid suckers were also directly tested to obtain sucking forces by a special testing arrangement. Inspired by the squid suckers, three types of sucker artefacts were developed for the arm skin of an octopus inspired robot. The first sucker artefact made of knitted nylon sheet reinforced silicone rubber has the same shape as the squid suckers. Like real squid suckers, this type of artefact also has a stalk that is connected to the arm skin and a ring to give radial support.The second design is a straight cylindrical structure with uniform wall thickness made of silicone rubber. One end of the cylinder is directly connected to the arm skin and the other end is open. The final design of the sucker has a cylindrical base and a concave meniscus top. The meniscus was formed naturally using the surface tension of silicone gel, which leads to a higher level of the liquid around the edge of a container. The wall thickness decreases towards the tip of the sucker opening. Sucking forces of all three types of sucker artefacts were measured. Advantages and isadvantages of each sucker type were discussed. The final design of suckers has been implemented to the arm skin prototypes.

Study of some physical properties of biodegradable films based on blends of gelatin and poly(vinyl alcohol) using a response-surface methodology

The aim of this work was to study the effect of the hydrolysis degree (HD) and the concentration (C(PVA)) Of two types of poly(vinyl alcohol) (PVA) and of the type (glycerol and sorbitol) and the concentration (C(P)) of plasticizers on some physical properties of biodegradable films based on blends of gelatin and PVA Using a response-surface methodology. The films were prepared with a film forming solutions (FFS) with 2 g of macromolecules (gelatin+PVA)/100 g de FFS. The responses analyzed were the mechanical properties, the solubility, the moisture Content. the color difference and the opacity. The linear model was statistically significant and predictive for puncture force and deformation. elongation at break, solubility in water, Moisture content and opacity. The CPVA affected strongly the elongation at break of the films. The interaction of the HD and the C(P) affected this property. Moreover. the puncture force was affected slightly by the C(PVA). Concerning the Solubility in water, the reduction of the HD increased it and this effect was greater for high CPVA Values. In general. the most important effect observed in the physical properties of the films was that of the plasticizer type and concentration. The PVA hydrolysis degree and concentration have an important effect only for the elongation at break, puncture deformation and solubility in water. (C) 2008 Elsevier B.V. All rights reserved.

Analyse titanium surface irradiated with laser, with and without deposited of durapatite

OBJETIVO: Estudar a superfície de implantes osseointegráveis utilizando discos de titânio irradiados com feixe de laser. MÉTODOS: A amostra foi irradiada com feixes de laser de alta intensidade (Nd-YAG), posteriormente depositado hidróxiapatita e submetido a tratamento térmico. Foi analisada sob MEV (Microscópio Eletrônico de Varredura) e realizada análise morfológica qualitativa com microfotografias em vários aumentos. RESULTADOS: A superfície irradiada com laser apresentou deformidade superficial e característica isomórfica; a aplicação de hidroxiapatita pelo método de biomimético aumentou quantitativamente a área da superfície de titânio. CONCLUSÃO: A deposição de hidroxiapatita apresentou melhor característica isomórfica e aumento quantitativo da área superficial estudada, a amostra demonstrou características não encontradas nos implantes disposto no mercado.

Surface and Biomechanical Study of Titanium Implants Modified by Laser With and Without Hydroxyapatite Coating, in Rabbits

Surface and biomechanical analysis of titanium implant surfaces modified by laser beam with and without hydroxyapatite. Titanium implants with 3 different surfaces were inserted into the tibias of 30 rabbits: group I (GI) machined surface (control group), group II irradiated with laser (GII), and group III irradiated with laser and hydroxyapatite coating applied-biomimetic method (GIII). Topographical analysis with scanning electron microscopy was made before surgery in the tibia. These rabbits were distributed into 2 periods of observation: 4 and 8 weeks postsurgery, after which biomechanical analysis (removal torque) was conducted. Statistical analysis used the Student-Newman-Keuls method. Surface showed roughness in GII and GIII. Biomechanical analysis demonstrated values with significant differences in GII and GIII. Titanium implants modified by laser irradiation can increase osseointegration during the initial phase.

Biomimetic calcium phosphate coating on Ti-7.5Mo alloy for dental application

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Laser ablation in titanium implants followed by biomimetic hydroxyapatite coating: Histomorphometric study in rabbits

Titanium surface texture and chemistry modification successfully improves the host response and consequently the bone-to-implant contact surrounding dental implants. The aim of the present study was to investigate, using histomorphometrical-analysis, the effects of titanium surface modification by laser-ablation (Nd:YAG) followed by thin chemical deposition of HA. Forty-eight rabbits received one implant by tibiae of AS-machined (MS), laser-modified (LMS), or biomimetic hydroxyapatite-coated (HA) surface. Bone-to-implant contact (BIC) and bone area (BBT) were evaluated after 4, 8, and 12 weeks, at cortical and cancellous regions. Average BIC in the cortical region was higher (P < 0.001) on the LMS and HA implants for all periods, with no differences between LMS and HA. For the cancellous area, the LMS and HA implants showed higher (P < 0.01) BIC than MS at the initial periods. The LMS and HA showed similar values in the cortical region, but a tendency of higher values for HA in the cancellous region was observed in all periods. For the BBT, the differences were found only between HA and MS after 4 weeks in the cortical region (P < 0.05), and after 12 weeks in the cancellous area (P < 0.05). Our results showed that HA biomimetic coating preceded by laser treatment induced the contact osteogenesis and allowed the formation of a more stable boneimplant interface, even in earlier periods. Microsc. Res. Tech., 2012. (C) 2012 Wiley Periodicals, Inc.

Biological Performance of Chemical Hydroxyapatite Coating Associated With Implant Surface Modification by Laser Beam: Biomechanical Study in Rabbit Tibias

Purpose: Considering the potential of the association between laser ablation and smaller scale hydroxyapatite (HA) coatings to create a stable and bioactive surface on titanium dental implants, the aim of the present study was to determine, by the removal torque test, the effects of a surface treatment created by laser-ablation (Nd:YAG) and, later, thin deposition of HA particles by a chemical process, compared to implants with only laser-ablation and implants with machined surfaces.Materials and Methods: Forty-eight rabbits received I implant by tibia of the following surfaces: machined surface (MS), laser-modified surface (LMS), and biomimetic hydroxiapatite coated surface (HA). After 4, 8, and 12 weeks of healing, the removal torque was measured by a torque gauge. The surfaces studied were analyzed according to their topography, chemical composition, and roughness.Results: Average removal torque in each period was 23.28, 24.0, and 33.85 Ncm to MS, 33.0, 39.87, and 54.57 Ncm to LMS, and 55.42, 63.71 and 64.0 Ncm to HA. The difference was statistically significant (P < .05) between the LMS-MS and HA-MS surfaces in all periods of evaluation, and between LMS-HA to 4 and 8 weeks of healing. The surface characterization showed a deep, rough, and regular topography provided by the laser conditioning, that was followed by the HA coating.Conclusions: Based on these results, it was possible to conclude that the implants with laser surface modification associated with HA biomimetic coating can shorten the implant healing period by the increase of bone implant interaction during the first 2 months after implant placement. (C) 2009 American Association of Oral and Maxillofacial Surgeons J Oral Maxillofac Surg 67:1706-1715, 2009

Flow injection analysis of paracetamol using a biomimetic sensor as a sensitive and selective amperometric detector

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Alumina/zirconia composite coated by biomimetic method

In this study, a bioactive zirconia-toughened alumina (ZTA) composite was developed for orthopedic applications. This composite was obtained by slip casting of suspension powder mixtures.Biomimetic processes were used to grow a bone-like apatite layer on composite substrates using sodium silicate solution as a nucleating agent and simulated body fluids. The composites, with or without coating, were characterized by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and scanning electron microscopy (SEM) with energy dispersion spectroscopy (EDS), and their apparent density was determined by the Archimedes method. The composites obtained by this process possessed the expected stiffness and dimensions and their density values were similar to those of the composite's theoretical density (98.8%TD). The morphology of the hydroxyapatite formed on the composite surface was homogeneous and composed of small globules, characterizing a carbonated hydroxyapatite. The results of the tests indicated that the method employed to produce the composite and its coating was efficient under the conditions of this study. (c) 2006 Elsevier B.V. All rights reserved.

Construction and application of an electrochemical sensor for paracetamol determination based on iron tetrapyridinoporphyrazine as a biomimetic catalyst of P450 enzyme

This work describes the construction and application of a biomimetic sensor for paracetamol determination in different samples. The sensor was prepared by modifying a glassy carbon electrode surface with a Nafion (R) membrane doped with FeTPyPz. The best performance of the sensor in 0.1 mol L-1 acetate buffer was at pH 3.6. Under these conditions, an oxidation potential of paracetamol was observed at 445 mV vs. Ag vertical bar AgCl. The sensor presented a linear response range between 4.0 and 420 mu mol L-1, a sensitivity of 46.015 mA L mol(-1) cm(-2), quantification and detection limits of 4.0 mu mol L-1 and 1.2 mu mol L-1, respectively. A detailed investigation about its electrochemical behavior and selectivity was carried out. The results suggested that FeTPyPz presents catalytic properties similar to P450 enzyme for paracetamol oxidation. Finally, the sensor was applied for paracetamol determination in commercial drugs and for the monitoring of its degradation in an electrochemical batch reactor effluent.

Inorganic-Organic Nanocomposite Assembly Using Collagen as a Template and Sodium Tripolyphosphate as a Biomimetic Analog of Matrix Phosphoprotein

Nanocomposites created with polycarboxylic acid alone as a stabilization agent for prenucleation clusters-derived amorphous calcium phosphate exhibit nonperiodic apatite deposition. In the present study, we report the use of inorganic polyphosphate as a biomimetic analog of matrix phosphoprotein for directing poly(acrylic acid)-stabilized amorphous nano-precursor phases to assemble into periodic apatite-collagen nanocomposites. The sorption and desorption characteristics of sodium tripolyphosphate to type I collagen were examined. Periodic nanocomposite assembly with collagen as a template was demonstrated with TEM and SEM using a Portland cement-based resin composite and a phosphate-containing simulated body fluid. Apatite was detected within the collagen at 24 h and became more distinct at 48 h, with prenucleation clusters attaching to the collagen fibril surface during the initial infiltration stage. Apatite-collagen nanocomposites at 72 h were heavily mineralized with periodically arranged intrafibrillar apatite platelets. Defect-containing nanocomposites caused by desorption of TPP from collagen fibrils were observed in regions lacking the inorganic phase.

Dental implants: Surface modification of cp-Ti using plasma spraying and the deposition of hydroxyapatite

The commercial pure titanium (cp-Ti) is currently being used with great success in dental implants. In this work we investigate how the cp-Ti implants can be improved by modifying the metal surface morphology, on which a synthetic material with properties similar to that of the inorganic part of the bone, is deposited to facilitate the bone/implant bonding. This synthetic material is the hydroxyapatite, HA, a calcium-phosphate ceramic. The surface modification consists in the application of a titanium oxide (TiO2) layer, using the thermal aspersion - plasma spray technique, with posterior deposition of HA, using the biomimetic method. The X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray (EDX) and Diffuse Reflectance Infrared Fourier Transform (DRIFT) techniques have been used for characterizing phases, microstructures and morphologies of the coatings. The TiO2 deposit shows a mixture of anatase, rutilo and TiO2-x phases, and a porous and laminar morphology, which facilitate the HA deposition. After the thermal treatment, the previously amorphous structured HA coating, shows a porous homogeneous morphology with particle size of about 2-2.5 μm, with crystallinity and composition similar to that of the biological HA.

In vivo evaluation of porous titanium implants with biomimetic coating

The osseointegration of porous titanium implants was evaluated in the present work. Implants were fabricated from ASTM grade 2 titanium by a powder metallurgy method. Part of these implants were submitted to chemical and thermal treatment in order to deposit a biomimetic coating, aiming to evaluate its influence on the osseointegration of the implants. The implants were characterized by Scanning Electron Microscopy (SEM), Electron Dispersive X-Ray Spectroscopy (EDS) and Raman Spectroscopy. Three coated and three control (uncoated) implants were surgically inserted into thirty albino rabbits' left and right tibiae, respectively. Tibiae samples were submitted to histological and histomorphometric analyses, utilizing SEM, optical microscopy and mechanical tests. EDS results indicated calcium (Ca) and phosphorous (P) at the surface and Raman spectra exhibited an intense peak, characteristic of hydroxyapatite (HA). Bone neoformation was detected at the bone-implant interface and inside the pores, including the central ones. The mean bone neoformation percentage in the coated implants was statistically higher at 15 days, compared to 30 and 45 days. The mechanical tests showed that coated implants presented higher resistance to displacement, especially after 30 and 45 days.