Thermodynamic Characterization of Rhamnolipid, Triton X-165 and Ethanol as well as Their Mixture Behaviour at the Water-Air Interface.

In many industrial fields, in medicine or pharmacy, there are used multi-component mixtures of surfactants as well as more and more often mixtures containing biosurfactants. Thus, in our study the mixtures of rhamnolipid (RL), ethanol (ET) and Triton X-165 (TX165) were applied. For these mixtures the surface tension of aqueous solutions with constant concentration and composition of ET and RL as well as the variable concentration of TX165 was measured. Based on the obtained results and the literature data, thermodynamic analyses of the adsorption process of ET, RL, TX165, binary mixtures of ET + RL, ET + TX165 and RL + TX165 as well as the ternary mixtures of RL + ET + TX165 at the water-air interface were made. This analysis allows to propose a new equation for calculation of the total ethanol concentration at the water-air interface using the Guggenheim-Adam adsorption isotherm. The constants in the Langmuir and Szyszkowski equations for each component of the studied mixtures as well as the composition of the mixed monolayer at the water-air interface were also successfully analysed based on the contribution of particular surface active compounds to the water surface tension reduction as well as based on the Frumkin isotherm of adsorption.

Effect of Spontaneous and Water-Based Passivation on Components and Parameters of Ti6Al4V (ELI Grade) Surface Tension and Its Wettability by an Aqueous Solution of Sucrose Ester Surfactants.

Solid wettability is especially important for biomaterials and implants in the context of microbial adhesion to their surfaces. This adhesion can be inhibited by changes in biomaterial surface roughness and/or its hydrophilic-hydrophobic balance. The surface hydrophilic-hydrophobic balance can be changed by the specifics of the surface treatment (proper conditions of surface preparation) or adsorption of different substances. From the practical point of view, in systems that include biomaterials and implants, the adsorption of compounds characterized by bacteriostatic or bactericidal properties is especially desirable. Substances that are able to change the surface properties of a given solid as a result of their adsorption and possess at least bacteriostatic properties include sucrose ester surfactants. Thus, in our studies the analysis of a specific surface treatment effect (proper passivation conditions) on a biomaterial alloy's (Ti6Al4V ELI, Grade 23) properties was performed based on measurements of the contact angles of water, formamide and diiodomethane. In addition, the changes in the studied solid surface's properties resulting from the sucrose monodecanoate (SMD) and sucrose monolaurate (SML) molecules' adsorption at the solid-water interface were also analyzed. For the analysis, the values of the contact angles of aqueous solutions of SMD and SML were measured at 293 K, and the surface tensions of the aqueous solutions of studied surfactants measured earlier were tested. From the above-mentioned tests, it was found that water environment significantly influences the components and parameters of Ti6Al4V ELI's surface tension. It also occurred that the addition of both SMD and SML to water (separately) caused a drop in the water contact angle on Ti6Al4V ELI's surface. However, the sucrose monolaurate surfactant is characterized by a slightly better tendency towards adsorption at the solid-water interface in the studied system compared to sucrose monodecanoate. Additionally, based on the components and parameters of Ti6Al4V ELI's surface tension calculated from the proper values of components and parameters of model liquids, it was possible to predict the wettability of Ti6Al4V ELI using the aqueous solutions of SMD and SML at various concentrations in the solution.

Studying the influence of surface topography on bacterial adhesion using spatially organized microtopographic surface patterns.

The influence of surface topography on bacterial adhesion has been investigated using a range of spatially organized microtopographic surface patterns generated on polydimethylsiloxane (PDMS) and three unrelated bacterial strains. The results presented indicate that bacterial cells actively choose their position to settle, differentiating upper and lower areas in all the surface patterns evaluated. Such selective adhesion depends on the cells' size and shape relative to the dimensions of the surface topographical features and surface hydrophobicity/hydrophilicity. Moreover, it was found that all the topographies investigated provoke a significant reduction in bacterial adhesion (30-45%) relative to the smooth control samples regardless of surface hydrophobicity/hydrophilicity. This remarkable finding constitutes a general phenomenon, occurring in both Gram-positive and Gram-negative cells with spherical or rod shape, dictated by only surface topography. Collectively, the results presented in this study demonstrate that spatially organized microtopographic surface patterns represent a promising approach to controlling/inhibiting bacterial adhesion and biofilm formation.

Electrodeposited Zinc Coatings for Biomedical Application: Morphology, Corrosion and Biological Behaviour.

The improvement of biodegradable metals is currently an active and promising research area for their capabilities in implant manufacturing. However, controlling their degradation rate once their surface is in contact with the physiological media is a challenge. Surface treatments are in the way of addressing the improvement of this control. Zinc is a biocompatible metal present in the human body as well as a metal widely used in coatings to prevent corrosion, due to its well-known metal protective action. These two outstanding characteristics make zinc coating worthy of consideration to improve the degradation behaviour of implants. Electrodeposition is one of the most practical and common technologies to create protective zinc coatings on metals. This article aims to review the effect of the different parameters involved in the electrochemical process on the topography and corrosion characteristics of the zinc coating. However, certainly, it also provides an actual and comprehensive description of the state-of-the-art of the use of electrodeposited zinc for biomedical applications, focusing on their capacity to protect against bacterial colonization and to allow cell adhesion and proliferation.

Bacterial Response to the Surface Aging of PLA Matrices Loaded with Active Compounds.

The use of active components in biomaterials improves the properties of existing ones and makes it possible to obtain new devices with antibacterial properties that prevent infections after implantation, thus guaranteeing the success of the implant. In this work, cetyltrimethylammonium bromide (CTAB) and magnesium particles were incorporated into polylactic acid (PLA) films to assess the extent to which progressive aging of the new surfaces resists bacterial colonization processes. For this purpose, the films' surface was characterized by contact angle measurements, ToF-SIMS and AFM, and adhesion, viability and biofilm growth of Staphylococcus epidermidis bacteria on these films were also evaluated. The results show that the inclusion of Mg and CTAB in PLA films changes their surface properties both before and after aging and also modifies bacterial adhesion on the polymer. Complete bactericidal activity is exhibited on non-degraded films and films with CTAB. This antibacterial behavior is maintained after degradation for three months in the case of films containing a higher amount of CTAB.

Influence of Solvent and Substrate on Hydrophobicity of PLA Films.

The study of the surface properties of materials is key in determining whether the material will be suitable for medical purposes. One of these properties is hydrophobicity, which is important when assessing its behavior against bacterial adhesion. In this work, we have studied the influence of the solvent (chloroform, acetone, and tetrahydrofuran) and the substrate (glass, PTFE, silicone, and Ti6Al4V) on which polylactic acid is deposited in solution to manufacture films by solvent-casting. Thus, it has been found that there are no significant differences in hydrophobicity and surface tension among the solvents evaluated, but there are significant differences with respect to the substrates: PLA films casted on silicone are hydrophobic, while those casted on the rest of the substrates are hydrophilic. This is related to the fact that the silicone interacts with the polymer modifying its spatial arrangement, exposing its methyl groups towards the interface with the air. In this way, it has been shown that, when manufacturing PLA films, it is important to choose the right surface on which to deposit them, depending on their desired function.

Surface Characterisation of Human Serum Albumin Layers on Activated Ti6Al4V.

Adpsortion of protein layers on biomaterials plays an important role in the interactions between implants and the bio-environment. In this context, human serum albumin (HSA) layers have been deposited on modified Ti6Al4V surfaces at different ultraviolet (UV-C) irradiation times to observe possible changes in the adsorbed protein layer. Protein adsorption was done from solutions at concentraions lower than the serum protein concentration, to follow the surface modifications at the beginning of the albumin adhesion process. For this purpose, the surface of the protein-coated samples has been characterized by time of flight secondary ion mass spectrometry (ToF-SIMS), contact angle and zeta potential measurements. The results obtained show a reduction in the total surface tension and zeta potential of samples treated with UV-C light when coated with a protein layer. Furthermore, the UV-C light treatment applied to titanium alloy surfaces is able to modify the conformation, orientation and packing of the proteins arranged in the adsorbed layer. Low irradiation time generates an unstable surface with the lowest protein adsorption and the highest hydrophobic/hydrophilic protein ratio, indicating a possible denaturalization of the protein on these surfaces. However, surface changes are stabilized after 15 h or UV-C irradiation, favoring the protein adsorption through electrical interactions.

Ultrasmall liquid droplets on solid surfaces: production, imaging, and relevance for current wetting research.

The investigation of micro- and nanoscale droplets on solid surfaces offers a wide range of research opportunities both at a fundamental and an applied level. On the fundamental side, advances in the techniques for production and imaging of such ultrasmall droplets will allow wetting theories to be tested down to the nanometer scale, where they predict the significant influence of phenomena such as the contact line tension or evaporation, which can be neglected in the case of macroscopic droplets. On the applied side, these advances will pave the way for characterizing a diverse set of industrially important materials such as textile or biomedical micro- and nanofibers, powdered solids, and topographically or chemically nanopatterned surfaces, as well as micro-and nanoscale devices, with relevance in diverse industries from biomedical to petroleum engineering. Here, the basic principles of wetting at the micro- and nanoscales are presented, and the essential characteristics of the main experimental techniques available for producing and imaging these droplets are described. In addition, the main fundamental and applied results are reviewed. The most problematic aspects of studying such ultrasmall droplets, and the developments that are in progress that are thought to circumvent them in the coming years, are highlighted.

Force spectroscopy-based simultaneous topographical and mechanical characterization to study polymer-to-polymer interactions in coated alginate microspheres.

Cell-laden hydrogel microspheres have shown encouraging outcomes in the fields of drug delivery, tissue engineering or regenerative medicine. Beyond the classical single coating with polycations, many other different coating designs have been reported with the aim of improving mechanical properties and in vivo performance of the microspheres. Among the most common strategies are the inclusion of additional polycation coatings and the covalent bonding of the semi-permeable membranes with biocompatible crosslinkers such as genipin. However, it remains challenging to characterize the effects of the interactions between the polycations and the hydrogel microspheres over time in vitro. Here we use a force spectroscopy-based simultaneous topographical and mechanical characterization to study polymer-to-polymer interactions in alginate microspheres with different coating designs, maintaining the hydrogels in liquid. In addition to classical topography parameters, we explored, for the first time, the evolution of peak/valley features along the z axis via thresholding analysis and the cross-correlation between topography and stiffness profiles with resolution down to tens of nanometers. Thus, we demonstrated the importance of genipin crosslinking to avoid membrane detachment in alginate microspheres with double polycation coatings. Overall, this methodology could improve hydrogel design rationale and expedite in vitro characterization, therefore facilitating clinical translation of hydrogel-based technologies.

Bacterial response to spatially organized microtopographic surface patterns with nanometer scale roughness.

In this study, the influence of nanometer scale roughness on bacterial adhesion and subsequent biofilm formation has been evaluated using spatially organized microtopographic surface patterns for four major opportunistic pathogens of the genus Staphylococcus (S. epidermidis and S. aureus) responsible for associated-biofilm infections on biomedical devices. The results presented demonstrated that regardless of the strain employed the initial adhesion events to these surfaces are directed by cell-surface contact points maximisation and thus, bacterial cells actively choose their position to settle based on that principle. Accordingly, bacterial cells were found to preferably adhere to the square corners and convex walls of recessed surface features rather than the flat or concave walls of equal protruding features. This finding reveals, for the first time, that the particular shape of the surfaces features employed potentially determined the initial location of the adhering cells on textured surfaces. It was further shown that all surfaces patterns investigated produce a significant reduction in bacterial adhesion (40-95%) and biofilm formation (22-58%). This important observation could not be related to physical constrains or increased solid surface hydrophobicity, as previously suggested by other authors using engineered topographies with microscale surface roughness. It is evident that other causes, such as nanoscale surface roughness-induced interaction energies, might be controlling the process of bacterial adhesion and biofilm formation on surfaces with well-defined nanoscale topography.

Corrosion behavior of surface modifications on titanium dental implant. In situ bacteria monitoring by electrochemical techniques.

The effects of surface modifications and bacteria on the corrosion behavior of titanium have been studied. Five surface modifications were analyzed: two acid etchings (op V, op N), acid etching + anodic oxidation (op NT), sandblasting + acid etching (SLA), and machined surfaces (mach). The corrosion behavior of the surface modifications was evaluated by following the standard ANSI/AAMI/ISO 10993-15:2000. Cyclic potentiodynamic and potentiostatic anodic polarization tests and ion release by ICP-OES after immersion for 7 days in 0.9% NaCl were carried out. Microbiologically induced corrosion (MIC) of low and high roughness (mach, op V) was assessed in situ by electrochemical techniques. Streptococcus mutans bacteria were resuspended in PBS at a concentration of 3 × 108 bacteria mL-1 and maintained at 37°C. MIC was measured through the open circuit potential, Eoc , and electrochemical impedance spectroscopy from 2 to 28 days. Potentiodynamic curves showed the typical passive behavior for all the surface modifications. The titanium ion release after immersion was below 3 ppb. In situ bacteria monitoring showed the decrease in Eoc from -0.065 (SD 0.067) Vvs. Ag/AgCl in mach and -0.115 (SD 0.084) Vvs. Ag/AgCl in op V, to -0.333 (SD 0.147) Vvs. Ag/AgCl in mach and -0.263 (SD 0.005) Vvs. Ag/AgCl in op V, after 2 and 28 days, respectively. A reduction of the oxide film resistance, especially in op V (54 MΩ cm2 and 6 MΩ cm2 , after 2 and 28 days, respectively) could be seen. Streptococcus mutans negatively affected the corrosion resistance of titanium. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 997-1009, 2018.

Balancing microbial and mammalian cell functions on calcium ion-modified implant surfaces.

Implant integration is a complex process mediated by the interaction of the implant surface with the surrounding ions, proteins, bacteria, and tissue cells. Although most implants achieve long-term bone-tissue integration, preventing pervasive implant-centered infections demands further advances, particularly in surfaces design. In this work, we analyzed classical microrough implant surfaces (only acid etched, AE; sandblasted then acid etching, SB + AE) and a new calcium-ion-modified implant surface (AE + Ca) in terms of soft- and hard-tissue integration, bacterial adhesion, and biofilm formation. We cultured on the surfaces primary oral cells from gingiva and alveolar bone, and three representative bacterial strains of the oral cavity, emulating oral conditions of natural saliva and blood plasma. With respect to gingiva and bone cells and in the presence of platelets and plasma proteins, AE + Ca surfaces yielded in average 86% higher adhesion, 44% more proliferation, and triggered 246% more synthesis of extracellular matrix biomolecules than AE-unmodified controls. Concomitantly, AE + Ca surfaces regardless of conditioning with saliva and/or blood plasma showed significantly less bacterial adhesion (67% reduction in average) and biofilm formation (40% reduction in average) than unmodified surfaces. These results highlight the importance of a calcium-rich hydrated interface to favor mammalian cell functions over microbial colonization at implant surfaces. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 421-432, 2018.

Direct Covalent Grafting of Phytate to Titanium Surfaces through Ti-O-P Bonding Shows Bone Stimulating Surface Properties and Decreased Bacterial Adhesion.

Myo-inositol hexaphosphate, also called phytic acid or phytate (IP6), is a natural molecule abundant in vegetable seeds and legumes. Among other functions, IP6 inhibits bone resorption. It is adsorbed on the surface of hydroxyapatite, inhibiting its dissolution and decreasing the progressive loss of bone mass. We present here a method to directly functionalize Ti surfaces covalently with IP6, without using a cross-linker molecule, through the reaction of the phosphate groups of IP6 with the TiO2 layer of Ti substrates. The grafting reaction consisted of an immersion in an IP6 solution to allow the physisorption of the molecules onto the substrate, followed by a heating step to obtain its chemisorption, in an adaptation of the T-Bag method. The reaction was highly dependent on the IP6 solution pH, only achieving a covalent Ti-O-P bond at pH 0. We evaluated two acidic pretreatments of the Ti surface, to increase its hydroxylic content, HNO3 30% and HF 0.2%. The structure of the coated surfaces was characterized by X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and ellipsometry. The stability of the IP6 coating after three months of storage and after sterilization with γ-irradiation was also determined. Then, we evaluated the biological effect of Ti-IP6 surfaces in vitro on MC3T3-E1 osteoblastic cells, showing an osteogenic effect. Finally, the effect of the surfaces on the adhesion and biofilm viability of oral microorganisms S. mutans and S. sanguinis was also studied, and we found that Ti-IP6 surfaces decreased the adhesion of S. sanguinis. A surface that actively improves osseointegration while decreasing the bacterial adhesion could be suitable for use in bone implants.

On the interactions of human bone cells with Ti6Al4V thermally oxidized by means of laser shock processing.

We investigated a Ti6Al4V alloy modified by means of laser peening in the absence of sacrificial coatings. As a consequence of the temperature rise during laser focusing, melting and ablation generated an undulated surface that exhibits an important increase in the content of titanium oxides and OH- ions. Human mesenchymal stem cells and osteoblasts cultured on the oxidized alloy develop noticeable filopodia and lamellipodia. Their paxillin-stained focal adhesions are smaller than in cells attached to the untreated alloy and exhibit a marked loss of colocalization with the ends of actin stress fibers. An important imbalance of phosphorylation and/or dephosphorylation of the focal adhesion kinase is detected in cells grown on the oxidized alloy. Although these mechanisms of adhesion are deeply altered, the surface treatment does not affect cell attachment or proliferation rates on the alloy. Human mesenchymal stem cells cultured on the treated alloy in media containing osteogenic inducers differentiate towards the osteoblastic phenotype to a higher extent than those on the untreated surface. Also, the specific functions of human osteoblasts cultured on these media are enhanced on the treated alloy. In summary, laser peening tailors the Ti6Al4V surface to yield an oxidized layer with increased roughness that allows the colonization and activities of bone-lineage cells.

Surface Topographical Changes of a Failing Acid-Etched Long-Term in Function Retrieved Dental Implant.

The aim of the present study was to report the main topographical and chemical changes of a failing 18-year in function retrieved acid-etching implant in the micro- and nanoscales. A partially edentulous 45 year old rehabilitated with a dental implant at 18 years of age exhibited mobility. After careful examination, a 3.25 × 13-mm press-fit dental implant was retrieved. Scanning electron microscope (SEM) analysis was carried out to study topographical changes of the retrieved implant compared with an unused implant with similar topographical characteristics. Moreover, X-ray photoelectron spectroscopy (XPS) analysis was used to study the surface composition of the retrieved failing implant. Clear changes related to the dual dioxide layer are present as visible in ≥×500 magnification. In addition, it was found that, for the retrieved implant, the surface composition consisted mainly of Ti2p, O1s, C1s, and Al2p. Also, a meaningful decrease of N and C was noticed, whereas the peaks of Ti2p, Al2p, and O1s increased when analyzing deeper (up to ×2000s) in the sample. It was shown that the superficial surface of a retrieved press-fit dual acid-etched implant 18 years after placement is impaired. However, the causes and consequences for these changes cannot be determined.

Bioinspired Quercitrin Nanocoatings: A Fluorescence-Based Method for Their Surface Quantification, and Their Effect on Stem Cell Adhesion and Differentiation to the Osteoblastic Lineage.

Polyphenol-based coatings have several potential applications in medical devices, such as cardiovascular stents, contrast agents, drug delivery systems, or bone implants, due to the multiple bioactive functionalities of these compounds. In a previous study, we fabricated titanium surfaces functionalized with flavonoids through covalent chemistry, and observed their osteogenic, anti-inflammatory, and antifibrotic properties in vitro. In this work, we report a fluorescence-based method for the quantification of the amount of flavonoid grafted onto the surfaces, using 2-aminoethyl diphenylborinate, a boronic ester that spontaneously forms a fluorescent complex with flavonoids. The method is sensitive, simple, rapid, and easy to perform with routine equipment, and could be applied to determine the surface coverage of other plant-derived polyphenol-based coatings. Besides, we evaluated an approach based on reductive amination to covalently graft the flavonoid quercitrin to Ti substrates, and optimized the grafting conditions. Depending on the reaction conditions, the amount of quercitrin grafted was between 64 ± 10 and 842 ± 361 nmol on 6.2 mm Ti coins. Finally, we evaluated the in vitro behavior of bone-marrow-derived human mesenchymal stem cells cultured on the quercitrin nanocoated Ti surfaces. The surfaces functionalized with quercitrin showed a faster stem cell adhesion than control surfaces, probably due to the presence of the catechol groups of quercitrin on the surfaces. A rapid cell adhesion is crucial for the successful performance of an implant. Furthermore, quercitrin-nanocoated surfaces enhanced the mineralization of the cells after 21 days of cell culture. These results indicate that quercitrin nanocoatings could promote the rapid osteointegration of bone implants.

Flavonoid-modified surfaces: multifunctional bioactive biomaterials with osteopromotive, anti-inflammatory, and anti-fibrotic potential.

Flavonoids are small polyphenolic molecules of natural origin with antioxidant, anti-inflammatory, and antibacterial properties. Here, a bioactive surface based on the covalent immobilization of flavonoids taxifolin and quercitrin on titanium substrates is presented, using (3-aminopropyl)triethoxysilane (APTES) as coupling agent. FTIR and XPS measurements confirm the grafting of the flavonoids to the surfaces. Using 2-aminoethyl diphenylborinate (DPBA, a flavonoid-specific dye), the modified surfaces are imaged by fluorescence microscopy. The bioactivity of the flavonoid-modified surfaces is evaluated in vitro with human umbilical cord derived mesenchymal stem cells (hUC-MSCs) and human gingival fibroblasts (HGFs) and compared to that of simple flavonoid coatings prepared by drop casting. Flavonoid-modified surfaces show anti-inflammatory and anti-fibrotic potential on HGF. In addition, Ti surfaces covalently functionalized with flavonoids promote the differentiation of hUC-MSCs to osteoblasts--enhancing the expression of osteogenic markers, increasing alkaline phosphatase activity and calcium deposition; while drop-casted surfaces do not. These findings could have a high impact in the development of advanced implantable medical devices like bone implants. Given the broad range of bioactivities of flavonoid compounds, these surfaces are ready to be explored for other biomedical applications, e.g., as stent surface or tumor-targeted functionalized nanoparticles for cardiovascular or cancer therapies.

Effect of two hydrocarbon and one fluorocarbon surfactant mixtures on the surface tension and wettability of polymers.

The advancing contact angle of water, formamide and diiodomethane on polytetrafluoroethylene (PTFE) and polymethyl methacrylate (PMMA) surfaces covered with the film of ternary mixtures of surfactants including p-(1,1,3,3-tetramethylbutyl) phenoxypoly(ethyleneglycols), Triton X-100 (TX100) and Triton X-165 (TX165) and the fluorocarbon surfactants, Zonyl FSN-100 (FSN100) or Zonyl FSO-100 (FSO100) was measured. The obtained results were used for the surface tension of PTFE and PMMA covered with this film determination from the Young equation on the basis of van Oss et al. and Neumann et al. approaches to the interfacial tension. The surface tension of PTFE and PMMA was also determined using the Neumann et al. equation and the contact angle values for the aqueous solutions of the above mentioned ternary surfactants mixtures which were taken from the literature. As follows from our calculations mainly the presence of the fluorocarbon surfactant in the mixture considerably changes the surface properties of PTFE and PMMA causing that in contrast to hydrocarbon surfactants and their mixtures there is no linear dependence between adhesion and surface tension in the whole range of concentration of the ternary mixtures of surfactants including the fluorocarbon one. The behavior of fluorocarbon surfactants at the polymer-air and polymer-water interfaces is quite different from those of hydrocarbons. In the case of fluorocarbon surfactants not only adsorption but also sorption can occur on the polymer surface.

Three-dimensional and chemical changes on the surface of a 3-year clinically retrieved oxidized titanium dental implant.

OBJECTIVE: To report the main topographical features in the micro- and nano-scales and to assess implant chemical changes of the surface of a 3-year clinically retrieved oxidized titanium dental implant, and compare them with a similar, unused implant. MATERIALS AND METHODS: The surface of the oxidized titanium dental implants was assessed by surface electron microscopy (SEM) analysis at increasing magnifications. X-ray photoelectron spectroscopy (XPS) measurement was performed to analyze the implants surface chemistry. XPS spectra were acquired before and after sputtering with an Ar(+) ion etching of 3keV. RESULTS: With a length of 10-40µm, and a width of 0.05-0.1µm, numerous cracks were ubiquitous along the implant surfaces. Chimney-like structures formed micropores between 1 and 5µm, with up to 40% of them partially or totally broken in the retrieved implant. In relation to chemical composition, Ti and O were predominant in both the unused and in the retrieved implant. N was present in high concentrations (11.49at%) at the retrieved implant surface, in contrast with those observed for the unused implant (1.14at%). Also, C was present in higher concentrations in the retrieved implant surface, while drastically decreased following the sputter-cleaning process. CONCLUSION: While cracks were ubiquitous present from the manufacturing, broken chimney-like structures forming micropores in the clinically retrieved implant may be attributable to excessive mechanical friction forces during the insertion of the implant. Chemical composition of the implant surface may be subjected to changes because of the in vivo environment, with increase of N and C, and decrease of Ca and P.

Functional living biointerphases.

Lactococcus lactis is modified to express a fibronectin fragment (FNIII7₋10) as a membrane protein. This interphase, based on a living system, can be further exploited to provide spatio-temporal factors to direct cell function at the material interface. This approach establishes a new paradigm in biomaterial surface functionalization for biomedical applications.