Véronique Migonney

Resin composite blocks via high-pressure high-temperature polymerization

OBJECTIVES The aim of this study was to thermo-polymerize under high pressure four commercially available dental resin composites to obtain and characterize composite blocks suitable for CAD/CAM procedures. METHODS Gradia (GC, Japan), Vita VM LC (Vita Zahnfabrik, Germany), Grandio (VOCO, Germany), and EsthetX (Dentsply, Germany), were selected for this study. Paradigm (3 M ESPE, USA), a CAD/CAM composite block, was included for comparison. Composite blocks were obtained through polymerization at high-temperature high-pressure (HT/HP). Samples for mechanical/physical characterizations were cut from Paradigm and HT/HP composite blocks while control samples were obtained by photo-polymerizing (PP) the materials in molds. Flexural strength (σ(f)), fracture toughness (K(IC)), hardness, and density (ρ) were determined and compared by pairwise t-tests (α=0.05). Fractured surfaces were characterized under a scanning electron microscope. RESULTS The results have shown that HT/HP polymerization resulted in a significant (p<0.05) increase in σ(f), hardness, and ρ for all composites investigated. Even if K(IC) of all materials was increased by HT/HP polymerization, significant increases were detected only for Gradia and EsthetX. The Weibull modulus of HT/HP polymerized composites was higher than that of PP counterparts. HT/HP materials had higher σ(f), Weibull modulus, and K(IC) compared to Paradigm. The most significant SEM observation of fractured K(IC) specimens from all the materials tested was the presence of fewer and smaller voids in HT/HP polymerized composites. SIGNIFICANCE The results of this study suggest that HT/HP polymerization could be used to obtain dental resin composite blocks with superior mechanical properties, suitable for CAD/CAM processing.

A new approach to graft bioactive polymer on titanium implants: Improvement of MG 63 cell differentiation onto this coating.

Integration of titanium implants into bone is only passive and the resulting fixation is mainly mechanical in nature, with anchorage failure. Our objective, to increase the biointegration of the implant and the bone tissue, could be obtained by grafting a bioactive ionic polymer to the surface of the titanium by a covalent bond. In this paper, we report the grafting of an ionic polymer model poly(sodium styrene sulfonate) (polyNaSS), in a two-step reaction procedure. Treatment of the titanium surface by a mixture of sulfuric acid and hydrogen peroxide allows the formation of titanium hydroxide and titanium peroxide. In the second reaction step, heating of a metal implant, placed in a concentrated solution of sodium styrene sulfonate monomer (NaSS), induces the decomposition of titanium peroxides with the formation of radicals capable of initiating the polymerization of NaSS. Various parameters, such as temperature of polymerization and time of polymerization, were studied in order to optimize the yield of polyNaSS grafting. Colorimetry, Fourier-transformed infrared spectra recorded in an attenuated total reflection, X-ray photoelectron spectroscopy techniques and contact angle measurements were applied to characterize the surfaces. MG63 osteoblastic cell response was studied on polished, oxidized and grafted titanium samples. Cell adhesion, alkaline phosphatase activity and calcium nodules formation were significantly enhanced on grafted titanium samples compared to unmodified surfaces.

Bioactive polymer grafting onto titanium alloy surfaces

Bioactive polymers bearing sulfonate (styrene sodium sulfonate, NaSS) and carboxylate (methylacrylic acid, MA) groups were grafted onto Ti6Al4V alloy surfaces by a two-step procedure. The Ti alloy surfaces were first chemically oxidized in a piranha solution and then directly subjected to radical polymerization at 70 degrees C in the absence of oxygen. The grafted surfaces were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and the toluidine blue colorimetric method. Toluidine blue results showed 1-5microgcm(-2) of polymer was grafted onto the oxidized Ti surfaces. Grafting resulted in a decrease in the XPS Ti and O signals from the underlying Ti substrate and a corresponding increase in the XPS C and S signals from the polymer layer. The ToF-SIMS intensities of the S(-) and SO(-) ions correlated linearly with the XPS atomic percent S concentrations and the ToF-SIMS intensity of the TiO(3)H(2)(-) ion correlated linearly with the XPS atomic per cent Ti concentration. Thus, the ToF-SIMS S(-), SO(-) and TiO(3)H(2)(-) intensities can be used to quantify the composition and amount of grafted polymer. ToF-SIMS also detected ions that were more characteristic of the polymer molecular structure (C(6)H(4)SO(3)(-) and C(8)H(7)SO(3)(-) from NaSS, C(4)H(5)O(2)(-) from MA), but the intensity of these peaks depended on the polymer thickness and composition. An in vitro cell culture test was carried out with human osteoblast-like cells to assess the influence of the grafted polymers on cell response. Cell adhesion after 30min of incubation showed significant differences between the grafted and ungrafted surfaces. The NaSS grafted surfaces showed the highest degree of cell adhesion while the MA-NaSS grafted surfaces showed the lowest degree of cell adhesion. After 4 weeks in vivo in rabbit femoral bones, bone was observed to be in direct contact with all implants. The percentage of mineralized tissue around the implants was similar for NaSS grafted and non-grafted implants (59% and 57%). The MA-NaSS grafted implant exhibited a lower amount of mineralized tissue (47%).

Assessment of fibronectin conformation adsorbed to polytetrafluoroethylene surfaces from serum protein mixtures and correlation to support of cell attachment in culture

Surfaces of polytetrafluoroethylene (PTFE) were exposed to buffered aqueous solutions containing radio-labeled human fibronectin ([125I]Fn), Fn/bovine serum albumin (BSA) binary mixtures of various ratios or whole human plasma dilutions for 1 h. Total adsorbed Fn and albumin adsorption following rinsing was quantified on this surface. 125I-labeled monoclonal antibodies against either the tenth type-III Fn repeat unit (containing the cell-binding RGDS integrin recognition motif) or the Fn amino-terminal domain were used to probe the accessibility of each of these respective Fn regions post-adsorption. Human umbilical vein endothelial cells (HUVECs) were cultured on PTFE surfaces pre-exposed to each of these protein adsorption conditions and compared to identical conditions on tissue culture polystyrene (TCPS). Fn adsorption to PTFE is dependent upon the concentration of albumin co-adsorbing from solution: albumin out-competes Fn for PTFE surface sites even at non-physiological Fn/HSA ratios 10–100-fold biased in Fn. Antibodies against Fn do not readily recognize Fn adsorbed on PTFE as the HSA co-adsorption concentration in either binary mixtures or in plasma increases, indicating albumin masking of adsorbed Fn. At Fn/HSA ratios rich in Fn (1 : 1, 1 :100), albumin co-adsorption actually improves anti-Fn antibody recognition of adsorbed Fn. HUVEC attachment efficiency to PTFE after protein adsorption correlates with amounts of Fn adsorbed and levels of anti-Fn antibody recognition of Fn on PTFE, linking cell attachment to integrin recognition of both adsorbed Fn density and Fn adsorbed conformation on PTFE surfaces.

A bioactive polymer grafted on titanium oxide layer obtained by electrochemical oxidation. Improvement of cell response

The anchorage failure of titanium implants in human body is mainly due to biointegration problem. The proposed solution is to graft a bioactive polymer at the surface of the implant in order to improve and control the interactions with the living system. In this paper, we describe the grafting of poly sodium styrene sulfonate on titanium surface by using a silanization reaction. The key point is to increase the TiOH content at the surface of the implant which can react with methoxy silane groups of 3-methacryloxypropyltrimethoxysilane (MPS). Two procedures were used: chemical oxidation and electrochemical oxidation. The last oxidation procedure was carried out in two different electrolytes: oxalic acid and methanol. These different oxidation methods allow controlling the roughness and the depth of the oxide layer. The methacryloyl group of MPS grafted at the titanium surface by silanization reaction is copolymerized with sodium styrene sulfonate using a thermal initiator able to produce radicals by heating. Colorimetric method, ATR-FTIR, XPS techniques and contact angle measurements were applied to characterize the surfaces. MG63 osteoblastic cell response was studied on polished, oxidized and grafted titanium samples. Cell adhesion, Alkaline Phosphatase activity and calcium nodules formation were significantly enhanced on grafted titanium surfaces compared to un-modified surfaces.

Properties of experimental urethane dimethacrylate-based dental resin composite blocks obtained via thermo-polymerization under high pressure

OBJECTIVES The aim of this study was to use high-pressure high-temperature (HP/HT) polymerization to produce urethane dimethacrylate (UDMA)-triethylene glycol dimethacrylate (TEGDMA) based resin composite blocks (RCB) suitable for dental computer-aided design/manufacture (CAD/CAM) applications and to compare their physical/mechanical properties to those of a commercial dental RCB. The null hypotheses tested were: (1) there are no differences in the physical/mechanical properties between HP/HT polymerized UDMA-TEGDMA RCB and a commercial RCB; (2) volume fraction filler (Vf) does not affect the physical/mechanical properties of HP/HT polymerized RCB. METHODS Four UDMA-based experimental RCB were manufactured under HP/HT conditions. A RCB manufactured under the same HP/HT conditions from a commercial resin composite (Z100) and its commercial counterpart CAD/CAM RCB (Paradigm MZ100) were used as controls. Flexural strength (σf), fracture toughness (KIC), and hardness were determined. The results were analyzed using one-way ANOVA, Scheffé multiple means comparisons (α=0.05), and Weibull statistics (for σf). Scanning electron microscopy was used to characterize fractured surfaces. RESULTS All HP/HT polymerized RCB had superior σf, KIC, and Weibull modulus compared to the commercial dental RCB. The experimental RCB had similar or superior properties compared to HP/HT polymerized Z100 RCB. Fewer and smaller porosities (not quantified) were apparent in HP/HT polymerized RCB. The experimental RCB that contained 65% Vf showed higher porosity, suggesting practical difficulties in filler incorporation beyond a certain Vf. CONCLUSIONS The results of this study suggested that RCB suitable for dental CAD/CAM applications could be obtained by HP/HT polymerization of resin composites based on pure UDMA.

Characterization of poly(Sodium Styrene Sulfonate) Thin Films Grafted from Functionalized Titanium Surfaces

Biointegration of titanium implants in the body is controlled by their surface properties. Improving surface properties by coating with a bioactive polymer is a promising approach to improve the biological performance of titanium implants. To optimize the grafting processes, it is important to fully understand the composition and structure of the modified surfaces. The main focus of this study is to provide a detailed, multitechnique characterization of a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film grafted from titanium surfaces via a two-step procedure. Thin titanium films (∼50 nm thick with an average surface roughness of 0.9 ± 0.2 nm) prepared by evaporation onto silicon wafers were used as smooth model substrates. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that the titanium film was covered with a TiO(2) layer that was at least 10 nm thick and contained hydroxyl groups present at the outermost surface. These hydroxyl groups were first modified with a 3-methacryloxypropyltrimethoxysilane (MPS) cross-linker. XPS and ToF-SIMS showed that a monolayer of the MPS molecules was successfully attached onto the titanium surfaces. The pNaSS film was grafted from the MPS-modified titanium through atom transfer radical polymerization. Again, XPS and ToF-SIMS were used to verify that the pNaSS molecules were successfully grafted onto the modified surfaces. Atomic force microscopy analysis showed that the film was smooth and uniformly covered the surface. Fourier transform infrared spectroscopy indicated that an ordered array of grafted NaSS molecules were present on the titanium surfaces. Sum frequency generation vibration spectroscopy and near edge X-ray absorption fine structure spectroscopy illustrated that the NaSS molecules were grafted onto the titanium surface with a substantial degree of orientational order in the styrene rings.

Heparin-like tubings. I. Preparation, characterization and biological in vitro activity assessment.

In order to prepare tubular materials which could be used in blood-circulating medical devices, polystyrene was grafted by irradiation on to polyethylene tubings. A chemical surface treatment was used which resulted in the functionalization of the inner face of the tubing. This procedure is described and the chemical assessment of the constitution of the functionalized polymer has been completed. Tubing, the inner face of which is made of polyethylene-polystyrene copolymer in which polystyrene moieties were substituted with sulphonate and aspartic acid sulphamid groups, was tested for antithrombic properties in a circulating device under controlled transport conditions and by use of purified proteins.

Heparin-like tubings: III. Kinetics and mechanism of thrombin, antithrombin III and thrombin-antithrombin complex adsorption under controlled-flow conditions

In previous papers, we described treated tubular materials which exhibit an heparin-like antithrombic activity under dynamic conditions. In order to ascertain the heparin-like mechanism of this activity, we have studied the interactions of thrombin, antithrombin III and thrombin-antithrombin III complex with the inner face of these treated tubings under controlled-flow conditions. Moreover, the kinetics of the adsorption of thrombin were studied at different flow rates to establish the rate-determining step.

An alternative quantitative acoustical and electrical method for detection of cell adhesion process in real-time

Sauerbrey [(1956), Z Phys 55:206–222] showed that the shift in resonance frequency of thickness shear mode (TSM) of a quartz crystal sensor is proportional to the mass, which is deposited on it. However, new powerful electrical circuits were developed that are capable of operating TSM quartz crystal sensors in fluids which enabled this method to be introduced into electrochemical and biological applications. These applications include the detection of virus capsids, bacteria, mammalian cells, the interaction of DNA and RNA with complementary strands, specific recognition of protein ligands by immobilized receptors, and last but not least the study of complete immunosensors. Piezoelectric quartz transducers allow a label‐free identification of molecules; they are more than mass sensors since the biosensor response is also influenced by the surface charge of adsorbed proteins, interfacial phenomena, surface roughness and viscoelastic properties of the adhered biomaterial. These new characteristics have recently been used to investigate cell, liposome, and protein adhesion onto surfaces, thus permitting the rapid determination of morphological cell changes as a response to pharmacological substances, and changes in the water content of biopolymers avoiding of time‐consuming methods. We validated an alternative quantitative acoustical engineering for cell adhesion process monitored by the TSM. Shear acoustical results (motional resistance) are further correlated to cell counting procedures and are sensitive of adhesion processes in real‐time. Biotechnol. Bioeng. 2011; 108:947–962.