Danieli C. Rodrigues

Titanium Corrosion Mechanisms in the Oral Environment: A Retrieval Study

Corrosion of titanium dental implants has been associated with implant failure and is considered one of the triggering factors for peri-implantitis. This corrosion is concerning, because a large amount of metal ions and debris are generated in this process, the accumulation of which may lead to adverse tissue reactions in vivo. The goal of this study is to investigate the mechanisms for implant degradation by evaluating the surface of five titanium dental implants retrieved due to peri-implantitis. The results demonstrated that all the implants were subjected to very acidic environments, which, in combination with normal implant loading, led to cases of severe implant discoloration, pitting attack, cracking and fretting-crevice corrosion. The results suggest that acidic environments induced by bacterial biofilms and/or inflammatory processes may trigger oxidation of the surface of titanium dental implants. The corrosive process can lead to permanent breakdown of the oxide film, which, besides releasing metal ions and debris in vivo, may also hinder re-integration of the implant surface with surrounding bone.

Foreign bodies associated with peri-implantitis human biopsies.

BACKGROUND Peri-implantitis is an inflammatory condition that can lead to implant loss. The aim of this descriptive retrospective study is to describe the histopathologic findings in soft tissue biopsies of implants with peri-implantitis. METHODS Thirty-six human peri-implantitis biopsies were analyzed using light microscopy (LM) and scanning electron microscopy (SEM). The composition of foreign materials found in the tissues was assessed using an energy dispersive x-ray spectrometer. RESULTS At the LM level, the inflammatory lesion of peri-implantitis was in most cases a mixture of subacute and chronic inflammation dominated by plasma cells. At the SEM level, radiopaque foreign bodies were identified in 34 of the 36 biopsies. The predominant foreign bodies found were titanium and dental cement. These foreign materials were surrounded by inflammatory cells. CONCLUSIONS At present, the exact mechanism for introduction of these materials and their role in peri-implantitis is unknown. Further research is warranted to determine their etiology and potential role in pathogenesis.

Preparation of TiO2 Nanoparticles Coated with Ionic Liquids: A Supramolecular Approach

Coated TiO2 nanoparticles by dicationic imidazolium-based ionic liquids (ILs) were prepared and studied by differential scanning calorimetry (DSC), dynamic light scattering (DLS), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and scanning electron microscopy (SEM). Three ILs with different hydrophobicity degrees and structural characteristics were used (IL-1, IL-2, and IL-3). The interaction between IL molecules and the TiO2 surface was analyzed in both solid state and in solution. The physical and chemical properties of coated nanoparticles (TiO2 + IL-1, TiO2 + IL-2, and TiO2 + IL-3) were compared to pure materials (TiO2, IL-1, IL-2, and IL-3) in order to evaluate the interaction between both components. Thermal behavior, diffraction pattern, and morphologic characteristics were evaluated in the solid state. It was observed that all mixtures (TiO2 + IL) showed different behavior from that detected for pure substances, which is an evidence of film formation. DLS experiments were conducted to determine film thickness on the TiO2 surface comparing the size (hydrodynamic radius, Rh) of pure TiO2 with coated nanoparticles (TiO2 + IL). Results showed the thickness of the film increased with hydrophobicity of the IL compound. TEM images support this observation. Finally, X-ray diffraction patterns showed that, in coated samples, no structural changes in TiO2 diffraction peaks were observed, which is related to the maintenance of the crystalline structure. On the contrary, ILs showed different diffraction patterns, which confirms the hypothesis of interactions happening between IL and the TiO2 nanoparticles surface.

In Vitro Investigation of the Effect of Oral Bacteria in the Surface Oxidation of Dental Implants

BACKGROUND Bacteria are major contributors to the rising number of dental implant failures. Inflammation secondary to bacterial colonization and bacterial biofilm is a major etiological factor associated with early and late implant failure (peri-implantitis). Even though there is a strong association between bacteria and bacterial biofilm and failure of dental implants, their effect on the surface of implants is yet not clear. PURPOSE To develop and establish an in vitro testing methodology to investigate the effect of early planktonic bacterial colonization on the surface of dental implants for a period of 60 days. MATERIALS AND METHODS Commercial dental implants were immersed in bacterial (Streptococcus mutans in brain-heart infusion broth) and control (broth only) media. Immersion testing was performed for a period of 60 days. During testing, optical density and pH of immersion media were monitored. The implant surface was surveyed with different microscopy techniques post-immersion. Metal ion release in solution was detected with an electrochemical impedance spectroscopy sensor platform called metal ion electrochemical biosensor (MIEB). RESULTS Bacteria grew in the implant-containing medium and provided a sustained acidic environment. Implants immersed in bacterial culture displayed various corrosion features, including surface discoloration, deformation of rough and smooth interfaces, pitting attack, and severe surface rusting. The surface features were confirmed by microscopic techniques, and metal particle generation was detected by the MIEB. CONCLUSION Implant surface oxidation occurred in bacteria-containing medium even at early stages of immersion (2 days). The incremental corrosion resulted in dissolution of metal ions and debris into the testing solution. Dissolution of metal ions and particles in the oral environment can trigger or contribute to the development of peri-implantitis at later stages.

Dicationic imidazolium-based ionic liquids: a new strategy for non-toxic and antimicrobial materials

New dicationic imidazolium-based ionic liquids (ILs) were synthesized, characterized and tested in regards to cytotoxicity and antimicrobial activity. Insertion of a new cationic head and use of organic anions increased the biocompatibility of the ILs developed. IC50 (concentration necessary to inhibit 50% of enzymatic activity) values obtained were considerably higher than those described for monocationic ILs, which indicates an improvement in cytocompatibility. Antimicrobial activity against bacterial species of clinical relevance in wounds and the oral environment was tested. The results showed that ILs were effective in inhibiting bacterial growth even below the minimum inhibitory concentration (MIC). It was observed that structural features that confer higher hydrophobicity to ILs decreased both the IC50 and MIC simultaneously. However, it was possible to establish an equilibrium between those two effects, which gives the safe range of concentrations that ILs can be employed. The results demonstrated that the dicationic-imidazolium-based ILs synthesized may constitute a potent strategy for applications requiring non-toxic materials exhibiting antimicrobial activity.

Commentary: The Case for Routine Maintenance of Dental Implants

The large majority of dental implants are successful over the long term. Failure is usually associated with infection, trauma, inflammation, or a combination of these factors. Early identification and appropriate treatment can identify and eliminate these problems in the majority of cases. Thus routine implant maintenance structured along the guidelines for patients with periodontal diseases is recommended.

Effects of decontamination solutions on the surface of titanium: investigation of surface morphology, composition, and roughness.

AIM To investigate the impact of treatments used to detoxify dental implants on the oxide layer morphology and to infer how changes in morphology created by these treatments may impact re-osseointegration of an implant. MATERIALS AND METHODS Pure titanium (cpTi) and the alloy Ti6Al4V were subjected to a series of chemical treatments and mechanical abrasion simulating surface decontamination of dental implants. The morphology and roughness of the surface layer before and after treatment with these solutions were investigated with optical and atomic force microscopy (OM, AFM). The solutions employed are typically used for detoxification of dental implants. These included citric acid, 15% hydrogen peroxide, chlorhexidine gluconate, tetracycline, doxycycline, sodium fluoride, peroxyacetic acid, and treatment with carbon dioxide laser. The treatments consisted of both immersions of samples in solution and rubbing with cotton swabs soaked in solution for 1, 2, and 5 min. Cotton swabs used were analyzed with energy dispersive spectroscopy (EDS). RESULTS The microscopy investigation showed that corrosion and pitting of the samples were present in both metal grades with immersion and rubbing methods when employing more acidic solutions, which had pH <3. Mildly acidic solutions caused surface discoloration when coupled with rubbing but did not cause corrosion with immersion. Neutral or basic treatments resulted in no signs of corrosion with both methods. EDS results revealed the presence of titanium particles on all rubbing samples. CONCLUSION It was demonstrated in this study that acidic environments coupled with rubbing are able to introduce noticeable morphological changes and corrosion on the surface of both titanium grades.

Ionic Liquid Coatings for Titanium Surfaces: Effect of IL Structure on Coating Profile

Dicationic imidazolium-based ionic liquids (ILs) having bis(trifluoromethylsulfonyl)imide (NTf2) and amino acid-based (methionine and phenylalanine) anionic moieties were synthesized and used to coat titanium surfaces using a dip-coating technique. Dicationic moieties with varying alkyl chains (8 and 10 carbons) and anions with distinct characteristics were selected to understand the influence of IL structural features on deposition profile. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used in this study to help elucidate intermolecular interactions within ILs as well as between ILs and TiO2 surfaces and to investigate IL coating morphology. Charge concentration on IL moieties, as well as the presence of functional groups that can interact via hydrogen bond, such as carboxylate and amino groups, were observed to influence the deposition profile. ILs containing amino acids as the anionic moiety were observed to interact strongly with TiO2, which resulted in more pronounced changes in Ti 2p binding energy. The higher hydrophobicity of the IL having NTf2 as the anionic moiety resulted in higher adhesion strength between the IL coating and TiO2.

Characterization of Cement Particles Found in Peri-implantitis-Affected Human Biopsy Specimens.

PURPOSE Peri-implantitis is a disease characterized by soft tissue inflammation and continued loss of supporting bone, which can result in implant failure. Peri-implantitis is a multifactorial disease, and one of its triggering factors may be the presence of excess cement in the soft tissues surrounding an implant. This descriptive study evaluated the composition of foreign particles from 36 human biopsy specimens with 19 specimens selected for analysis. The biopsy specimens were obtained from soft tissues affected by peri-implantitis around cement-retained implant crowns and compared with the elemental composition of commercial luting cement. MATERIALS AND METHODS Nineteen biopsy specimens were chosen for the comparison, and five test cements (TempBond, Telio, Premier Implant Cement, Intermediate Restorative Material, and Relyx) were analyzed using scanning electron microscopy equipped with energy dispersive x-ray spectroscopy. This enabled the identification of the chemical composition of foreign particles embedded in the tissue specimens and the composition of the five cements. Statistical analysis was conducted using classification trees to pair the particles present in each specimen with the known cements. RESULTS The particles in each biopsy specimen could be associated with one of the commercial cements with a level of probability ranging between .79 and 1. TempBond particles were found in one biopsy specimen, Telio particles in seven, Premier Implant Cement particles in four, Relyx particles in four, and Intermediate Restorative Material particles in three. CONCLUSION Particles found in human soft tissue biopsy specimens around implants affected by peri-implant disease were associated with five commercially available dental cements.

Preparation and Characterization of Injectable Brushite Filled-Poly (Methyl Methacrylate) Bone Cement

Powder-liquid poly (methyl methacrylate) (PMMA) bone cements are widely utilized for augmentation of bone fractures and fixation of orthopedic implants. These cements typically have an abundance of beneficial qualities, however their lack of bioactivity allows for continued development. To enhance osseointegration and bioactivity, calcium phosphate cements prepared with hydroxyapatite, brushite or tricalcium phosphates have been introduced with rather unsuccessful results due to increased cement viscosity, poor handling and reduced mechanical performance. This has limited the use of such cements in applications requiring delivery through small cannulas and in load bearing. The goal of this study is to design an alternative cement system that can better accommodate calcium-phosphate additives while preserving cement rheological properties and performance. In the present work, a number of brushite-filled two-solution bone cements were prepared and characterized by studying their complex viscosity-versus-test frequency, extrusion stress, clumping tendency during injection through a syringe, extent of fill of a machined void in cortical bone analog specimens, and compressive strength. The addition of brushite into the two-solution cement formulations investigated did not affect the pseudoplastic behavior and handling properties of the materials as demonstrated by rheological experiments. Extrusion stress was observed to vary with brushite concentration with values lower or in the range of control PMMA-based cements. The materials were observed to completely fill pre-formed voids in bone analog specimens. Cement compressive strength was observed to decrease with increasing concentration of fillers; however, the materials exhibited high enough strength for consideration in load bearing applications. The results indicated that partially substituting the PMMA phase of the two-solution cement with brushite at a 40% by mass concentration provided the best combination of the properties investigated. This alternative material may find applications in systems requiring highly injectable and viscous cements such as in the treatment of spinal fractures and bone defects.