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Although deterioration of silicone maxillofacial prostheses is severely accentuated in smoking patients, the phenomenon has not been systematically studied. To address a gap in the literature concerning the stability of maxillofacial prostheses during service, in this contribution, the effect of cigarette smoke on the aspect and physical properties of M511 silicone elastomer was evaluated. The aspect, surface, and overall properties of the silicone material, pigmented or not, were followed by AFM, color measurements, FTIR, water contact angle measurements, TGA‐DTG and DSC, hardness and compression stress–strain measurements. The types of the contaminants adsorbed were assessed by XRF, ESI‐MS, MALDI‐MS, and NMR spectral analyses. Important modifications in color, contact angle, surface roughness, local mechanical properties, and thermal properties were found in the silicone material for maxillofacial prostheses after exposure to cigarettes smoke. The presence of lead, nicotine, and several other organic compounds adsorbed into the silicone material was emphasized. Slight decrease in hardness and increase in Young's modulus was found. The combined data show important impact of cigarette smoke on the silicone physical properties and could indicate chemical transformations by secondary cross‐linking. To our knowledge, this is the first study making use of complementary physical methods to assess the effect of cigarette smoke on the aspect and integrity of silicone materials for maxillofacial prostheses. [ABSTRACT FROM AUTHOR]

Although it is known (from the observations of medical professionals) that cigarette smoke negatively affects maxillofacial prostheses, especially through staining/discoloration, systematic research in this regard is limited. Herein, the color modifications of M511 maxillofacial silicone, unpigmented and pigmented with red or skin tone pigments, covered with mattifiers, or with makeup and mattifiers, and directly exposed to cigarette smoke, were investigated by spectrophotometric measurements in the CIELab and RGB color systems. The changes in color parameters are comparatively discussed, showing that the base silicone material without pigmentation and coating undergoes the most significant modifications. Visible and clinically unacceptable changes occurred after direct exposure to only 20 cigarettes. By coating and application of makeup, the material is more resistant to color changes, which suggests that surface treatments provide increased protection to adsorption of the smoke components. The dynamic water vapor sorption (DVS) measurements indicate a decrease of the sorption capacity in pigmented versus unpigmented elastomers, in line with the changes in color parameters. [ABSTRACT FROM AUTHOR]

The biomedical applications of silicones are countless due to their outstanding properties. In dentistry, silicone for maxillofacial and plastic surgery has become indispensable, from both physiological and aesthetic points of view. In this mini-review, silicone materials for dentistry and facial prostheses are discussed, focusing on their properties and alterations when exposed for long periods to different environments. A significant number of studies reported in the literature have been conducted in vitro, mimicking some of the main degradative factors which have been identified as triggers for discoloration and deterioration of the mechanical properties. Among these, in artificial aging and accelerated natural aging studies, UV radiation is considered the most important. Other weathering factors, biological contamination, and disinfection agents may have dramatic effects as well. Several general properties of silicones are described at the beginning, with a focus on biocompatibility, cross-linking mechanisms, and applications in dentistry and maxillofacial prosthetics. We discuss the ongoing cross-linking and/or possible exudation after manufacturing, which also affects the stability of the prosthesis over time, and possibly the patient. Next, the main environmental factors that affect the prostheses in service are presented, including the role of cigarettes smoke, which has been discussed very little so far. A few aspects, such as biofilm formation, its negative effects, and proposed solutions to overcome this phenomenon regarding silicones, are also described. We conclude by proposing a set of topics for future research and development based on the gaps that have been identified in the literature. Although silicones are probably irreplaceable in maxillofacial prosthetics, improvements in terms of base materials, additives, surface treatments, and maintenance are possible and necessary for long-lasting and safer prostheses. [ABSTRACT FROM AUTHOR]

Amassing remarkable properties, silicones are practically indispensable in our everyday life. In most classic applications, they play a passive role in that they cover, seal, insulate, lubricate, water-proof, weather-proof etc. However, silicone science and engineering are highly innovative, seeking to develop new compounds and materials that meet market demands. Thus, the unusual properties of silicones, coupled with chemical group functionalization, has allowed silicones to gradually evolve from passive materials to active ones, meeting the concept of "smart materials", which are able to respond to external stimuli. In such cases, the intrinsic properties of polysiloxanes are augmented by various chemical modifications aiming to attach reactive or functional groups, and/or by engineering through proper cross-linking pattern or loading with suitable fillers (ceramic, magnetic, highly dielectric or electrically conductive materials, biologically active, etc.), to add new capabilities and develop high value materials. The literature and own data reflecting the state-of-the art in the field of smart silicones, such as thermoplasticity, self-healing ability, surface activity, electromechanical activity and magnetostriction, thermo-, photo-, and piezoresponsivity are reviewed. [ABSTRACT FROM AUTHOR]

Two disiloxanes with pyridyl or isocyanide functional groups, as well as silica materials carrying pyridyl or thiol functionalities were used as ligands for Pt(IV) and Fe(III) ions. The molecular and silica-supported metal complexes were tested in a model hydrosilylation reaction between 1,3-divinyl tetramethyldisiloxane and 1,1,3,3-tetramethyldisiloxane, conducted in (pseudo)-heterogeneous conditions. The new hydrosilylation catalysts afforded 75-100 % conversion and 87-93 % selectivity, based on NMR data, while some of them presented recyclability; they were also successful in silicones crosslinking at room temperature. In particular, the iron-isocyanide disiloxane complex is proposed as a promising, cheap, unsophisticated and stable catalyst, capable to act in heterogeneous conditions, without the need of dry solvent or inert atmosphere. Silica-supported Pt or Pt/Pd catalysts, obtained with commercial or recovered noble metals precursors, presented high conversion and increased regioselectivity in the tested process, being reusable, and are efficient in other hydrosilylation reactions, useful in organic and silicon chemistry. [ABSTRACT FROM AUTHOR]

Isocyanides (isonitriles) are unique organic compounds that contain a formally divalent carbon. Herein, the synthesis of 1,3‐bis(isocyanopropyl)tetramethyldisiloxane was performed by a modified carbylamine method, using a phase transfer agent. Spectral methods (nuclear magnetic resonance [NMR], Fourier transform infrared spectroscopy [FT‐IR], and electrospray ionization mass spectrometry [ESI‐MS]) were used to confirm the structure. Energy gap of 1.86 eV (measured by diffuse reflectance spectroscopy [DRS]), high dielectric permittivity (15 at 10 kHz), and conductivity value in the order of 10−7 S·cm−1 place this compound in the range of wide‐bandgap semiconductors. The synthesis of Pt, Ag, and Fe metal complexes without organic co‐ligands and their catalytic activity were also investigated. The Pt complex was active in hydrosilylation reaction and in reduction of p‐nitrophenol, whereas the Ag complex was found effective in alkaline decomposition of hydrogen peroxide. The Fe complex is a new and cheap heterogeneous hydrosilylation catalyst and also showed very good catalytic behavior in heterogeneous Fenton‐like photodecomposition of Congo Red in various photo‐irradiation conditions, with 100% color removal efficiency after 60 min under sunlight. Thus, a simple path for siloxane‐containing materials with promising applications is open. [ABSTRACT FROM AUTHOR]