Synthesis of polymerizable betulin maleic diester derivative for dental restorative resins with antibacterial activity.

OBJECTIVE: Bisphenol A glycidyl methacrylate (Bis-GMA) is of great importance for dental materials as the preferred monomer. However, the presence of bisphenol-A (BPA) core in Bis-GMA structure causes potential concerns since it is associated with endocrine diseases, developmental abnormalities, and cancer lesions. Therefore, it is desirable to develop an alternative replacement for Bis-GMA and explore the intrinsic relationship between monomer structure and resin properties. METHODS: Here, the betulin maleic diester derivative (MABet) was synthesized by a facile esterification reaction using plant-derived betulin and maleic anhydride as raw materials. Its chemical structure was confirmed by 1H and 13C NMR spectra, FT-IR spectra, and HR-MS, respectively. The as-synthesized MABet was then used as polymerizable comonomer to partially or completely substitute Bis-GMA in a 50:50 Bis-GMA: TEGDMA resin (5B5T) to formulate dental restorative resins. These were then determined for the viscosity behavior, light transmittance, real-time degree of conversion, residual monomers, mechanical performance, cytotoxicity, and antibacterial activity against Streptococcus mutans (S. mutans) in detail. RESULTS: Among all experimental resins, increasing the MABet concentration to 50 wt% made the resultant 5MABet5T resin have a maximum in viscosity and appear dark yellowish after polymerization. In contrast, the 1MABet4B5T resin with 10 wt% MABet possessed comparable shear viscosity and polymerization conversion (46.6 ± 1.0% in 60 s), higher flexural and compressive strength (89.7 ± 7.8 MPa; 345.5 ± 14.4 MPa) to those of the 5B5T control (48.5 ± 0.6%; 65.7 ± 6.7 MPa; 223.8 ± 57.1 MPa). This optimal resin also had significantly lower S. mutans colony counts (0.35 ×108 CFU/mL) than 5B5T (7.6 ×108 CFU/mL) without affecting cytocompatibility. SIGNIFICANCE: Introducing plant-derived polymerizable MABet monomer into dental restorative resins is an effective strategy for producing antibacterial dental materials with superior physicochemical property.

Influência da espessura da cerâmica no comportamento biomecânico, sobrevivência e na translucidez de coroas monolíticas / Influence of ceramic thickness on biomechanical behavior, survival and translucency of monolithic crowns

Apesar do aumento do uso de coroas monolíticas, seu desempenho, em diferentes aspectos, ainda não foi determinado. Inicialmente, este projeto investigou o comportamento biomecânico de diferentes coroas monolíticas convencionais sobre dentes e a distribuição de tensões na camada de cimento (Artigo 1). Como objetivo principal, este estudo avaliou o efeito do princípio do mínimo preparo dental no comportamento biomecânico, confiabilidade e translucidez de coroas monolíticas posteriores em cerâmica. No entanto, para definir o substrato a ser utilizado para receber as coroas usinadas, uma análise complementar foi desenvolvida para observar o comportamento da restauração sobre diferentes substratos através da análise por elementos finitos (Artigo 2). E para o Artigo 3, cento e vinte e seis coroas foram fabricadas e divididas (n = 21 / gr) de acordo com o material (zircônia de alta translucidez -YZHT, silicato de lítio reforçado com zircônia - ZLS e cerâmica híbrida -HC) e espessura (0,5 ­ subgrupo .5 ou 1 mm ­ subgrupo 1). A concentração de tensão de tração foi calculada pelo método dos elementos finitos, as coroas adesivamente cimentadas foram fadigadas pelo teste step-stress para calcular a confiabilidade de missões a 600 e 900 N a 100.000 ciclos; e, a translucidez foi analisada em 10 discos de cada material e espessura. Maior concentração de tensão de tração foi observada em coroas mais finas e com módulo de elasticidade mais alto. As coroas YZHT foram suspensas quando a fadiga atingiu a carga de 1.500N, sendo utilizado Weibull 1-parâmetro para analisar os dados. A confiabilidade foi afetada apenas pela espessura em 900 N. ZLS.5 apresentou sobrevida semelhante à HC.5, que foi semelhante aos grupos que apresentaram 100% de sobrevivência. YZHT mostrou a maior resistência característica e dispersão de dados. ZLS1 (22,3 ± 1,4) apresentou maior translucidez que HC1 (19,2 ± 0,6) e YZHT1 (12,0 ± 2,9), enquanto ZLS.5 e HC.5 foram semelhantes (26,5 ± 2,3, 26,7 ± 2,2) e superiores a YZHT.5 (12,7 ± 1,2). O HC.5 combinou alta confiabilidade e translucidez com baixa concentração de tensão, produzindo melhor desempenho da coroa e preservação dos dentes(AU)

Despite the increased use of monolithic crowns, their performance in different aspects has not yet been determined. Initially, this project investigated the biomechanical behavior of different conventional monolithic crowns on teeth and the stress distribution in the cement layer (Article 1). As main purpose, this study evaluated the effect of minimal dental preparation principle on the biomechanical behavior, reliability and translucency of posterior monolithic ceramic crowns. However, to define the substrate to be used to receive the machined crowns, a complementary analysis was developed to observe the restoration behavior on different substrates using the finite element analysis (Article 2). And for Article 3, one-hundred twenty six crowns were divided (n=21/gr) according to the material (High translucent zirconia - YZHT, Zirconia reinforced lithium silicate - ZLS and Hybrid ceramic - HC) and thickness (0.5 or 1 mm). Tensile stress concentration was calculated using the finite element method, the crowns were adhesivelly cemented and step stress fatigued to calculate reliability for missions at 600 and 900 N at 100,000 cycles; and, the translucency was analyzed in 10 discs of each material and thickness. Higher stress concentration was found in thinner crowns and those with higher elastic modulus. YZHT crowns were suspended when fatigue reached 1,500N load, thus 1-parameter Weibull was used to analyse the data. Reliability was only affected by thickness at 900 N. ZLS.5 showed similar survival to HC.5, which was similar to the groups that presented 100% survival. YZHT showed the highest strength and data scattering. ZLS1 (22.3 ± 1.4) presented higher translucency than HC1 (19.2 ± 0.6) and YZHT1 (12.0 ± 2.9), whereas ZLS.5 and HC.5 were similar to each other (26.5 ± 2.3, 26.7 ± 2.2) and superior to YZHT.5 (12.7 ± 1.2). HC.5 combined high reliability and translucency with low stress concentration, yielding better crown performance and tooth preservation(AU)

Comportamento biomecânico e sobrevivência de coroas de cerâmica híbrida implantosuportadas confeccionadas por diferentes técnicas / Biomechanical behavior and survival of implant-supported hybrid ceramic crowns made by different techniques

O presente estudo teve como objetivo investigar a probabilidade de sobrevivência e distribuição de tensão de restaurações de cerâmica infiltrada por polímero sobre implantes. Setenta e cinco coroas suportadas por implantes foram divididas de acordo com a técnica de fabricação, usando uma base de titânio(Tibase): CME - Solução protética de duas peças composta por uma coroa cimentada no pilar híbrido (Tibase + mesoestrutura cerâmica); MC - Solução protética de peça única composta por uma coroa cimentada diretamente sobre o Tibase; e MP - Solução protética de peça única composta por uma coroa cimentada em um Tibase com orifício de acesso para parafuso. Todas as coroas foram fadigadas pelo teste stepwise (intervalo de carga de 50 N a cada 20.000 ciclos até 1200 N e 350.000 ciclos). As coroas falhadas foram inspecionadas sob microscopia eletrônica de varredura e a probabilidade de sobrevivência foi analisada usando os testes Log-Rank e Willcoxon. Uma geometria tridimensional de cada grupo foi modelada e analisada pelo método dos elementos finitos. Resultados de deformação total, tensão de von-Misses, tensão principal máxima e microdeformação foram solicitados sob carga axial de 900 N. Log-Rank (p = 0,17) e Willcoxon (p = 0,11) revelaram uma probabilidade de sobrevivência semelhante entre as técnicas de fabricação sob 300 e 900 N. Independentemente da sobrevivência semelhante entre CME e MC, MP mostrou resistência característica superior e menor variação de dados. Maior concentração de tensão foi observada no perfil de emergência da coroa independente do grupo. A fractografia possibilitou identificar que a direção de propagação de trinca ocorreu da cervical para oclusal. É possível concluir que a sobrevivência de uma restauração implanto-suportada com cerâmica vítrea infiltrada por polímero independe da técnica utilizada para sua confecção; e que a região do perfil de emergência da coroa protética sempre deve ser avaliada nas consultas periódicas devido a grande prodominância de falhas nessa área(au)

The present study aimed to investigate the survival probability and the stress distribution of a polymer infiltrate ceramic restorations cemented on a chairside titanium­base manufactured using different techniques. Seventy-five implant-supported crowns were divided according to the manufacturing technique using a chairside titanium­base: CME - Two-piece prosthetic solution composed by a crown cemented on the hybrid abutment; MC - One-piece prosthetic solution composed by a crown direct cemented on a titanium base; and MP - One-piece prosthetic solution composed by a crown cemented on a Tibase with screw access hole. All crowns were staircase fatigued (load step of 50 N in each 20,000 cycles until 1200 N and 350,000 cycles). The failed crowns were inspected under scanning electron microscopy. And the survival probability using Log-Rank and Willcoxon tests. One threedimensional geometry from each group were modeled and analyzed using the finite element method. Results in total deformation, von-Misses stress, maximum principal stress and microstrain were requested under 900 N axial load. Log-Rank (p = 0.17) and Willcoxon (p = 0.11) revealed similar survival probability between the techniques at 300 and 900 N. Regardless of the similar survival between CME and MC, MP showed superior characteristic strength and less data variation. Higher stress concentration was observed in the emergence profile of the crown regardless the group design. Fractography analysis allowed to identify that the crack propagation direction occurred from cervical to occlusal. It is possible to conclude that the survival of an implant-supported restoration with polymer infiltrated ceramic network is not influence by the technique used to make it; and that the emergence profile of the prosthetic crown must always be evaluated due to the great incidence of failures in this area(AU)

Avaliação do desgaste fisiológico da camada de caracterização aplicada sobre cerâmicas odontológicas / Evaluation of the physiological wear of the applied characterization layer on dental ceramics

O presente estudo teve por objetivo avaliar o comportamento da camada de caracterização sobre zircônia de alta translucidez (YZHT, Vita YZ HT), cerâmica feldspática (FD/VMII, Vita Mark II) e silicato de lítio reforçado por zircônia (ZLS, Vita Suprinity) frente à simulação de desgaste fisiológico variando os antagonistas em YZHT, esteatita e cerâmica híbrida com polímero (Vita Enamic). Foram obtidos 120 discos (ø 12 mm, 1,2 mm de espessura) cerâmicos, sendo 30 de YZHT e FD, e 60 de ZLS, através de corte de blocos para CAD/CAM. As amostras de YZHT foram sinterizadas, e na sequência os grupos YZHT e FD receberam a camada de caracterização. A caracterização das amostras de ZLS foi realizada no mesmo ato da cristalização (ZLS1, etapa única) ou em queima posterior a cristalização (ZLS2, duas etapas). A caracterização foi realizada de acordo com as recomendações do fabricante e todas as amostras receberam aplicação de glaze e consequente queima. Os espécimes foram divididos em subgrupos (n=10) de acordo com os antagonistas: esteatita, cerâmica híbrida ou zircônia; em seguida, foram submetidos à simulação do desgaste fisiológico. Os parâmetros de rugosidade média (Ra) e largura média dos elementos do perfil de rugosidade (Rsm) foram analisados em diferentes momentos da simulação de desgaste fisiológico desde o início até o final da ciclagem. Após os 15.000 ciclos foram calculados a perda de massa dos discos cerâmicos e dos pistões antagonistas. Os resultados foram analisados estatisticamente por Anova 2 fatores e Tukey (p<0,05). Antes do desgaste, as cerâmicas não apresentaram diferenças para os parâmetros de rugosidade, Ra (p=0,3348), Rz (p=0,5590) e Rsm (p=0,5330). Os antagonistas não apresentaram diferenças para os parâmetros, Ra (p=0,0541) e Rsm (p=0,0613), enquanto que o parâmetro Rz (p=0,000) apresentou diferença, já que a esteatita (18,98 ± 2,98 µm) apresentou uma maior rugosidade média quando analisada a altura máxima do perfil quando comparado com os antagonistas em enamic (12,35 ± 0,91 µm) e zircônia (11,47 ± 0,89 µm). Após o desgaste, as cerâmicas continuaram sem apresentar diferenças estatísticas para os parâmetros de rugosidade, Ra (p=0,488), Rz (p=0,681) e Rsm (p=0,256). Os antagonistas não apresentaram diferença para o parâmetro Ra (p=0,124), porém, apresentaram diferença para o parâmetro Rz (p=0,000), já que a esteatita (57,98 ± 4,11 µm) apresentou uma maior média para tal parâmetro quando comparado com os antagonistas em enamic (44,86 ± 2,34 µm) e zircônia (37,81 ± 1,40 µm); e para o parâmetro Rsm (p=0,000), já que as médias da esteatita (502,72 ± 72,20 µm), enamic (385,67 ± 24,84 µm) e zircônia (268,94 ± 27,99 µm) apresentaram diferenças entre si. O tipo de cerâmica (p<0,0001) influenciou a perda de massa das amostras e a interação entre cerâmica e antagonista (p=0,0098), com isso influenciou a perda de massa dos pistões antagonistas. O grupo ZLS 2 apresentou a maior perda de massa entre os grupos testados. Todos os antagonistas testados apresentaram perda de massa semelhante contra o FD, enquanto a esteatita apresentou maior perda de massa quando testadas com amostras YHZT, ZLS 1 e ZLS 2. Todas as cerâmicas apresentaram rugosidade semelhante antes e após a simulação de desgaste. As amostras de cerâmicas apresentaram uma perda de massa semelhante. No entanto, a queima adicional da caracterização da cerâmica de silicato de lítio reforçado por zircônia favoreceu uma maior perda de massa, sem que houvesse alteração de sua resistência(AU)

The present study aimed to evaluate the behavior of the characterization layer on high translucency zirconia (YZHT, Vita YZ HT), feldspar ceramic (FD / VMII, Vita Mark II) and zirconia reinforced lithium silicate (ZLS, Vita Suprinity) compared to the simulation of physiological wear, varying the antagonists in YZHT, steatite and hybrid ceramic with polymer (Vita Enamic). 120 ceramic discs (ø 12 mm, 1.2 mm thick) were obtained, 30 from YZHT and FD, and 60 from ZLS, by cutting blocks for CAD / CAM. The YZHT samples were sintered, and in the sequence the groups YZHT and FD received the characterization layer. The characterization of the ZLS samples was carried out in the same act of crystallization (ZLS1, single step) or in burning after crystallization (ZLS2, two steps). The characterization was carried out according to the manufacturer's recommendations and all samples received application of glaze and consequent burning. The specimens were divided into subgroups (n = 10) according to the antagonists: steatite, hybrid ceramic or zirconia; then, they were submitted to the simulation of physiological wear. The parameters of average roughness (Ra) and average width of the elements of the roughness profile (Rsm) were analyzed at different moments of the simulation of physiological wear from the beginning to the end of the cycle. After 15,000 cycles, the mass loss of the ceramic discs and antagonistic pistons was calculated. The results were analyzed statistically by Anova 2 factors and Tukey (p <0.05). Before wear, the ceramics showed no differences for the roughness parameters, Ra (p = 0.3348), Rz (p = 0.5590) and Rsm (p = 0.5330). The antagonists showed no differences for the parameters, Ra (p = 0.0541) and Rsm (p = 0.0613), while the parameter Rz (p = 0.000) showed a difference, since steatite (18.98 ± 2) , 98 µm) presented a higher average roughness when the maximum profile height was analyzed when compared with the antagonists in enamic (12.35 ± 0.91 µm) and zirconia (11.47 ± 0.89 µm). After wear, the ceramics continued to show no statistical differences for the roughness parameters, Ra (p = 0.488), Rz (p = 0.681) and Rsm (p = 0.256). The antagonists showed no difference for the Ra parameter (p = 0.124), however, they showed a difference for the Rz parameter (p = 0.000), since steatite (57.98 ± 4.11 µm) showed a higher average for such parameter when compared with antagonists in enamic (44.86 ± 2.34 µm) and zirconia (37.81 ± 1.40 µm); and for the parameter Rsm (p = 0.000), since the averages of steatite (502.72 ± 72.20 µm), enamic (385.67 ± 24.84 µm) and zirconia (268.94 ± 27.99 µm ) showed differences between them. The type of ceramic (p <0.0001) influenced the loss of mass of the samples and the interaction between ceramic and antagonist (p = 0.0098), thereby influencing the loss of mass of the antagonist pistons. The ZLS 2 group showed the greatest loss of mass among the tested groups. All tested antagonists showed similar mass loss against FD, while steatite showed greater mass loss when tested with YHZT, ZLS 1 and ZLS 2 samples. All ceramics showed similar roughness before and after wear simulation. The ceramic samples showed a similar mass loss. However, the additional burning of the characterization of the zirconia-reinforced lithium silicate ceramic favored a greater loss of mass, without altering its strength(AU)

Novel Bioactive and Therapeutic Dental Polymeric Materials to Inhibit Periodontal Pathogens and Biofilms.

Periodontitis is a common infectious disease characterized by loss of tooth-supporting structures, which eventually leads to tooth loss. The heavy burden of periodontal disease and its negative consequence on the patient's quality of life indicate a strong need for developing effective therapies. According to the World Health Organization, 10⁻15% of the global population suffers from severe periodontitis. Advances in understanding the etiology, epidemiology and microbiology of periodontal pocket flora have called for antibacterial therapeutic strategies for periodontitis treatment. Currently, antimicrobial strategies combining with polymer science have attracted tremendous interest in the last decade. This review focuses on the state of the art of antibacterial polymer application against periodontal pathogens and biofilms. The first part focuses on the different polymeric materials serving as antibacterial agents, drug carriers and periodontal barrier membranes to inhibit periodontal pathogens. The second part reviews cutting-edge research on the synthesis and evaluation of a new generation of bioactive dental polymers for Class-V restorations with therapeutic effects. They possess antibacterial, acid-reduction, protein-repellent, and remineralization capabilities. In addition, the antibacterial photodynamic therapy with polymeric materials against periodontal pathogens and biofilms is also briefly described in the third part. These novel bioactive and therapeutic polymeric materials and treatment methods have great potential to inhibit periodontitis and protect tooth structures.

Biocompatible alkyl cyanoacrylates and their derivatives as bio-adhesives.

Cyanoacrylate adhesives and their homologues have elicited interest over the past few decades owing to their applications in the biomedical sector, extending from tissue adhesives to scaffolds to implants to dental material and adhesives, because of their inherent biocompatibility and ability to polymerize solely with moisture, thanks to which they adhere to any substrate containing moisture such as the skin. The ability to tailor formulations of alkyl cyanoacrylate to form derivative compounds to meet application requirements along with their biodegradability in conjunction with their inherent biocompatibility make them highly sought after candidates in the biomedical sector. There has been extensive exploration of cyanoacrylate adhesives and their homologue systems in biomedical applications, but no consolidated literature of the vast data is available. The ability of cyanoacrylate adhesives to cure at low temperatures and without the need for any hardener, which is attributed to the high-strength bonding interaction between two non-amalgamating substrates, with their ease of dispersion and self-curing, avoids the curtailing of the effective utilization of such adhesives in biomedical engineering applications as bio glues for amalgamating tissues, implants, scaffolds etc. This article consolidates copious work on cyanoacrylate adhesives and their derived systems which are functional in versatile biomedical engineering applications such as bio glues, dental material and adhesives and other potential applications.

In vitro and in vivo studies of anti-bacterial copper-bearing titanium alloy for dental application.

OBJECTIVE: A novel copper-bearing titanium alloy (Ti-Cu) was fabricated for dental application that is expected to efficiently restrain the growth of bacteria and discourage biofilm formation. The aim of this study was to investigate both the antibacterial activity and biofilm inhibition of Ti-Cu alloy in vitro, and the antibacterial effect of Ti-Cu implant in early stage of peri-implantitis in vivo. METHODS: Staphylococcus aureus and Escherichia coli were selected to evaluate the antibacterial activity of Ti-Cu alloy and Ti served as control. The antibacterial rate, attached bacteria and developed biofilms were studied from quantitative antibacterial test, biofilm observation and bacterial morphological examination. Electrochemical tests were used to investigate the corrosion property of Ti-Cu alloy. Furthermore, both Ti and Ti-Cu dental implants were manufactured and then implanted in the mandibular premolar sites of beagle dogs for 3 months with ligature-infected treatment. Implant-tissue samples were prepared for radiographic analysis, Micro-CT evaluation and histological examination. RESULTS: Ti-Cu alloy was found to efficiently kill the attached bacteria by ways of damaging cell membranes and cell walls and strongly inhibit the biofilm formation. However, Ti-Cu alloy had excellent corrosion resistance similar with Ti. Further, Ti-Cu dental implants showed superior capacities of inhibiting the bone resorption caused by bacterial infection and enhancing bone formation. SIGNIFICANCE: Ti-Cu alloy strongly inhibited biofilm formation in vitro and prevented bacterial infection associated with dental implant in vivo, making it great potential for application in dental implants with excellent antibacterial viability and positive effect against bone resorption induced by peri-implantitis.

Fabrication and characterisation of a novel biomimetic anisotropic ceramic/polymer-infiltrated composite material.

OBJECTIVE: To fabricate and characterise a novel biomimetic composite material consisting of aligned porous ceramic preforms infiltrated with polymer. METHOD: Freeze-casting was used to fabricate and control the microstructure and porosity of ceramic preforms, which were subsequently infiltrated with 40-50% by volume UDMA-TEGDMA polymer. The composite materials were then subjected to characterisation, namely density, compression, three-point bend, hardness and fracture toughness testing. Samples were also subjected to scanning electron microscopy and computerised tomography (Micro-CT). RESULTS: Three-dimensional aligned honeycomb-like ceramic structures were produced and full interpenetration of the polymer phase was observed using micro-CT. Depending on the volume fraction of the ceramic preform, the density of the final composite ranged from 2.92 to 3.36g/cm3, compressive strength ranged from 206.26 to 253.97MPa, flexural strength from 97.73 to 145.65MPa, hardness ranged from 1.46 to 1.62GPa, and fracture toughness from 3.91 to 4.86MPam1/2. SIGNIFICANCE: Freeze-casting provides a novel method to engineer composite materials with a unique aligned honeycomb-like interpenetrating structure, consisting of two continuous phases, inorganic and organic. There was a correlation between the ceramic fraction and the subsequent, density, strength, hardness and fracture toughness of the composite material.

Preparation of a low viscosity urethane-based composite for improved dental restoratives.

Several new urethane-based dimethacrylates were synthesized, characterized and used to formulate the resin composites. Compressive strength (CS) was used as a screen tool to evaluate the mechanical property of the formed composites. Flexural strength, diametral tensile strength, water sorption, degree of conversion and shrinkage of the composites were also evaluated. The results show that most of the synthesized urethane-based dimethacrylates were solid, which are not suitable to dental filling restorations. However, it was found that liquid urethane-based dimethacrylates could be derivatized using asymmetrical methacrylate synthesis. Not only the newly synthesized urethane-based dimethacrylates showed lower viscosity values but also their constructed composites exhibited higher mechanical strengths. Without triethyleneglycol dimethacrylate (TEGDMA) addition, the new urethane-constructed composites showed significantly lower water sorption and shrinkage.

Ion-releasing dental restorative composites containing functionalized brushite nanoparticles for improved mechanical strength.

OBJECTIVES: This study describes the synthesis of brushite nanoparticles (CaHPO4·2H2O) functionalized with triethylene glycol dimethacrylate (TEGDMA) and their application in dental restorative composites with remineralizing capabilities. METHODS: Nanoparticles were synthesized, with TEGDMA being added to one of the precursor solutions at three different molar ratios (0:1, 0.5:1 and 1:1, in relation to the ammonium phosphate precursor). Then, they were added (10 vol%) to a photocurable dimethacrylate matrix containing 50 vol% of reinforcing glass particles. The resulting composites were tested for degree of conversion, biaxial flexural strength and elastic modulus (after 24h and 28days in water), and ion release (over a 28-day period). Commercial composites (one microhybrid and one microfilled) were tested as controls. RESULTS: The final TEGDMA content in the functionalizing layer was modulated by the molar ratio added to the precursor solution. Functionalization reduced nanoparticle size, but did not reduce agglomeration. Improved mechanical properties were found for the composite containing nanoparticles with higher TEGDMA level in comparison to the composite containing non-functionalized nanoparticles or those with a low TEGDMA level. All brushite composites presented statistically significant reductions in strength after 28 days in water, but only the material with high-TEGDMA nanoparticles retained strength similar to the microhybrid commercial control. Overall, ion release was not affected by functionalization and presented steady levels for 28 days. SIGNIFICANCE: Though agglomeration was not reduced by functionalization, the improvement in the matrix-nanoparticle interface allowed for a stronger material, without compromising its remineralizing potential.

Synthesis and characterization of Ciprofloxacin-containing divinyl oligomers and assessment of their biodegradation in simulated salivary esterase.

OBJECTIVE: Two leading causes contributing to dental restoration replacement are the marginal breakdown at the composite/dentin interface and secondary caries mediated by bacteria. The objective of the present study was to synthesize oligomers which incorporated enhanced bio-stability but would also be able to generate antimicrobial function if they underwent degradation. METHODS: Stability was incorporated into the oligomers by generating structural features that would physically hinder the availability of hydrolytically sensitive groups in the oligomers. As a proof-of concept for the antibacterial feature, antimicrobial function was achieved by covalently incorporating Ciprofloxacin (CF) into the backbone of cross-linking divinyl oligomers (referred to as EDV and HLH-CFPEG). The hydrolytic stability of the oligomers was studied in simulated human salivary esterase and compared to the commercial monomer 2,2-bis[4(2-hydroxy-3-methacryloxypropoxy)-phenyl]propane (BisGMA). RESULTS: Both drug oligomers were found to be significantly more stable than BisGMA. Upon degradation, both drug oligomers released CF differentially in free form. Polymer synthesis from resin formulations containing 15wt% HLH-CFPEG showed a high degree of vinyl group conversion and gel content, and under hydrolytic conditions showed the release of CF during a 28-day monitoring study period. SIGNIFICANCE: HLH-CFPEG can be used in dental resin adhesive systems for local delivery of CF to the marginal interface. Minimizing the growth of Streptococcus mutans at the marginal site can improve longevity by reducing esterase activity derived specifically from S. mutans.

Mechanical properties and fracture behavior of flowable fiber reinforced composite restorations.

OBJECTIVE: The aim was to evaluate the effect of short glass-fiber/filler particles proportion on fracture toughness (FT) and flexural strength (FS) of an experimental flowable fiber-reinforced composite (Exp-SFRC) with two methacrylate resin formulations. In addition, we wanted to investigate how the fracture-behavior of composite restorations affected by FT values of SFRC-substructure. METHODS: Exp-SFRC was prepared by mixing 50wt% of dimethacrylate based resin matrix (bisGMA or UDMA based) to 50wt% of various weight fractions of glass-fiber/particulate filler (0:50, 10:40, 20:30, 30:20, 40:10, 50:0wt%, respectively). FT and FS were determined for each experimental material following standards. Specimens (n=8) were dry stored (37°C for 2 days) before they were tested. Four groups of posterior composite crowns (n=6) composed of different Exp-SFRCs as substructure and surface layer of commercial particulate filler composite were fabricated. Crowns were statically loaded until fracture. Failure modes were visually examined. The results were statistically analysed using ANOVA followed by post hoc Tukey's test. RESULTS: ANOVA revealed that ratio of glass-fiber/particulate filler had significant effect (p<0.05) on tested mechanical properties of the Exp-SFRC with both monomer systems. Exp-SFRC (50wt%) had significantly higher FT (2.6MPam1/2) and FS (175.5MPa) (p<0.05) compared to non-reinforced material (1.3MPam1/2, 123MPa). Failure mode analysis of crown restorations revealed that FT value of the substructure directly influenced the failure mode. SIGNIFICANCE: This study shows that short glass-fibers can significantly reinforce flowable composite resin and the FT value of SFRC-substructure has prior importance, as it influences the crack arresting mechanism.

Physicochemical properties of discontinuous S2-glass fiber reinforced resin composite.

The objective of this study was to investigate several physicochemical properties of an experimental discontinuous S2-glass fiber-reinforced resin composite. The experimental composite was prepared by mixing 10 wt% of discontinuous S2-glass fibers with 27.5 wt% of resin matrix and 62.5 wt% of particulate fillers. Flexural strength (FS) and modulus (FM), fracture toughness (FT), work of fracture (WOF), double bond conversion (DC), Vickers hardness, volume shrinkage (VS) and fiber length distribution were determined. These were compared with two commercial resin composites. The experimental composite showed the highest FS, WOF and FT compared with two control composites. The DC of the experimental composite was comparable with controls. No significant difference was observed in VS between the three tested composites. The use of discontinuous glass fiber fillers with polymer matrix and particulate fillers yielded improved physical properties and substantial improvement was associated with the use of S2-glass fiber.

Physical and chemical properties of model composites containing quaternary ammonium methacrylates.

OBJECTIVE: Investigate physical and chemical properties of model composites formulated with quaternary ammonium salt monomers (QAS) at different concentrations and alkyl chains lengths METHODS: QAS with 12 dimethylaminododecyl methacrylate (DMADDM) and 16 dimethylaminohexadecyl methacrylate (DMAHDM) chains lengths were synthesized and incorporated at 5 and 10% in model composites, resulting in four groups: G12.5 (DMADDM 5%), G12.10 (DMADDM 10%), G16.5 (DMAHDM 5%), G16.10 (DMAHDM 10%). One group was used as control group (CG 0%). Degree of conversion (DC); water sorption (WS) and solubility (SL); hygroscopic expansion (HE); degradation temperature (DT); glass transition temperature (Tg) and polymerization shrinkage (PS) were determined. Knoop hardness (KNH), flexural strength (FS) and elastic modulus (EM) were measured before and after storage Data were submitted to ANOVA and Tukey's test (p≤0.05). RESULTS: DC ranged between 76.1 (G12.10) and 70.7 (G16.5) %; CG had the lowest WS, SL and HE. There was no statistical difference for PS and FS. KHN values ranged between 30.2 (GC) and 25 (G16.10) and after storage the performance was depended on QAS concentration and chain length. For EM, CG had the highest values before and after storage and no difference was observed in the QAS groups before storage. After storage, the results were dependent on QAS concentration (3.5-4.3GPa). SIGNIFICANCE: In general, the addition of QAS increased composite's degradation compared with the CG. In the tested QAS, the addition of DMADDM at 5% concentration resulted in a less degradable material.

Effectiveness of the DHMAI monomer in the development of an antibacterial dental composite.

OBJECTIVE: Development of antibacterial dental composites is the ultimate goal to decrease carious disease occurrence and increase the restoration longevity. For this purpose, the quaternary ammonium dimethyl-hexadecyl-methacryloxyethyl-ammonium iodide (DHMAI) and the methacryloyloxyethylphosphorylcholine (MPC) have been incorporated in experimental methacrylate-based composite resins. This aims to first investigate the effect of each alone and then their combined effect. METHODS: Synthesized DHMAI and commercial MPC were added either alone or combined at different concentrations to experimental dental composite. Flexural strength (FS) and modulus (FM) were tested to select the optimal concentrations. Only selected composites were evaluated for Vickers hardness (HV) and the degree of conversion (DC) using fourier transform infrared spectroscopy analysis (FTIR-ATR). Antibacterial activity was assessed using tests on colony-forming unit (CFU), scanning electron microscopy (SEM) and Alamarblue assay to measure the metabolic activity. Streptococcus mutans biofilm was chosen to be grown on the composite surfaces during 96h at 37°C. RESULTS: Incorporation of 7.5% DHMAI in composite improved the degree of conversion and gave a strong antibacterial effect with a reduction of (∼98%) in CFU and (∼50%) of metabolic activity with acceptable mechanical properties. Addition of MPC to DHMAI affects mechanical properties of composites without providing a better antibacterial activity. SIGNIFICANCE: Composites with DHMAI greatly reduced S. mutans biofilm and improved the degree of conversion without scarifying the composites' mechanical properties. DHMAI may have wide applicability to other dental materials in order to inhibit caries and improve the longevity of restorations.

Phase composition and morphology characteristics of ceria-stabilized zirconia powders obtained via sol-gel method with various pH conditions.

PURPOSE: High purity, fine crystalline, degradation-free at low temperature powders have attracted special interest in CAD/CAM prosthetic dentistry full ceramic restorations. This study reports the preparation and characterisation of zirconia-ceria (0.9 ZrO2 0.1 CeO2) powders. Materials were obtained from zirconium-n-alkoxide and cerium nitrate hexahydrate in the pH 2-4 and 8-10. METHODS: Zirconia- ceria powders were obtained with the sol-gel method in a humid-free environment. Thermal analysis (TGA/DTA) of the as-prepared materials was made for an assessment of its behaviour at elevated temperatures. Specimens were dried at 80 °C and calcinated in two stages: at 300 °C with soaking time 2.5 h and 850 °C with holding time 2.5 h, in order to evaluate the phase transformations. Thermal analyses of the as-dried powders were made for an assessment of its thermal behaviour during heat treatment up to 1000 °C. By X-ray diffraction (XRD), polymorphs of ZrO2 were identified. Additionally, scanning electron microscopy (SEM) and laser particle size distribution (PSD) were involved for characterisation of morphology of the powders. RESULTS: A correlation between the pH of the colloidal system and the morphology of the as-obtained powders were found. Based on analysis (SEM, PSD), structures were identified known as soft and hard agglomerates. CONCLUSIONS: It can be stated that differences found between powder morphology were dependent on the value pH used, which can be crucial for powder densification during sintering and compacting green bodies which, as a consequence, may be crucial for the lifetime of zirconia prostheses. Correlations between phase composition and pH are difficult to grasp, and require further, more sophisticated, studies.

Chemical passivation as a method of improving the electrochemical corrosion resistance of Co-Cr-based dental alloy.

PURPOSE: The purpose of the study was to evaluate corrosion resistance of Wirobond C® alloy after chemical passivation treatment. METHODS: The alloy surface undergone chemical passivation treatment in four different media. Corrosion studies were carried out by means of electrochemical methods in saline solution. Corrosion effects were determined using SEM. RESULTS: The greatest increase in the alloy polarization resistance was observed for passive layer produced in Na2SO4 solution with graphite. The same layer caused the highest increase in corrosion current. Generally speaking, the alloy passivation in Na2SO4 solution with graphite caused a substantial improvement of the corrosion resistance. The sample after passivation in Na2SO4 solution without graphite, contrary to others, lost its protective properties along with successive anodic polarization cycles. The alloy passivation in Na3PO4 solution with graphite was the only one that caused a decrease in the alloy corrosion properties. The SEM studies of all samples after chemical passivation revealed no pit corrosion - in contrast to the sample without any modification. CONCLUSIONS: Every successive polarization cycle in anodic direction of pure Wirobond C® alloy enhances corrosion resistance shifting corrosion potential in the positive direction and decreasing corrosion current value. The chemical passivation in solutions with low pH values decreases susceptibility to electrochemical corrosion of Co-Cr dental alloy. The best protection against corrosion was obtained after chemical passivation of Wirobond C® in Na2SO4 solution with graphite. Passivation with Na2SO4 in solution of high pH does not cause an increase in corrosion resistance of WIROBOND C. Passivation process increases alloy resistance to pit corrosion.

Anti-biofouling phosphorylated HEMA and PEGMA block copolymers show high affinity to hydroxyapatite.

Four types of phosphorylated 2-hydroxyethyl methacrylate and poly(ethylene glycol) methyl ether methacrylate (PEGMA) block copolymers were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization and post-phosphorylation. These polymers were composed of different phosphate segments and similar PEG brushes. Polymers with defined phosphate segments were investigated to determine the optimal bonding affinity to hydroxyapatite (HAp). Polymers containing short phosphate segments (as low as 23 mer) were capable of immobilizing on HAp surfaces in situ in a short coating time with considerable durability. After surface modification, the dense PEG brushes altered the interfacial properties of HAp. The protein adsorption on the polymer-grafted HAp was drastically reduced compared with the bare HAp. Furthermore, the presence of the PEG brushes on the HAp surface resulted in bacterial inhibition. The polymer with the shortest phosphate segment (23 mer) showed superior inhibition ability.

Synthesis and characterization of a novel resin monomer with low viscosity.

OBJECTIVE: In this study, we designed and synthesized a novel macromolecule (tetramethyl bisphenol F acrylate, TMBPF-Ac) with low viscosity, excellent mechanical properties, and good biocompatibility. It could be used as a monomer for dental resin composites, which could reduce the risk of human exposure to bisphenol A derivatives in the oral environment. In addition, the monomer could be used without diluent, thereby avoiding the negative effect of a diluent METHODS: TMBPF-Ac was synthesized by a multistep condensation reaction. Its structure was confirmed by 1H NMR spectra. Different resin mixtures were prepared, and then a number of performance and cytotoxicity tests were performed on these specimens. RESULTS: 1H NMR spectra showed that the structure of TMBPF-Ac was in accordance with the design. The viscosity of TMBPF-Ac was obviously lower than that of bisphenol-A diglycidyl methacrylate. The three kinds of resins used in this study were in line with ISO 4049:2009 and ISO 10993-5:2009. TMBPF-Ac-based resin had better physical and biological properties.

Novel urethane-based polymer for dental applications with decreased monomer leaching.

The aim of this study was to synthesize and characterize new multifunctional-urethane-methacrylate monomers to be used as the organic matrix in restorative dental composites, and evaluate the main physical-chemical properties of the resulting material. Bis-GMA (bisphenol-A-diglycidylmethacrylate) and GDMA (glycerol dimethacrylate) were modified by reacting the hydroxyl groups with isocyanate groups of urethane-methacrylate precursors to result in the new monomeric systems U-(bis-GMA)-Mod and U-(GDMA)-Mod, U=Urethane and Mod=Modified. The modifications were characterized by FTIR and 1H NMR. The final monomeric synthesized system was used to prepare dental resins and composites. The physical-chemical properties were evaluated and compared with those of bis-GMA composites with varying filler contents or unfilled resins. U-(bis-GMA)-Mod and U-(GDMA)-Mod can be used to prepare dental restorative composites, with some foreseeable advantages compared with bis-GMA composites. One significant advantage is that these composites have the potential to be less toxic, once they presented a reduction of 50% in leaching of unreacted monomers extracted by solvent.