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)

Synthesis, characterization, biocompatibility of hydroxyapatite-natural polymers nanocomposites for dentistry applications.

Hydroxyapatite (HA), the main mineral component of bones and teeth, was synthesized by using the reaction between calcium nitrate tetrahydrate Ca(NO3)2∙4H2O and diammonium hydrogen phosphate (NH4)2HPO4 (DAHP) with a chemical precipitation method. The objective of this study is to utilize novel inorganic-organic nanocomposites for biomedical applications. HA is an inorganic component (75% w) and chitosan, alginate and albumin (Egg white) are organic components of nanocomposites (25% w). Nanocomposites were prepared in deionized water solutions, at room temperature, using a mechanical and magnetic stirrer for 48 h. The microstructure and morphology of sintered n-HAP were tested at different preheating temperature and laser sintering speed with scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR).

Effective dentin restorative material based on phosphate-terminated dendrimer as artificial protein.

In clinic, it calls for effective and simple materials to repair etched dentin. Bioinspired by the natural mineralization process guided by noncollagenous proteins (NCPs), in this work, we synthesized the fourth generation phosphate-terminated polyamidoamine dendrimer (G4-PO3H2) by one-step modification. We used FT-IR and 1H NMR to characterize the structure of G4-PO3H2, and MTT assay to prove its biocompatibility. It was applied as the analog of dentin phosphophoryn (DPP: a type of NCPs) to repair dentin, due to its similar dimensional scale, topological architecture and peripheral functionalities to that of DPP. By the characterization of SEM and XRD, the effective regeneration of human dentin induced by G4-PO3H2 is characterized and illustrated both in vitro (artificial saliva) and in vivo (oral cavity of rats). It is noted that the thickness of the regenerated mineral layers are more than 10 µm both in vitro and in vivo. The design strategy of G4-PO3H2 may be valuable for researchers in the fields of material science, stomatology and medicine to prepare various promising restorative nano-materials for biomineralized hard tissues such as bone and teeth.

Development of swellable local implants of a polyethyleneimine-poly(vinyl pyrrolidone) (PEI-PVP) hydrogel as a socket filler.

In this study, hydrogels composed of polyethyleneimine (PEI) and poly(vinyl pyrrolidone) K90 (PVP) cross-linked with various concentrations (0, 0.125, 0.25 and 0.5%) of glutaraldehyde were evaluated as a hydrogel filler for the local delivery of lidocaine after tooth extraction. The drug-release kinetics, swellability, cytotoxicity and wound healing after tooth extraction of these non-cross-linked and cross-linked PEI-PVP hydrogels were examined in male beagles and compared to values using Spongostan(®). Results demonstrated that the extent of cross-linking influenced the swelling of the resulting hydrogel, but the drug-release rates were similar. No significant changes were observed in gingival fibroblasts in contact with the PEI- PVP hydrogels or Spongostan(®). In the in vivo study, PEI-PVP hydrogels showed good retention in the socket for 2 days and showed comparable wound-healing rates within 2 weeks with those of Spongostan(®). In conclusion, PEI-PVP hydrogels are suitable for use as socket-dressing materials, and the release of local anaesthesia from PEI-PVP hydrogels can be sustained for a desirable period of time to prevent pain after a tooth extraction.

Synthesis and characterization of dimethacrylates containing quaternary ammonium functionalities for dental applications.

OBJECTIVES: The widespread incidence of recurrent caries highlights the need for improved dental restorative materials. The objective of this study was to synthesize low viscosity ionic dimethacrylate monomers (IDMAs) that contain quaternary ammoniums groups (antimicrobial functionalities) and are compatible with existing dental dimethacrylate-based monomers. Such monomers have the potential to copolymerize with other methacrylate monomers and produce antibacterial polymers. METHODS: Two monomers (IDMA-1 and IDMA-2) were synthesized using the Menschutkin reaction and incorporated at 0-30% (by mass) into a 1:1 (by mass) bisphenol A glycerolate dimethacrylate (BisGMA):triethylene glycol dimethacrylate (TEGDMA) resin. Resin viscosity was quantified using rheology, and polymer degree of conversion (DC) and surface charge density were measured using Fourier transform infrared spectroscopy (FTIR) and fluorescein binding, respectively. Effects of IDMA-1 on initial attachment of Streptococcus mutans and on viability and metabolic activity (via reductase enzymes) of RAW 264.7 macrophage-like cells were quantified. RESULTS: IDMA-1 and IDMA-2 were prepared and characterized. IDMA-1 was miscible with BisGMA:TEGDMA and slightly increased the resin viscosity and DC. As expected, polymeric surface charge density increased with increasing IDMA-1. Incorporation of 10% IDMA-1 into BisGMA:TEGDMA reduced bacterial colonization without affecting viability or metabolic activity of mammalian cells. Increasing IDMA-1 up to 30% had no additional effect on bacterial coverage, but ≥20% IDMA-1 significantly reduced macrophage density, viability, and metabolic activity. Leachables from polymers containing IDMA-1 were not cytotoxic. SIGNIFICANCE: The Menschutkin reaction provides a facile, convenient means to synthesize new monomers with quaternary ammonium groups for dental and medical applications.

Apatite microtopographies instruct signaling tapestries for progenitor-driven new attachment of teeth.

Dimension and structure of extracellular matrix surfaces have powerful influences on cell shape, adhesion, and gene expression. Here we show that natural tooth root topographies induce integrin-mediated extracellular matrix signaling cascades in tandem with cell elongation and polarization to generate physiological periodontium-like tissues. In this study we replanted surface topography instructed periodontal progenitors into rat alveolar bone sockets for 8 and 16 weeks, resulting in complete reattachment of tooth roots to the surrounding alveolar bone with a periodontal fiber apparatus closely matching physiological controls along the entire root surface. Displacement studies and biochemical analyses confirmed that progenitor-based engineered periodontal tissues were similar to control teeth and uniquely derived from preimplantation green fluorescent protein (GFP)-labeled progenitors. Together, these studies illustrate the capacity of natural extracellular surface topographies to instruct progenitor cell populations to fully regenerate complex cellular and structural morphologies of tissues once lost to disease. We suggest that our strategy could be used for the replantation of teeth lost due to trauma or as a novel approach for tooth replacement using tooth-shaped replicas.

Synthesis of collagen-like sequential polypeptides containing O-phospho-L-hydroxyproline and preparation of electrospun composite fibers for possible dental application.

A synthetic route is described for collagen-like polypeptides constructed from O-phospho-L-hydroxyproline [Hyp(PO(3)H(2))] residues. Using the synthetic polypeptides and a natural protein, gelatin, fine fibers and their network structures (ESNWs) were prepared via electrospinning. The composite ESNWs can induce the mineralization of calcium phosphate. The phosphoryl groups of the Hyp(PO(3)H(2)) residues affect both the crystalline phase and amount of the calcium phosphate, depending on the chemical structure in the repeating sequence. The composite ESNWs can be developed as a biocompatible replacement of the extracellular matrix of hard tissues, and thus can be applied as dental materials for restoration of dental cavities or as a sealant for pits and fissures.

Synthesis and evaluation of ethylene glycol 3-diethylamino-propionate methacrylate as a polymerizable amine coinitiator for dental application.

OBJECTIVE: The primary objective of this study was to synthesize and characterize ethylene glycol 3-diethylamino-propionate methacrylate (EGDPM) as a polymerizable coinitiator to replace the commercial amine coinitiator. The 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]-propane (Bis-GMA) and triethylene glycol dimethylacrylate (TEGDMA) resin mixture was polymerized by camphorquinone/EGDPM initiator system under visible light irradiation. The mechanical properties, water sorption and solubility of cured samples were also evaluated. METHODS: EGDPM was synthesized via Michael-Addition reaction and characterized using FTIR and 1H NMR spectroscopy. Photopolymerization kinetics of the dental resin mixtures were monitored by real-time IR (RTIR). The mechanical properties of cured samples were recorded by dynamic mechanical analyzer (DMA). And the water sorption and solubility of cured samples were detected according to ISO 4049. RESULTS: Both the double bond conversion and the rate of polymerization of the resin mixtures increased as increasing the concentration of EGDPM but were lower than that of ethyl-4-dimethylaminobenzoate (EDMAB) and 2-(dimethylamine)ethyl methacrylate (DMEM) as a coinitiator at some concentration. When it served as diluent, the final double bond conversion was comparable to that of EDMAB, and the rate of polymerization was higher than that of DMEM. The modulus and T(g) of the cured samples were very close. Water sorption and solubility of the samples were almost the same except that of EGDPM as diluent. CONCLUSIONS: EGDPM was synthesized by Michael-Addition reaction. It could be used as a potential coinitiator but not suitable as diluent for dental composite.