Rare A-Type, Spiro-Type, and Highly Oligomeric Proanthocyanidins from \u3cem\u3ePinus massoniana\u3c/em\u3e

An investigation of the dental bioactive proanthocyanidin (PAC) oligomer fractions led to three structurally distinct new PACs (1–3) from pine bark. Pinutwindoublin (1) is the first reported trimer with double A-type interflavanyl linkages (2α→O→5,4α→6 and 2α→O→7,4α→8). Pinuspirotetrin (2) represents the first reported PAC tetramer with a heterodimeric framework consisting of one spiro-type and one A-type dimer. Pinumassohexin (3) was elucidated as a mixed A + B-type hexamer that consists of a peanut-derived tetramer, peanut procyanidin E, and an A-type dimer (5). Compound 3 increased the modulus of elasticity of dentin by an impressive 4.3 times at a concentration of 0.65%

Effect of Dentin Biomodification Delivered by Experimental Acidic and Neutral Primers on Resin Adhesion

Objectives Proanthocyanidins (PACs) are biocompounds mimicking native collagen cross-links. The effective and practical delivery of any biocompound is pivotal for clinical usage. The aim was to investigate the dentin biomodification and effective formation of dentin–resin biointerfaces of two highly bioactive PAC-rich extracts, Vitis vinifera (Vv) and Camellia sinensis (Cs), delivered using neutral (NP) or acidic (AP) rinse-out primer approaches. Methods The depth of dentin demineralization (optical profilometry), dentin biomodification (apparent modulus of elasticity, collagen auto-fluorescence) and properties of dentin–resin interfaces (microtensile bond strength - μTBS, and micro-permeability) were investigated. NP consisted of either 15% Vv or Cs applied for 60 s after surface etching; while AP contained 15% Vv or Cs in either 35% glycolic acid or tartaric acid applied for 30 s or 60 s. Data were analyzed using ANOVA and post-hoc tests (α = 0.05). Results The depth of demineralization was statistically higher when applied for 60 s, regardless of rinse-out primer approach (p \u3c 0.001). Compared to the AP strategy, NP exhibited statistically higher apparent modulus of elasticity, regardless of PAC extract (p \u3c 0.001). Highest μTBS were obtained for NPVv, which were statistically similar to APGAVv, when applied for 60 s (p \u3c 0.001); both resulted in a dramatic decrease of the interfacial permeability. NPCs group showed the lowest μTBS (p \u3c 0.001). Conclusions A combination of high bond strength and low micro-permeability can be accomplished using glycolic acid with the mid- and high-PAC oligomer enriched extract (Vv). Cs extract containing mostly catechins and dimeric PACs, was found unsuitable for resin-dentin adhesion despite exhibiting high initial dentin biomodification. Clinical significance This study provides a new conceptual delivery of PAC-mediated dentin biomodification and conservative dentin surface etching using rinse-out primers. The strategy requires a specific combination of PAC source, α-hydroxy acid, and application time

Tri- and Tetrameric Proanthocyanidins with Dentin Bioactivities from \u3cem\u3ePinus massoniana\u3c/em\u3e

Guided by dentin biomechanical bioactivity, this phytochemical study led to the elucidation of an extended set of structurally demanding proanthocyanidins (PACs). Unambiguous structure determination involved detailed spectroscopic and chemical characterization of four A-type dimers (2 and 4–6), seven trimers (10–16), and six tetramers (17–22). New outcomes confirm the feasibility of determining the absolute configuration of the catechol monomers in oligomeric PACs by one-dimensional (1D) and two-dimensional (2D) NMR. Electronic circular dichroism as well as phloroglucinolysis followed by mass spectrometry and chiral phase high-performance liquid chromatography (HPLC) analysis generated the necessary chiral reference data. In the context of previously reported dentin-bioactive PACs, accurately and precisely assigned 13C NMR resonances enabled absolute stereochemical assignments of PAC monomers via (i) inclusion of the 13C NMR γ-gauche effect and (ii) determination of differential 13C chemical shift values (ΔδC) in comparison with those of the terminal monomer (unit II) in the dimers 2 and 4–6. Among the 13 fully elucidated PACs, eight were identified as new, and one structure (11) was revised based on new knowledge gained regarding the subtle, stereospecific spectroscopic properties of PACs

Remineralization potential of resin composites containing TEGDMA-functionalized calcium phosphate particles

O objetivo deste estudo foi avaliar o efeito de compósitos experimentais contendo nanopartículas de fosfato dicálcico dihidratado (DCPD) na remineralização de lesões artificiais em esmalte, em função do conteúdo de partículas de DCPD e da funcionalização destas com dimetacrilato de trietileno glicol (TEGDMA). Cinco compósitos contendo uma concentração equimolar de dimetacrilato de glicidila bisfenol A (BisGMA) e TEGDMA e 60 vol% de partículas foram manipulados. A fase inorgânica foi constituída por partículas de vidro de bário silanizadas e 0% (controle: Sem DCPD), 10% ou 20% (em volume) de partículas de DCPD, funcionalizadas (F) ou não (NF) com TEGDMA. Foram produzidas lesões artificiais subsuperficiais em fragmentos de esmalte humano mediante a imersão destes em 30 ml de solução desmineralizante (pH 5.0) por 12 dias a 37°C. Os blocos de esmalte foram divididos em 6 grupos (n=6 - 10), de acordo ao compósito aplicado na lesão: Sem DCPD, 20% DCPD NF, 20% DCPD F, 10% DCPD NF, 10% DCPD F além de um grupo sem a aplicação do compósito (Sem tratamento, ST) e expostos a ciclagem de pH (16 dias, 4 h em solução desmineralizante/pH=5 e 20 h em solução remineralizante/pH=7). As soluções foram trocadas a cada 4 dias, e coletadas para calcular o conteúdo de cálcio e fosfato mediante espectrofotometria. Os corpos de prova foram seccionados longitudinalmente e avaliados mediante microradiografia transversal (TMR). Os parâmetros analisados foram a profundidade da lesão (LD, ?m), a perda mineral integrada (?Z, vol%.?m) e a média da perda mineral (R). Foi calculado o ??Z (%, [100x(?Zinitial - ?Ztreatment)/?Zinitial]) para estimar a porcentagem de remineralização. Os dados foram submetidos a análise de variância (ANOVA) a um critério e o teste de Tukey para comparações múltiplas (alfa = 0.05). Todos os grupos restaurados mostraram recuperação mineral entre 3 a 23%. Houve diferencia significativa entre o ??Z do grupo ST e os contendo DCPD funcionalizado. No entanto, devido à alta dispersão de dados (particularmente no grupo Sem DCPD), não foi observada diferença significativa entre os grupos cuja lesão foi recoberta por compósito. Todos os grupos contendo DCPD mostraram maior recuperação mineral nos terços médio e profundo da lesão. O grupo ST mostrou desmineralização adicional. A concentração de íons cálcio e fosfato no meio de imersão não foi influenciada pela presença de DCPD, independentemente da funcionalização ou da porcentagem de DCDP no compósito. Concluiu-se que os compósitos contendo DCPD foram capazes de promover a recuperação mineral nas áreas mais profundas da lesão.The aim of the study was to evaluate the effect of experimental composites containing dicalcium phosphate dihydrate (DCPD) nanoparticles on remineralization of artificial enamel lesions, as a function of DCPD particle content and their functionalization with triethylene glycol dimethacrylate (TEGDMA). Five composites containing equal parts (in mols) of bisphenol A glycidyl methacrylate (BisGMA) and TEGDMA and 60 vol% of filler content were manipulated. Filler phase was constituted by silanized barium glass (BG) and 0% (control: no DCPD), 10% or 20% (by volume) of DPCD particles, either functionalized (F) or non-functionalized (NF) with TEDGMA. Artificial subsurface lesions were produced in human enamel fragments by immersing them in 30 ml of demineralization solution (pH 5.0) for 12 days at 37°C. Fragments were divided into six groups (n= 6 - 10), according to the composite applied on the lesion: no DCPD, 20% DCPD NF, 20% DCPD F, 10% DCPD NF, 10% DCPD F plus an unrestored group (non treated, NT) and exposed to pH cycling (16 days, 4 h in demineralization solution/pH=5 and 20 h in remineralization solution/pH=7). Every 4 days the solutions used were changed and collected to calculate calcium and phosphate content through spectrophotometry. Specimens were sectioned longitudinally and evaluated using transverse microradiography (TMR) for lesion depth (LD, in ?m) and integrated mineral loss (?Z, vol%.?m). ??Z% [100x(?Zinitial - ?Ztreatment)/?Zinitial] was used to estimate remineralization. Data were analyzed by one-way ANOVA/Tukey test (alpha: 0.05 for all tests). All restored groups showed enamel remineralization, ranging from 3% to 23%. Significant differences were observed between NT group and groups containing functionalized DCPD. However, due to high data scattering (particularly in the group without DCPD), no statistically significant differences were found between the groups that had their lesions covered by composite. Groups containing DCPD showed more mineral recovery in the middle and the deepest third of the lesion. NT group showed further demineralization. Calcium and phosphate ion concentrations were not influenced by the DCPD particle content or its functionalization with TEGDMA. In conclusion, all composites containing DCPD particles were able to promote mineral recovery of the enamel lesion, mainly on the deeper areas of the lesion

Bond strength between layers of silorane and methacrylate-based materials

A resina de silorano e a sua polimerização catiônica apresentam diferenças quanto aos materiais a base de metacrilato. Como materiais restauradores, estes poderiam ser utilizados juntos, no entanto suas moléculas diferentes poderiam provocar incompatibilidade. Por isso é importante avaliar a união interfacial desses materiais tendo como objetivo a comparação da resistência de união a microtração entre camadas de Filtek P90 aderidas a Filtek Z350, Filtek P90 ou Vitremer utilizando Adper Single Bond 2 ou o Sistema Adesivo P90. Os substratos dos espécimes a serem testados foram fabricados utilizando uma matriz de silicone (5mm x 5mm x 2.5mm) e fotoativados por 40 segundos (Blue Star 3, Microdont; 1076mW/cm2). De acordo com o grupo testado, foi usada ou não uma camada de adesivo fotoativado por 10 segundos. O segundo substrato (2,5mm) foi aplicado e fotoativado por 40 segundos. Os espécimes foram secionados com formato de palito, com uma área de 0,64mm2, e armazenados em água destilada a 37ºC por 24 horas. Realizou-se o teste de microtração utilizando a máquina de ensaios universal com uma velocidade de 0,5mm/min. Foi analizado o tipo de fratura resultante. Os resultados foram analisados utilizando ANOVA e o teste de Tukey (p<0.05). A média e desvio-padrão dos resultados da resistência de união em MPa são: G1 Pad (P90/adesivo P90/P90) 50.9±15.3, G2 P (P90/sem adesivo/P90) 40.2±10.2, G3 Z (Z350/sem adesivo/Z350) 62.1±15.2, G4 Ppol (P90/sem adesivo, tira de poliéster/P90) 28.8±9.2, G5 ZadP (Z350/adesivo P90/P90) 62.1±8.2, G6 PSBZ (P90/Single Bond 2/Z350) 37.1±12.5, G7 ZSB (Z350/Single Bond 2/Z350) 54.3±12.3, G8 VitrZ (Vitremer/Single Bond 2/Z350) 37.4±7.4 e G9 VitrP (Vitremer/adesivo P90/P90) 34.9±4.1. Diferença significativa foi observada entre os grupos G2 e G3, e G5 e G6. Não foi observada diferencia significativa entre os grupos G8 e G9, G5 e G7, G1 e G6. Dentro das limitações do estudo, pode-se concluir que a resina de silorano demonstrou propriedades de adesão similares quando aderida com resina de metacrilato. Valores significativamente menores foram observados entre camadas de P90 (G2) quando comparados com Z350 (G3).Silorane resin and its cationic polymerization are different from resin-based materials. As restorative materials, their use together could cause some incompatibility that raises the question about the importance of interfacial bonding properties. This study aimed to compare the microtensile bond strengths between layers of Filtek P90 bonded with itself, Filtek Z350 or Vitremer using Adper Single Bond 2 and P90 Adhesive System. Initially, substrates for the testing specimens were fabricated using a silicone mold (5mm x 5mm x 2.5mm) and light-cured for 40 s (Blue Star 3, Microdont; 1076mW/cm2). According to the testing group, it was used or not an adhesive layer, light-cured for 10 s. The second increment (2.5mm) was cured for 40 s. The specimens were sectioned in beams with 0.64mm2 cross-sectional area and stored in distilled water at 37ºC for 24 h. Microtensile bond strength test was performed using a universal testing machine with a 0.5mm/min crosshead speed. Failure modes were assessed. Values were calculated in MPa. Data were analyzed with ANOVA and Tukeys post-hoc tests at a 5% significance level. Microtensile bond strength means and standard deviation are: G1 Pad (P90/P90 adhesive/P90) 50.9±15.3, G2 P (P90/without adhesive/P90) 40.2±10.2, G3 Z (Z350/without adhesive/Z350) 62.1±15.2, G4 Ppol (P90/without adhesive, polyester strip/P90) 28.8±9.2, G5 ZadP (Z350/P90 adhesive/P90) 62.1±8.2, G6 PSBZ (P90/Single Bond 2/Z350) 37.1±12.5, G7 ZSB (Z350/Single Bond 2/Z350) 54.3±12.3, G8 VitrZ (Vitremer/Single Bond 2/Z350) 37.4±7.4 e G9 VitrP (Vitremer/P90 adhesive/P90) 34.9±4.1. Significant difference was showed among G2 and G3, G5 and G6. No significant difference was found between G8 and G9, G5 and G7, G1 and G6. Conclusions: Within the limitations of this study, it can be concluded that silorane composite showed similar bonding properties when bonded with methacrylate-based materials. Significantly lower bond strength was observed between layers of P90 than of Z350

Rare A-Type, New Spiro-Type, and Highly Oligomeric Proanthocyanidins from Pinus massoniana

Isolation of underivatized PACs led to three new, structurally unique PACs (1-3) from pine bark. Pinutwindoublin (1) is the first known trimer with double A-type interflavanyl linkages (2α→O→5,4α→6 and 2α→O→7,4α). Pinuspirotetrin (2) represents the first PAC tetramer with a heterodimeric framework consisting of one spiro-type and one A-type dimer. Pinumassohexin (3) was elucidated as a mixed A + B type hexamer that consists of the tetramer, peanut procyanidin E, and an A-type dimer (5).</div

Trends in restorative composites research:what is in the future?

Abstract Clinical trials have identified secondary caries and bulk fracture as the main causes for composite restoration failure. As a measure to avoid frequent reinterventions for restoration replacement, composites with some sort of defense mechanism against biofilm formation and demineralization, as well as materials with lower susceptibility to crack propagation are necessary. Also, the restorative procedure with composites are very time-consuming and technically demanding, particularly concerning the application of the adhesive system. Therefore, together with bulk-fill composites, self-adhesive restorative composites could reduce operator error and chairside time. This literature review describes the current stage of development of remineralizing, antibacterial and self-healing composites. Also, an overview of the research on fiber-reinforced composites and self-adhesive composites, both introduced for clinical use in recent years, is presented

Tri- and Tetrameric Proanthocyanidins with Dentin Bioactivities from Pinus massoniana

Guided by dentin biomechanical bioactivity, this phytochemical study led to the elucidation of an extended set of structurally demanding proanthocyanidins (PACs). Unambiguous structure determination involved detailed spectroscopic and chemical characterization of four A-type dimers (2, 4–6), seven trimers (10–16), and six tetramers (17–22). New outcomes confirm the feasibility of determining the absolute configuration of the catechol monomers in oligomeric PACs by 1D and 2D NMR. Electronic circular dichroism (ECD) as well as phloroglucinolysis followed by MS and chiral phase HPLC analysis generated the necessary chiral reference data

A Dynamic Mechanical Method to Assess Bulk Viscoelastic Behavior of the Dentin Extracellular Matrix

Objectives To develop a protocol for assessment of the bulk viscoelastic behavior of dentin extracellular matrix (ECM), and to assess relationships between induced collagen cross-linking and viscoelasticity of the dentin ECM. Methods Dentin ECM was treated with agents to induce exogenous collagen cross-linking: proanthocyanidins (PACs) from Vitis vinifera – VVe, PACs from Pinus massoniana - PMe, glutaraldehyde – (GA), or kept untreated (control). A dynamic mechanical strain sweep method was carried out in a 3-point bending submersion clamp at treatment; after protein destabilization with 4 M urea and after 7-day, 6-month, and 12-month incubation in simulated body fluid. Tan δ, storage (E’), loss (E”), and complex moduli (E*) were calculated and data were statistically analyzed using two-way ANOVA and post-hoc tests (α = 0.05). Chemical analysis of dentin ECM before and after protein destabilization was assessed with ATR-FTIR spectroscopy. Results Significant interactions between study factors (treatment vs. time points, p \u3c 0.001) were found for all viscoelastic parameters. Despite a significant decrease in all moduli after destabilization, PAC-treated dentin remained statistically higher than control (p \u3c 0.001), indicating permanent mechanical enhancement after biomodification. Covalently crosslinked, GA-treated dentin was unaffected by destabilization (p = 0.873) and showed the lowest damping capacity (tan δ) at all time points (p \u3c 0.001). After 12 months, the damping capacity of PMe and VVe groups decreased significantly. Changes in all amide IR resonances revealed a partial chemical reversal of PAC-mediated biomodification. Significance Viscoelastic measurements and IR spectroscopy aid in elucidating the role of inter-molecular collagen cross-linking in the mechanical behavior of dentin ECM

B‑type Proanthocyanidins with Dentin Biomodification Activity from Cocoa (Theobroma cacao)

To enable translational studies, a scalable preparative isolation scheme was developed for underivatized cocoa (Theobroma cacao) proanthocyanidins (PACs), affording six all-B-type oligomeric PACs, including a new tetramer 4. Their structures, including absolute configuration, were unambiguously established by comprehensive spectroscopic and chemical methods. Evaluation of the PACs’ dentin biomodification properties employed dynamic mechanical and infrared spectroscopic analyses in dentin bioassay models. PAC treatment enhanced the biomechanical strength of dentin by 5- to 15-fold compared to untreated dentin. Among the PAC agents, the pentamer, cinnamtannin A3 (6), led to the highest complex modulus value of 131 MPa, whereas the “branched” tetramer, 4, showed the lowest, yet still significant bioactivity. This study of specifically singly linked medium-length oligomeric PACs indicates that the linkage site is paramount in determining the potency of these PACs as dentin biomodifiers