Prodelphinidins enhance dentin matrix properties and promote adhesion to methacrylate resin.

Objective: Investigate the bioactivity and stability of Rhodiola rosea (RR) fractions as a natural source of prodelphinidin gallate (PDg) on dentin collagen via analysis of the viscoelastic and resin-dentin adhesive properties of the dentin matrix.

Methods: The biomimicry and stability of RR subfractions (F1, F2, F3 and F4) with collagen were determined by dynamic mechanical analysis (DMA). DMA used a strain sweep method to assess the dentin matrix viscoelastic properties [storage (E'), loss (E"), and complex (E*) moduli and tan δ] after treatment, 7-, 30- and 90-days of storage in simulated body fluids (SBF).

Modulatory role of terminal monomeric flavan-3-ol units in the viscoelasticity of dentin.

Flavan-3-ol monomers are the building blocks of proanthocyanidins (PACs), natural compounds from plants shown to mediate specific biologic activities on dentin. While the stereochemistry of the terminal flavan-3-ols, catechin (C) versus epicatechin (EC), impacts the biomechanical properties of the dentin matrix treated with oligomeric PACs, structure-activity relationships driving this bioactivity remain elusive. To gain insights into the modulatory role of the terminal monomers, two highly congruent trimeric PACs from Pinus massoniana only differing in the stereochemistry of the terminal unit (Trimer-C vs.

Unprecedented Benzoquinone Motifs Reveal Post-Oligomerizational Modification of Proanthocyanidins.

Proanthocyanidins (PACs) are complex flavan-3-ol polymers with stunning chemical complexity due to oxygenation patterns, oxidative phenolic ring linkages, and intricate stereochemistry of their heterocycles and inter-flavan linkages. Being promising candidates for dental restorative biomaterials, trace analysis of dentin bioactive cinnamon PACs now yielded novel trimeric ( and ) and tetrameric () PACs with unprecedented - and benzoquinone motifs (benzoquinonoid PACs). Challenges in structural characterization, especially their absolute configuration, prompted the development of a new synthetic-analytical approach involving comprehensive spectroscopy, including NMR with quantum mechanics-driven H iterative functionalized spin analysis (HifSA) plus experimental and computational electronic circular dichroism (ECD).

B-Type Oligomers from Expand the Procyanidin Chemical Space and Exhibit Dental Bioactivity.

Investigation of a pine bark extract for bioactive proanthocyanidin oligomers resulted in the isolation of structurally related dimeric B-type procyanidin derivatives, -. This includes scalemic mixtures of gambiriin A1 () and A2 () and their newly described optical antipodes, -gambiriin A1 () and -gambiriin A2 (), respectively, as well as a racemic mixture of the newly described (-)gambiriin A5 (/). Furthermore, the study now fully characterizes the previously reported optically pure dimers gambiriin B1 () and gambirflavan D1 (), and characterized the novel B-type procyanidin trimer, (gambirifuran C1).

B-type Proanthocyanidins with Dentin Biomodification Activity from Cocoa ().

To enable translational studies, a scalable preparative isolation scheme was developed for underivatized cocoa () proanthocyanidins (PACs), affording six all-B-type oligomeric PACs, including a new tetramer . 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.

Proanthocyanidin Tetramers and Pentamers from Bark and Their Dentin Biomodification Bioactivities.

To enable the further exploration of structure-activity relationships (SARs) of proanthocyanidins (PACs) with dentin biomodification abilities, was selected for scaled-up purification of mixed A-/B-type, medium-size PAC oligomers. Sequential purification by centrifugal partition chromatography (CPC), Sephadex LH-20, and semiprep HPLC chromatography yielded four underivatized tetrameric (-) and two pentameric (-) PACs. Their unambiguous structural characterization involved extensive spectral and chemical degradation approaches to show that epicatechin units are connected by plant-specific combinations of doubly linked A- and singly linked B-type interflavanyl bonds.

Biomimetic Growth of Metal-Organic Frameworks for the Stabilization of the Dentin Matrix and Control of Collagenolysis.

The dentin matrix is a collagenous scaffold structurally involved in anchoring resin-based materials to the tooth. Time-dependent degradation of this scaffold at the resin-dentin interface remains a core problem in adhesive dentistry, limiting the service life of dental fillings. This study explored the use of emergent materials termed metal-organic frameworks (MOFs)─formed by the self-assembly of metal ions and organic building blocks─to safeguard the collagen integrity in the functional dentin matrix.

Surface-Directed Mineralization of Fibrous Collagen Scaffolds in Simulated Body Fluid for Tissue Engineering Applications.

The use of polymer additives that stabilize fluidic amorphous calcium phosphate is key to obtaining intrafibrillar mineralization of collagen in vitro. On the other hand, this biomimetic approach inhibits the nucleation of mineral crystals in unconfined extrafibrillar spaces, that is, extrafibrillar mineralization. The extrafibrillar mineral content is a significant feature to replicate from hard connective tissues such as bone and dentin as it contributes to the final microarchitecture and mechanical stiffness of the biomineral composite.

Proanthocyanidin encapsulation for sustained bioactivity in dentin bioadhesion: A two-year study.

Objectives: To determine the long-term effect on the stability of dentin-resin interfaces after the addition of polylactide (PLA) capsules containing proanthocyanidin (PAC) to adhesive resin.

Methods: Sub-micron (SM) and micron (M) size capsules containing PACs were produced using a combination of emulsification and solvent evaporation techniques and characterized. Human dentin surfaces (n = 8) were etched (35% glycolic acid) and primed (15% enriched Vitis vinifera extract solution - VV), followed by the application of an experimental adhesive containing 0 (control), 1.

The stoic tooth root: how the mineral and extracellular matrix counterbalance to keep aged dentin stable.

Aging is a physiological process with profound impact on the biology and function of biosystems, including the human dentition. While resilient, human teeth undergo wear and disease, affecting overall physical, psychological, and social human health. However, the underlying mechanisms of tooth aging remain largely unknown.

Paradoxical effects of galloyl motifs in the interactions of proanthocyanidins with collagen-rich dentin.

Plant-derived proanthocyanidins (PACs) mediate physicochemical modifications to the dentin extracellular matrix (ECM). The structure-activity relationships of PACs remain largely unknown, mostly due to the varied complex composition of crude extracts, as well as the challenges of purification and mechanistic assessment. To assess the role of galloylated PACs as significant contributors to high yet unstable biomodification activity to the dentin ECM, we removed the galloyl moieties (de-galloylation) via enzymatic hydrolysis from three galloyl-rich PAC-containing extracts (Camellia sinensis, Vitis vinifera, and Hamamelis virginiana).

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.

Rare A-Type, Spiro-Type, and Highly Oligomeric Proanthocyanidins from .

An investigation of the dental bioactive proanthocyanidin (PAC) oligomer fractions led to three structurally distinct new PACs (-) from pine bark. Pinutwindoublin () is the first reported trimer with double A-type interflavanyl linkages (2α→O→5,4α→6 and 2α→O→7,4α→8). Pinuspirotetrin () represents the first reported PAC tetramer with a heterodimeric framework consisting of one spiro-type and one A-type dimer.

Tri- and Tetrameric Proanthocyanidins with Dentin Bioactivities from .

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 ( and ), seven trimers (), and six tetramers (). 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.

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.

On the bulk biomechanical behavior of densely cross-linked dentin matrix: The role of induced-glycation, regional dentin sites and chemical inhibitor.

Collagen glycation takes place under physiological conditions during chronological aging, leading to the formation of advanced glycation end-products (AGEs). AGEs accumulation induces non-enzymatic collagen cross-links increasing tissue stiffness and impairing function. Here, we focused on determining the cumulative effect of induced glycation on the mechanical behavior of highly collagen cross-linked dentin matrices and assess the topical inhibition potential of aminoguanidine.

Regional contribution of proteoglycans to the fracture toughness of the dentin extracellular matrix.

This study investigated the contribution of small leucine rich proteoglycans (SLRPs) to the fracture toughness of the dentin extracellular matrix (ECM) by enzymatically-assisted selective removal of glycosaminoglycan chains (GAGs) and proteoglycans (PGs) core protein. We adapted the Mode III trouser tear test to evaluate the energy required to tear the dentin ECM. Trouser-shaped dentin specimens from crown and root were demineralized.

In vitro remineralization of artificial enamel caries with resin composites containing calcium phosphate particles.

The aim of the study was to evaluate the effect of experimental composites containing dicalcium phosphate dihydrate (DCPD) on remineralization of enamel lesions. Five resin-based composites containing equal parts (in mols) of bisphenol-A glycidyl dimethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA), and 60 vol % of fillers were manipulated. Filler phase was constituted by silanized barium glass and 0, 10, or 20 vol % of DPCD particles, either functionalized (F) or nonfunctionalized (NF) with TEGDMA.

Development of calcium phosphate/ethylene glycol dimethacrylate particles for dental applications.

This study describes the synthesis of dicalcium phosphate dihydrate (DCPD) particles in the presence of different ethylene glycol dimethacrylates (EGDMA, ethylene glycol/EG units: 1, 2, 3 or 4) at two monomer-to-ammonium phosphate molar ratios (1:1 and 2:1), as a strategy to develop CaP-monomer particles with improved interaction with resin matrices. Particles displaying high surface areas and organic contents were added to a photocurable BisGMA-TEGDMA resin and the resulting materials were tested for degree of conversion (DC), biaxial flexural strength (BFS), flexural modulus, and ion release. Data were subjected to one-way ANOVA or Kruskal-Wallis/Dunn test (alpha: 0.

Mechanical characterization and ion release of bioactive dental composites containing calcium phosphate particles.

Objective: to verify the effect of the addition of dicalcium phosphate dihydrate (DCPD) particles functionalized with di- or triethylene glycol dimethacrylate (DEGDMA or TEGDMA) on the degree of conversion (DC), post-gel shrinkage (PS), mechanical properties, and ion release of experimental composites.

Methods: Four composites were prepared containing a BisGMA/TEGDMA matrix and 60 vol% of fillers. The positive control contained only barium glass fillers, while in the other composites 15 vol% of the barium was replaced by DCPD.

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

Objectives: This study describes the synthesis of brushite nanoparticles (CaHPO·2HO) 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).

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

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.

Synthesis and characterization of silver phosphate/calcium phosphate mixed particles capable of silver nanoparticle formation by photoreduction.

Silver phosphate is a semi-conductor sensitive to UV-Vis radiation (<530nm). Exposure to radiation removes electrons from the oxygen valence shell, which are scavenged by silver cations (Ag), forming metallic silver (Ag) nanoparticles. The possibility of silver nanoparticle formation in situ by a photoreduction process was the basis for the application of mixed calcium phosphate/silver phosphate particles as remineralizing and antibacterial fillers in resin-based dental materials.