Currently, the functional monomer 10-methacryloyloxy-decyl-dihydrogen-phosphate (10-MDP) was documented to chemically bond to zirconia ceramics. However, little research has been conducted to unravel the underlying mechanisms. This study aimed to assess the chemical interaction and to demonstrate the mechanisms of coordination between 10-MDP and zirconium oxide using ¹H and ³¹P magic angle spinning (MAS) nuclear magnetic resonance (NMR) and two dimensional (2D) ¹H → ³¹P heteronuclear correlation (HETCOR) NMR. In addition, shear bond-strength (SBS) tests were conducted to determine the effect of 10-MDP concentration on the bonding effectiveness to zirconia. These SBS tests revealed a 10-MDP concentration-dependent SBS with a minimum of 1-ppb 10-MDP needed. ³¹P-NMR revealed that one P-OH non-deprotonated of the PO₃H₂ group from 10-MDP chemically bonded strongly to zirconia. ¹H-³¹P HETCOR NMR indicated that the 10-MDP monomer can be adsorbed onto the zirconia particles by hydrogen bonding between the P=O and Zr-OH groups or via ionic interactions between partially positive Zr and deprotonated 10-MDP (P-O⁻). The combination of ¹H NMR and 2D ¹H-³¹P HETCOR NMR enabled to describe the different chemical states of the 10-MDP bonds with zirconia; they not only revealed ionic but also hydrogen bonding between 10-MDP and zirconia.

CAD-CAM blocks to fabricate semi-direct and indirect restorations are available in different sorts of ceramics as well as composite. In order to bond restorations prepared out of composite blocks into tooth cavities, it is recommended to gently sandblast the surface prior to the application of a primer/adhesive. Today, the effect of sandblasting composite block surfaces has not thoroughly been investigated. In this study, the ultra-structure of composite CAD-CAM blocks was investigated with special attention to the effect of sandblasting on the surface topography and of silanization on the bonding performance. Five different composite CAD-CAM blocks were involved. We correlatively investigated their structural and chemical composition using X-ray diffraction (XRD), energy dispersion spectroscopy (EDS), scanning electron microscopy (SEM) and (scanning) transmission electron microscopy ((S)TEM). The effect of sandblasting was also imaged in cross-section and at the interface with composite cement. Finally, we measured the shear bond strength to the sandblasted block surface with and without silanization. All composite blocks revealed a different ultra-structure. Sandblasting increased surface roughness and resulted in an irregular surface with some filler exposure. Sandblasting also damaged the surface. When the sandblasted composite blocks were silanized, superior bonding receptiveness in terms of higher bond strength was achieved except for Shofu Block HC. Sandblasting followed by silanization improved the bond strength to composite CAD-CAM blocks. However, sandblasting may also damage the composite CAD-CAM block surface. For the composite CAD-CAM block Shofu Block HC, the damage was so severe that silanization did not improve bond strength.

Besides chemically interacting with hard tooth tissue, acidic functional monomers of self-etch adhesives should etch the prepared tooth surface to dissolve the smear layer and to provide surface micro-retention. Although the etching efficacy of functional monomers is commonly determined in terms of pH, the pH of adhesives cannot accurately be measured. Better is to measure the hydroxyapatite (HAp)–dissolving capacity, also considering that functional monomers may form monomer-Ca salts. Here, the etching efficacy of 6 functional monomers (GPDM, phenyl-P, MTEGP, 4-META, 6-MHP and 10-MDP) was investigated. Solutions containing 15 wt% monomer, 45 wt% ethanol, and 40 wt% water were prepared. Initially, we observed enamel surfaces exposed to monomer solution by scanning electron microscopy (SEM). X-ray diffraction (XRD) was employed to detect monomer-Ca salt formation. Phenyl-P exhibited a strong etching effect, while 10-MDP–treated enamel showed substance deposition, which was identified by XRD as 10-MDP–Ca salt. To confirm these SEM/XRD findings, we determined the etching efficacy of functional monomers by measuring both the concentration of Ca released from HAp using inductively coupled plasma–atomic emission spectroscopy (ICP-AES) and the amount of monomer-Ca salt formation using ³¹P magic-angle spinning (MAS) nuclear magnetic resonance (NMR). ICP-AES revealed that the highest Ca concentration was produced by phenyl-P and the lowest Ca concentration, almost equally, by 4-META and 10-MDP. Only 10-MDP formed 10-MDP–Ca salts, indicating that 10-MDP released more Ca from HAp than was measured by ICP-AES. Part of the released Ca was consumed to form 10-MDP–Ca salts. It is concluded that the repeatedly reported higher bonding effectiveness of 10-MDP–based adhesives must not only be attributed to the more intense chemical bonding of 10-MDP but also to its higher etching potential, a combination the other functional monomers investigated lack.

Background. In the era of biology-driven endodontics, vital pulp therapies are regaining popularity as a valid clinical option to postpone root-canal treatment. In this sense, many different materials are available in the market for pulp-capping purposes. Objectives. The main aim of this systematic review and meta-analysis was to examine literature regarding cytotoxicity and bioactivity of pulp-capping agents by exposure of human dental pulp cells of primary origin to these materials. A secondary objective was to evaluate the inflammatory reaction and reparative dentin-bridge formation induced by the different pulp-capping agents on human pulp tissue. Data sources. A literature search strategy was carried out on PubMed, EMBASE and the Web of Science databases. The last search was done on 1 May 2020. No filters or language restrictions were initially applied. Two researchers independently selected the studies and extracted the data. Study selection included eligibility criteria, participants and interventions, study appraisal and synthesis methods. In vitro studies were included when human dental pulp cells of primary origin were (in) directly exposed to pulp-capping agents. Parallel or split-mouth randomized or controlled clinical trials (RCT or CCT) were selected to investigate the effects of different pulp-capping agents on the inflammation and reparative bridge-formation capacity of human pulp tissue. Data were synthesized via odds ratios (95% confidence interval) with fixed or random effects models, depending on the homogeneity of the studies. The relative risks (95% confidence interval) were presented for the sake of interpretation. Results. In total, 26 in vitro and 30 in vivo studies were included in the systematic review and meta-analysis, respectively. The qualitative analysis of in vitro data suggested that resin-free hydraulic calcium-silicate cements promote cell viability and bioactivity towards human dental pulp cells better than resin-based calcium-silicate cements, glass ionomers and calcium-hydroxide cements. The meta-analysis of the in vivo studies indicated that calcium-hydroxide powder/saline promotes reparative bridge formation better than the popular commercial resin-free calcium-silicate cement Pro-Root MTA (Dentsply-Sirona), although the difference was borderline non-significant (p = 0.06), and better than calcium-hydroxide cements (p < 0.0001). Moreover, resin-free pulp-capping agents fostered the formation of a complete reparative bridge better than resin-based materials (p < 0.001). On the other hand, no difference was found among the different materials tested regarding the inflammatory effect provoked at human pulp tissue. Conclusions. Calcium-hydroxide (CH) powder and Pro-Root MTA (Dentsply-Sirona) have shown excellent biocompatibility in vitro and in vivo when tested on human cells and teeth. Their use after many years of research and clinical experience seems safe and proven for vital pulp therapy in healthy individuals, given that an aseptic environment (rubber dam isolation) is provided. Although in vitro evidence suggests that most modern hydraulic calcium-silicate cements promote bioactivity when exposed to human dental pulp cells, care should be taken when these new materials are clinically applied in patients, as small changes in their composition might have big consequences on their clinical efficacy. Key findings (clinical significance). Pure calcium-hydroxide powder/saline and the commercial resin-free hydraulic calcium-silicate cement Pro-Root MTA (Dentsply-Sirona) are the best options to provide a complete reparative bridge upon vital pulp therapy. Systematic review registration number. PROSPERO registration number: CRD42020164374.