Polyelectrolytes such as polyaspartic acid (PAsp) are critical in biomimetic mineralization as stabilizers of amorphous calcium phosphate (ACP) precursors and as nucleation inhibitors similar to non-collagenous proteins (NCPs). Nevertheless, the application of polyelectrolyte–calcium complexes as a pre-precursor, such as PAsp–Ca complexes, in the mineralization of collagen is unexplored. Herein, we propose a polyelectrolyte–Ca complex pre-precursor (PCCP) process for collagen mineralization. By combining three-dimensional (3D) STORM, potential measurements, and cryogenic transmission electron microscopy with molecular dynamics simulations, we show that liquid-like electropositive PAsp–Ca complexes along with free calcium ions infiltrate electronegative collagen fibrils. The PAsp–Ca complexes are immobilized within the fibrils via chelation and hydrogen bonds, and outward movement of free calcium ions is prevented while phosphate and hydroxide are recruited through electrostatic attractions. Afterwards, ACP instantly forms and gradually crystallizes. The PCCP process not only unites two distinct crystallization pathways (classical (free Ca/P ions) and non-classical (polyelectrolyte–Ca complexes)), but also provides a novel strategy for rapid biomimetic mineralization of collagen.

We propose a novel fluorescent adhesive-assisted biomimetic mineralization strategy, based on which 1 wt% of sodium fluorescein and 25 wt% of polyacrylic acid stabilized amorphous calcium phosphate (PAA-ACP) nanoparticles were incorporated into a mild self-etch adhesive (Clearfil S3 Bond) as a fluorescent mineralizing adhesive. The characterization of the PAA-ACP nanoparticles indicates that they were spherical particles clustered together, each particle with a diameter of approximately 20–50 nm, in a metastable phase with two characteristic absorption peaks (1050 cm⁻¹ and 580 cm⁻¹). Our results suggest that the fluorescent mineralizing adhesive was non-cytotoxic with minimal esthetic interference and its fluorescence intensity did not significantly decrease within 6 months. Our data reveal that the fluorescent mineralizing adhesive could induce the extra- and intra-fibrillar remineralization of the reconstituted type I collagen, the demineralized enamel and dentin substrate. Our data demonstrate that a novel fluorescent adhesive-assisted biomimetic mineralization strategy will pave the way to design and produce anti-carious materials for the prevention of dental caries.

To evaluate the effects of airborne particle abrasion (APA) combined with MDP-containing resin cement, a glass-ceramic spray deposition (GCSD) method on the shear bond strengths (SBSs) and durability of 3 mol% yttrium oxide-stabilized zirconia ceramic (3Y-TZP) compared with lithium disilicate glass ceramics (LDGC). 3Y-TZP disks were randomly treated as follows: for Group APA+MDP, 3Y-TZP was abrased using 50 μm Al₂O₃ particles under 0.1 Mpa and bonded with MDP-containing resin cement; for Group GCSD, 3Y-TZP was treated with the GCSD method, etched by 5% HF for 90 s, silanized and bonded with resin cement without MDP. Group LDGC was bonded as the Group GCSD. X-ray diffraction (XRD), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and energy dispersive X-ray detector (EDX) were used to analyze the surface chemical and micro-morphological changes of the ceramics before bonding. The bonded ceramic specimens were randomly divided into subgroups, and the SBSs were determined before and after 10,000 thermocycling. The SBSs were analyzed with a one-way ANOVA analysis. Failure modes were determined with optical microscopy and SEM. The XRD, ATR-FTIR and XPS results identified the formation of lithium disilicate and zirconium silicate on 3Y-TZP after GCSD. The SEM micrographs revealed that 3Y-TZP surfaces were roughened by APA, while 3Y-TZP with GCSD and LDGC surfaces could be etched by HF to be porous. The APA treatment combined with MDP-containing resin cement produced the high immediate zirconia shear bond strengths (SBSs: 37.41 ± 13.51 Mpa) that was similar to the SBSs of the LDGC (34.87 ± 11.02 Mpa, p > 0.05), but, after thermocycling, the former dramatically decreased (24.00 ± 6.86 Mpa, maximum reduction by 35.85%) and the latter exhibited the highest SBSs (30.72 ± 7.97 Mpa, minimum reduction by 11.9%). The 3Y-TZP with GCSD treatment displayed the lower zirconia SBSs before thermocycling (27.03 ± 9.76 Mpa, p < 0.05), but it was similar to the 3Y-TZP treated with APA and MDP containing resin cement after thermocycling (21.84 ± 7.03 vs. 24.00 ± 6.86 Mpa, p > 0.05). The APA combined with MDP-containing resin cement could achieve the high immediate zirconia SBSs of those of the LDGC, but it decreased significantly after thermocycling. The GCSD technique could yield the immediate zirconia SBSs similar to those of LDGC before thermocycling, and long-term zirconia SBSs were similar to those of 3Y-TZP treated with APA followed by MDP-containing resin cement after thermocycling. Hence, the GCSD technique could enrich zirconia surface treatments and is an alternative to zirconia surface pretreatment for 3Y-TZP bond durability.

Background: Widespread exposure to phthalates may raise the probability of various diseases. However, the association of phthalate metabolites with periodontitis remains unclear. Methods: Totally 3402 participants from the National Health and Nutrition Examination Survey (NHANES) 2009 to 2014 cycles were enrolled in the cross-sectional investigation. We utilized weighted logistic regression to evaluate the association of ten phthalate metabolites with periodontitis. Restricted cubic spline analysis was applied to investigate potential nonlinear relationships. Results: The weighted prevalence of periodontitis in the study was 42.37%. A one standard deviation (SD) rise in log-transformed levels of mono-2-ethyl-5-carboxypenty phthalate (MECPP), mono-n-butyl phthalate (MnBP), mono-(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP), mono-isobutyl phthalate (MiBP), mono-(2-ethyl-5-oxohexyl) phthalate (MEOHP), and mono-benzyl phthalate (MBzP) was associated with higher odds of periodontitis, with odds ratios (95% confidence intervals) of 1.08 (1.02-1.14), 1.07 (1.02-1.11), 1.10 (1.05-1.15), 1.05 (1.01-1.09), 1.09 (1.04-1.14), and 1.08 (1.03-1.13), respectively. Individuals with the highest quartile concentrations of MECPP, MnBP, MEHHP, MEOHP, and MBzP were associated with 32%, 20%, 30%, 25%, and 26% increased odds of periodontitis, respectively, compared to those with the lowest quartile. Additionally, mono-(3-carboxypropyl) phthalate (MCPP) demonstrated an interesting inverted J-shaped relationship with periodontitis. Conclusions: The findings indicate an association of certain phthalate metabolites with periodontitis among US adults.