The application of calcium coacervates (CCs) may hold promise for dental hard tissue remineralization. The aim of this study was to evaluate the effect of the infiltration of artificial enamel lesions with a CC and its single components including polyacrylic acid (PAA) compared to that of the self-assembling peptide P₁₁-4 in a pH-cycling (pHC) model. Enamel specimens were prepared from bovine incisors, partly varnished, and stored in demineralizing solution (DS; pH 4.95; 17 d) to create two enamel lesions per sample. The specimens were randomly allocated to six groups (n = 15). While one lesion per specimen served as the no-treatment control (NTC), another lesion (treatment, T) was etched (H₃PO₄, 5 s), air-dried and subsequently infiltrated for 10 min with either a CC (10 mg/mL PAA, 50 mM CaCl₂ (Ca) and 1 M K₂HPO₄ (PO₄)) (groups CC and CC + DS) or its components PAA, Ca or PO₄. As a commercial control, the self-assembling peptide P₁₁-4 (Curodont^TM Repair, Credentis, Switzerland) was tested. The specimens were cut perpendicularly to the lesions, with half serving as the baseline (BL) while the other half was exposed to either a demineralization solution for 20 d (pH 4.95; group CC + DS) or pHC for 28 d (pH 4.95, 3 h; pH 7, 21 h; all five of the other groups). The difference in integrated mineral loss between the lesions at BL and after the DS or pHC, respectively, was analyzed using transversal microradiography (ΔΔZ = ΔZ_pHC − ΔZ_baseline). Compared to the NTC, the mineral gain in the T group was significantly higher in the CC + DS, CC and PAA (p < 0.05, Wilcoxon). In all of the other groups, no significant differences between treated and untreated lesions were detected (p > 0.05). Infiltration with the CC and PAA resulted in a consistent mineral gain throughout the lesion body. The CC as well as its component PAA alone promoted the remineralization of artificial caries lesions in the tested pHC model. Infiltration with PAA further resulted in mineral gain in deeper areas of the lesion body.

Hydrogels represent multifarious functional materials due to their diverse ranges of applicability and physicochemical properties. The complex coacervation of polyacrylate and calcium ions or polyamines with phosphates has been uncovered to be a fascinating approach to synthesizing of multifunctional physically crosslinked hydrogels. To obtain this wide range of properties, the synthesis pathway is of great importance. For this purpose, we investigated the entire mechanism of calcium/polyacrylate, as well as phosphate/polyamine coacervation, starting from early dynamic ion complexation by the polymers, through the determination of the phase boundary and droplet formation, up to the growth and formation of thermodynamically stable macroscopic coacervate hydrogels. By varying the synthesis procedure, injectable hydrogels, as well as plastic coacervates, are presented, which cover a viscosity range of three orders of magnitude. Furthermore, the high calcium content of the calcium/polyacrylate coacervate (~19 wt.%) enables the usage of those coacervates as an ions reservoir for the formation of amorphous and crystalline calcium-containing salts like calcium carbonates and calcium phosphates. The exceptional properties of the coacervates obtained here, such as thermodynamic stability, viscosity/plasticity, resistance to acids, and adhesive strength, combined with the straightforward synthesis and the character of an ions reservoir, open a promising field of bioinspired composite materials for osteology and dentistry.

The investigation of mineralization and demineralization processes is important for the understanding of many phenomena in daily life. Many crystalline materials are exposed to decay processes, resulting in lesions, cracks, and cavities. Historical artifacts, for example, often composed of calcium carbonate (CaCO3), are damaged by exposure to acid rain or temperature cycles. Another example for lesions in a crystalline material is dental caries, which lead to the loss of dental hard tissue, mainly composed of hydroxyapatite (HAp). The filling of such cavities and lesions, to avoid further mineral loss and enable or support the remineralization, is a major effort in both areas. Nevertheless, the investigation of the filling process of these materials into the cavities is difficult due to the non-transparency and crystallinity of the concerned materials. In order to address this problem, we present a transparent, inexpensive, and reusable test system for the investigation of infiltration and crystallization processes in situ, being able to deliver datasets that could potentially be used for quantitative evaluation of the infiltration process. This was achieved using a UV-lithography-based micro-comb test system (MCTS), combined with self-assembled monolayers (SAMs) to mimic the surface tension/wettability of different materials, like marble, sandstone, or human enamel. Moreover, the potential of this test system is illustrated by infiltration of a CaCO3 crystallization solution and a hydroxyapatite precursor (HApP) into the MCTS.