Exploring the Potential of Nonclassical Crystallization Pathways to Advance Cementitious Materials.

Understanding the crystallization of cement-binding phases, from basic units to macroscopic structures, can enhance cement performance, reduce clinker use, and lower CO emissions in the construction sector. This review examines the crystallization pathways of C-S-H (the main phase in PC cement) and other alternative binding phases, particularly as cement formulations evolve toward increasing SCMs and alternative binders as clinker replacements. We adopt a perspective, which recognizes the existence of critical intermediate steps between ions in solution and the final crystalline phases, such as solute ion associates, dense liquid phases, amorphous intermediates, and nanoparticles.

Cationic Coacervates: Novel Phosphate Ionic Reservoir for the Mineralization of Calcium Phosphates.

Cationic complex coacervates are contemplated for various medical applications controlling carrier or release processes. Here, lower poly(allylamine hydrochloride) (15 kg/mol) and (hydrogen)phosphate as cross-linking units were chosen to facilitate a sufficient coacervation and subsequently a controllable phosphate release, essential for consecutive mineralization reactions. In addition, the rheological characteristics of the obtained coacervates were assessed, exhibiting a pronounced liquid character, which enables beneficial properties toward remineralization applications such as high wettability and moldability.

Modular Toolkit of Multifunctional Block Copoly(2-oxazoline)s for the Synthesis of Nanoparticles.

Post-polymerization modification provides an elegant way to introduce chemical functionalities onto macromolecules to produce tailor-made materials with superior properties. This concept was adapted to well-defined block copolymers of the poly(2-oxazoline) family and demonstrated the large potential of these macromolecules as universal toolkit for numerous applications. Triblock copolymers with separated water-soluble, alkyne- and alkene-containing segments were synthesized and orthogonally modified with various low-molecular weight functional molecules by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and thiol-ene (TE) click reactions, respectively.

Ubiquitin Designer Proteins as a New Additive Generation toward Controlling Crystallization.

Proteins controlling mineralization in vivo are diverse, suggesting that there are various ways by which mineralization can be directed in bioinspired approaches. While well-defined three-dimensional (3D) structures occur in biomineralization proteins, the design of synthetic, soluble, bioinspired macromolecules with specific, reproducible, and predictable 3D arrangements of mineral-interacting functions poses an ultimate challenge. Thus, the question of how certain arrangements of such functions on protein surfaces influence mineralization and in what ways specific alterations subsequently affect this process remains elusive.

A non-classical view on calcium oxalate precipitation and the role of citrate.

Although calcium oxalates are relevant biominerals, their formation mechanisms remain largely unresolved. Here, we investigate the early stages of calcium oxalate formation in pure and citrate-bearing solutions. Citrate is used as a well-known oxalate precipitation inhibitor; moreover, it resembles the functional domains of the biomolecules that modulate biomineralization.