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Biomimetic hydroxyapatites are widely explored for their potential applications in the repair of mineralized tissues, particularly dental enamel, which is acellular and, thus, not naturally reformed after damage. Enamel is formed with a highly-controlled hierarchical structure, which is difficult to replicate up to the macroscale. A biomimetic approach is thus warranted, based on the same principles that drive biomineralization in vivo. Herein, a strategy for the design of enamel-like architectures is described, utilizing enzymes embedded in polyelectrolyte multilayers to generate inorganic phosphate locally, and provide a favorable chemical environment for the nucleation and growth of minerals. Moreover, a method is proposed to build up seriated mineral layers with scalable thicknesses, continuous mineral growth, and tunable morphology. Results show the outstanding growth of cohesive mineral layers, yielding macroscopic standalone fluoride and/or carbonate-substituted hydroxyapatite materials with comparable crystal structure and composition to native human mineralized tissues. This strategy presents a promising path forward for the biomimetic design of biomineral materials, particularly relevant for restorative applications, with an exquisite level of synthetic control over multiple orders of magnitude., (© 2024 Wiley‐VCH GmbH.)

We report the use of Zr-based metal-organic frameworks (MOFs) MOF-545 and MOF-545(Cu) as supports to prepare catalysts with uniformly and highly dispersed Ni nanoparticles (NPs) for CO 2 hydrogenation into CH 4 . In the first step, we studied the MOF support under catalytic conditions using operando diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, ex situ characterizations (PXRD, XPS, TEM, and EDX-element mapping), and DFT calculations. We showed that the high-temperature conditions undoubtedly confer a potential for catalytic functionality to the solids toward CH 4 production, while no role of the Cu could be evidenced. The MOF was shown to be transformed into a catalytically active material, amorphized but still structured with dehydroxylated Zr-oxoclusters, in line with DFT calculations. In the second step, Ni@MOF-545 catalysts were prepared using either impregnation (IM) or double solvent (DS) methods, followed by a dry reduction (R) route under H 2 to immobilize Ni NPs. The highest catalytic activity was obtained with the Ni@MOF-545 DS R catalyst (595 mmol CH4 g Ni -1 h -1 ) with 100% CH 4 selectivity and 60% CO 2 conversion after ∼3 h. The higher catalytic activity of Ni@MOF-545 DS R is a result of much smaller (∼5 nm) and better dispersed Ni NPs than in the IM sample (20-40 nm), the latter exhibiting sintering. The advantages of the encapsulation of Ni NPs by the DS method and of the use of a MOF-545-based support are discussed, highlighting the interest of designing yet-unexplored Zr-based MOFs loaded with Ni NPs for CO 2 hydrogenation.

Clusters and oxo-clusters are drawing attention for their amazing physical properties, especially at the scale of the single molecule. However, chemical methods to organize them individually on a surface are still lacking. In this study we show that it is possible to periodically organize individual polyoxometalates thanks to their ordering by a new supramolecular assembly.

We report the synthesis of a stable heterogeneous catalyst based on copper metal nanoparticles with oxidized surface supported on ZIF-8 for the oxidation of benzyl alcohol under mild temperature and using air as a sustainable oxygen source as well as for the implementation of the tandem "one-pot" catalytic system allowing the sustainable synthesis of benzylidene malononitrile. The influence of the reduction process applied to form the nanoparticle upon the catalyst texture and its performances was extensively examined. After ZIF-8 impregnation with a copper chloride precursor, the reduction of cupric ions into Cu 0 nanoparticles was carried out according to two procedures: (i) by soaking the solid into a solution of NaBH 4 and (ii) by submitting it to a flow of gaseous H 2 at 340 °C. The in-depth physicochemical characterization and comparison of the resulting two types of Cu/ZIF-8 materials reveal significant differences: the reduction with NaBH 4 led to the formation of 16 nm sized Cu 0 nanoparticles (NP) mainly localized on the external surface of the ZIF-8 crystals together with ZnO nanocrystallites, while the reduction under H 2 flow resulted in Cu 0 nanoparticles with a mean size of 22 nm embedded within the bulk of ZIF-8 crystals. More, when NaBH 4 was used to reduce cupric ions, ZnO particles were highlighted by high-resolution microcospy imaging. Formation of ZnO impurities was confirmed by the photoluminescence analysis of ZIF-8 after NaBH 4 treatment. In contrast, ZnO was not detected on ZIF-8 treated with H 2 . Both types of Cu 0 NPs supported on ZIF-8 were found to be active as catalysts toward the aerobic oxidation of benzyl alcohol under moderate temperature ( T < 80 °C) and using air as a sustainable O 2 source. Benzaldehyde yield of 66% and selectivity superior to 90% were obtained with the Cu/ZIF-8 catalyst prepared under H 2 flow after 24 h under these conditions. The same material could be recycled 5 times without loss of activity, unlike the catalysts synthesized with NaBH 4 , as a result of the leaching of the surface copper NPs over the consecutive catalytic cycles. Finally, the most stable catalyst was successfully implemented in a tandem "one-pot" catalytic system associating benzyl alcohol oxidation and Knoevenagel condensation to synthesize benzylidene malononitrile.

While it has long been mimicked by simple precipitation reactions under biologically relevant conditions, calcium phosphate biomineralization is a complex process, which is highly regulated by physicochemical factors and involves a variety of proteins and other biomolecules. Alkaline phosphatase (ALP), in particular, is a conductor of sorts, directly regulating the amount of orthophosphate ions available for mineralization. Herein, we explore enzyme-assisted mineralization in the homogeneous phase as a method for biomimetic mineralization and focus on how relevant ionic substitution types affect the obtained minerals. For this purpose, mineralization is performed over a range of enzyme substrate concentrations and fluoride concentrations at physiologically relevant conditions (pH 7.4, T = 37 °C). Refinement of X-ray diffraction data is used to study the crystallographic unit cell parameters for evidence of ionic substitution in the lattice, and infrared (IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) are used for complementary information regarding the chemical composition of the minerals. The results show the formation of substituted hydroxyapatite (HAP) after 48 h mineralization in all conditions. Interestingly, an expansion of the crystalline unit cell with an increasing concentration of the enzyme substrate is observed, with only slight changes in the particle morphology. On the contrary, by increasing the amount of fluoride, while keeping the enzyme substrate concentration unchanged, a contraction of the crystalline unit cell and the formation of elongated, well-crystallized rods are observed. Complementary IR and XPS data indicate that these trends are explained by the incorporation of substituted ions, namely CO 3 2- and F - , in the HAP lattice at different positions.