An NMR Study of Biomimetic Fluorapatite - Gelatine Mesocrystals

The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers and with experimental observations of an amorphous cover layer in biominerals

Advances of Non-Classical Crystallization Towards Self-Purification of Precious Metal Nanoparticles Mixtures

In this work, we use particle-mediated crystallization to separate mixtures of precious metal nanoparticles of different size and shape.<br /

Mechanics of twisted hippuric acid crystals untwisting as they grow

Spontaneous twisting of single crystals is a common growth induced deformation. But as twisted crystals thicken they can untwist, restoring a straight form. The mechanics of this process was studied for vapor grown needle-like crystals of N-benzoylglycine (hippuric acid) and N-(2-thienylcarbonyl)glycine, and analyzed by phenomenological models. The elastic stress at the crystal tip undergoes plastic relaxation leading to the twisting deformations. As the crystal grows and thickens it partially untwists showing linear increases of the twist period with crystal thickness. Such behavior was simulated with a model that assumes the constant density of defects in successive growth layers. However, transmission electron microscopy does not reveal any dislocations or other extended defects typically associated with plastic deformation. Published data on other materials show the linear dependencies of pitch on thickness suggesting comparable untwisting mechanisms for different materials.publishe

Hemolysin coregulated protein 1 as a molecular gluing unit for the assembly of nanoparticle hybrid structures

Hybrid nanoparticle (NP) structures containing organic building units such as polymers, peptides, DNA and proteins have great potential in biosensor and electronic applications. The nearly free modification of the polymer chain, the variation of the protein and DNA sequence and the implementation of functional moieties provide a great platform to create inorganic structures of different morphology, resulting in different optical and magnetic properties. Nevertheless, the design and modification of a protein structure with functional groups or sequences for the assembly of biohybrid materials is not trivial. This is mainly due to the sensitivity of its secondary, tertiary and quaternary structure to the changes in the interaction (e.g., hydrophobic, hydrophilic, electrostatic, chemical groups) between the protein subunits and the inorganic material. Here, we use hemolysin coregulated protein 1 (Hcp1) from Pseudomonas aeruginosa as a building and gluing unit for the formation of biohybrid structures by implementing cysteine anchoring points at defined positions on the protein rim (Hcp1_cys3). We successfully apply the Hcp1_cys3 gluing unit for the assembly of often linear, hybrid structures of plasmonic gold (Au NP), magnetite (Fe3O4 NP), and cobalt ferrite nanoparticles (CoFe2O4 NP). Furthermore, the assembly of Au NPs into linear structures using Hcp1_cys3 is investigated by UV–vis spectroscopy, TEM and cryo-TEM. One key parameter for the formation of Au NP assembly is the specific ionic strength in the mixture. The resulting network-like structure of Au NPs is characterized by Raman spectroscopy, showing surface-enhanced Raman scattering (SERS) by a factor of 8·104 and a stable secondary structure of the Hcp1_cys3 unit. In order to prove the catalytic performance of the gold hybrid structures, they are used as a catalyst in the reduction reaction of 4-nitrophenol showing similar catalytic activity as the pure Au NPs. To further extend the functionality of the Hcp1_cys3 gluing unit, Fe3O4 and CoFe2O4 NPs are aligned in a magnetic field and connected by utilization of cysteine-modified Hcp1. After lyophilization, a fiber-like material of micrometer scale length can be observed. The Fe3O4 Hcp1_cys3 fibers show superparamagnetic behavior with a decreasing blocking temperature and an increasing remanent magnetization leading to a higher squareness value of the hysteresis curve. Thus the Hcp1_cys3 unit is shown to be very versatile in the formation of new biohybrid materials with enhanced magnetic, catalytic and optical properties

Intergrowth and Interfacial Structure of Biomimetic Fluorapatite–Gelatin Nanocomposite: A Solid-State NMR Study

The model system fluorapatite–gelatin allows mimicking the formation conditions on a lower level of complexity compared to natural dental and bone tissues. Here, we report on solid-state NMR investigations to examine the structure of fluorapatite–gelatin nanocomposites on a molecular level with particular focus on organic–inorganic interactions. Using ³¹P, ¹⁹F, and ¹H MAS NMR and heteronuclear correlations, we found the nanocomposite to consist of crystalline apatite-like regions (fluorapatite and hydroxyfluorapatite) in close contact with a more dissolved (amorphous) layer containing first motifs of the apatite crystal structure as well as the organic component. A scheme of the intergrowth region in the fluorapatite–gelatin nanocomposite, where mineral domains interact with organic matrix, is presented

Structural Relationship between Calcite-Gelatine Composites and Biogenic (Human) Otoconia

Biogenic otoconia (ear dust) are composite materials of calcite with about 2 wt.-% proteins showing an average longitudinal size of about 10 mu m. The tiny biomineral particles are situated in the inner ear (in the maculae) and act as sensors for gravity and linear acceleration. Our comparative study of calcitegelatine composites (grown by double diffusion) and human otoconia is based on decalcification experiments, scanning electron microscopy, TEM and X-ray investigations in order to obtain a complete picture of the 3D structure and morphogenesis of the materials. Otoconia as calciteprotein composites display a cylindrical body with terminal rhombohedral faces intersecting at the pointed ends. As evidenced by TEM on focused ion beam cuts, both the artificial composites and human otoconia show a particular distribution of areas with different volume densities leading to a dumbbell-shape of the more dense parts consisting of rhombohedral branches (with end faces) and a less ordered, less dense area (the belly region). The peculiar inner architecture of otoconia with its dumbbell-shaped mass/density distribution is assumed to be necessary for optimal sensing of linear accelerations

Morphogenesis of Magnetite Mesocrystals: Interplay Between Nanoparticle Morphology and Solvation Shell

In this study, faceted mesocrystals have been assembled from the dispersion of truncated cubic-shaped iron oxide nanoparticles stabilized by oleic acid (OA) molecules using the non-solvent “gas phase diffusion technique” into an organic solvent. The effects of synthesis conditions as well as of the nanoparticle size and shape on the structure and morphogenesis of mesocrystals were examined. The interactions of OA capped iron oxide nanoparticles with solvent molecules were probed by analytical ultracentrifugation and double difference pair distribution function analysis. It was shown that the structure of the organic shell significantly depends on the nature and polarity of solvent molecules