Natural and synthetic nanopores directing osteogenic differentiation of human stem cells.

Bone regeneration is a highly orchestrated process crucial for endogenous healing procedures after accidents, infections or tumor therapy. Changes in surface nanotopography are known to directly affect the formation of osteogenic cell types, although no direct linkage to the endogenous nanotopography of bone was described so far. Here we show the presence of pores of 31.93 ±â€¯0.97 nm diameter on the surface of collagen type I fibers, the organic component of bone, and demonstrate these pores to be sufficient to induce osteogenic differentiation of adult human stem cells. We further applied SiO2 nanoparticles thermally cross-linked to a nanocomposite to artificially biomimic 31.93 ±â€¯0.97 nm pores, which likewise led to in vitro production of bone mineral by adult human stem cells. Our findings show an endogenous mechanism of directing osteogenic differentiation of adult stem cells by nanotopological cues and provide a direct application using SiO2 nanocomposites with surface nanotopography biomimicking native bone architecture.

Exceptionally strong, stiff and hard hybrid material based on an elastomer and isotropically shaped ceramic nanoparticles.

In this work the fabrication of hard, stiff and strong nanocomposites based on polybutadiene and iron oxide nanoparticles is presented. The nanocomposites are fabricated via a general concept for mechanically superior nanocomposites not based on the brick and mortar structure, thus on globular nanoparticles with nanosized organic shells. For the fabrication of the composites oleic acid functionalized iron oxide nanoparticles are decorated via ligand exchange with an α,ω-polybutadiene dicarboxylic acid. The functionalized particles were processed at 145 °C. Since polybutadiene contains double bonds the nanocomposites obtained a crosslinked structure which was enhanced by the presence of oxygen or sulfur. It was found that the crosslinking and filler percolation yields high elastic moduli of approximately 12-20 GPa and hardness of 15-18 GPa, although the polymer volume fraction is up to 40%. We attribute our results to a catalytically enhanced crosslinking reaction of the polymer chains induced by oxygen or sulfur and to the microstructure of the nanocomposite.

Organically linked iron oxide nanoparticle supercrystals with exceptional isotropic mechanical properties.

It is commonly accepted that the combination of the anisotropic shape and nanoscale dimensions of the mineral constituents of natural biological composites underlies their superior mechanical properties when compared to those of their rather weak mineral and organic constituents. Here, we show that the self-assembly of nearly spherical iron oxide nanoparticles in supercrystals linked together by a thermally induced crosslinking reaction of oleic acid molecules leads to a nanocomposite with exceptional bending modulus of 114 GPa, hardness of up to 4 GPa and strength of up to 630 MPa. By using a nanomechanical model, we determined that these exceptional mechanical properties are dominated by the covalent backbone of the linked organic molecules. Because oleic acid has been broadly used as nanoparticle ligand, our crosslinking approach should be applicable to a large variety of nanoparticle systems.

Oriented attachment explains cobalt ferrite nanoparticle growth in bioinspired syntheses.

Oriented attachment has created a great debate about the description of crystal growth throughout the last decade. This aggregation-based model has successfully described biomineralization processes as well as forms of inorganic crystal growth, which could not be explained by classical crystal growth theory. Understanding the nanoparticle growth is essential since physical properties, such as the magnetic behavior, are highly dependent on the microstructure, morphology and composition of the inorganic crystals. In this work, the underlying nanoparticle growth of cobalt ferrite nanoparticles in a bioinspired synthesis was studied. Bioinspired syntheses have sparked great interest in recent years due to their ability to influence and alter inorganic crystal growth and therefore tailor properties of nanoparticles. In this synthesis, a short synthetic version of the protein MMS6, involved in nanoparticle formation within magnetotactic bacteria, was used to alter the growth of cobalt ferrite. We demonstrate that the bioinspired nanoparticle growth can be described by the oriented attachment model. The intermediate stages proposed in the theoretical model, including primary-building-block-like substructures as well as mesocrystal-like structures, were observed in HRTEM measurements. These structures display regions of substantial orientation and possess the same shape and size as the resulting discs. An increase in orientation with time was observed in electron diffraction measurements. The change of particle diameter with time agrees with the recently proposed kinetic model for oriented attachment.

Antifreeze glycopeptide diastereomers.

Antifreeze glycopeptides (AFGPs) are a special class of biological antifreeze agents, which possess the property to inhibit ice growth in the body fluids of arctic and antarctic fish and, thus, enable life under these harsh conditions. AFGPs are composed of 4-55 tripeptide units -Ala-Ala-Thr- glycosylated at the threonine side chains. Despite the structural homology among all the fish species, divergence regarding the composition of the amino acids occurs in peptides from natural sources. Although AFGPs were discovered in the early 1960s, the adsorption mechanism of these macromolecules to the surface of the ice crystals has not yet been fully elucidated. Two AFGP diastereomers containing different amino acid configurations were synthesized to study the influence of amino acid stereochemistry on conformation and antifreeze activity. For this purpose, peptides containing monosaccharide-substituted allo-L- and D-threonine building blocks were assembled by solid-phase peptide synthesis (SPPS). The retro-inverso AFGP analogue contained all amino acids in D-configuration, while the allo-L-diastereomer was composed of L-amino acids, like native AFGPs, with replacement of L-threonine by its allo-L-diastereomer. Both glycopeptides were analyzed regarding their conformational properties, by circular dichroism (CD), and their ability to inhibit ice recrystallization in microphysical experiments.

Influence of sequential modifications and carbohydrate variations in synthetic AFGP analogues on conformation and antifreeze activity.

Certain Arctic and Antarctic ectotherm species have developed strategies for survival under low temperature conditions that, among others, consist of antifreeze glycopeptides (AFGP). AFGP form a class of biological antifreeze agents that exhibit the ability to inhibit ice growth in vitro and in vivo and, hence, enable life at temperatures below the freezing point. AFGP usually consist of a varying number of (Ala-Ala-Thr)(n) units (n=4-55) with the disaccharide ß-D-galactosyl-(1→3)-α-N-acetyl-D-galactosamine glycosidically attached to every threonine side chain hydroxyl group. AFGP have been shown to adopt polyproline II helical conformation. Although this pattern is highly conserved among different species, microheterogeneity concerning the amino acid composition usually occurs; for example, alanine is occasionally replaced by proline in smaller AFGP. The influence of minor and major sequence mutations on conformation and antifreeze activity of AFGP analogues was investigated by replacement of alanine by proline and glycosylated threonine by glycosylated hydroxyproline. The target compounds were prepared by using microwave-enhanced solid phase peptide synthesis. Furthermore, artificial analogues were obtained by copper-catalyzed azide-alkyne cycloaddition (CuAAC): propargyl glycosides were treated with polyproline helix II-forming peptides comprising (Pro-Azp-Pro)(n) units (n=2-4) that contained 4-azidoproline (Azp). The conformations of all analogues were examined by circular dichroism (CD). In addition, microphysical analysis was performed to provide information on their inhibitory effect on ice recrystallization.

From nanoscale liquid spheres to anisotropic crystalline particles of tin: decomposition of decamethylstannocene in organic solvents.

Routes are presented for synthesizing nano- and mesostructured ß-tin particles in the form of monocrystalline spheres, cubes, and bars, as well as polycrystalline rods and needles, by the decomposition of decamethylstannocene in organic solvents under various conditions. The formation of the observed shapes is based on the presence of liquidlike and of partly crystalline droplets. These particle stages allow structure-determining processes such as entire coalescence, oriented superficial coalescence or superficial induced crystallization. Entire coalescence and oriented superficial coalescence take place in the absence of surfactants; the superficially induced crystallization occurs in the presence of ionic additives. The observed tin morphologies depend on the competition between droplet growth and crystallization behavior. The different tin particles are investigated by electron microscopy (SEM, TEM, HRTEM), selected area electron diffraction (SAED), and differential scanning calorimetry (DSC).