Tag Archives: Emil Zolotoyabko

Discovering why your teeth aren’t perfectly crack-resistant

This helps make your teeth crack-resistant?

Caption: Illustration shows complex biostructure of dentin: the dental tubuli (yellow hollow cylinders, diameters appr. 1 micrometer) are surrounded by layers of mineralized collagen fibers (brown rods). The tiny mineral nanoparticles are embedded in the mesh of collagen fibers and not visible here. Credit: JB Forien @Charité

Caption: Illustration shows complex biostructure of dentin: the dental tubuli (yellow hollow cylinders, diameters appr. 1 micrometer) are surrounded by layers of mineralized collagen fibers (brown rods). The tiny mineral nanoparticles are embedded in the mesh of collagen fibers and not visible here. Credit: JB Forien @Charité

A June 10, 2015 Helmholtz Zentrum Berlin (HZB) press release (also on EurekAlert) explains how the illustration above relates to the research,

Human teeth have to serve for a lifetime, despite being subjected to huge forces. But the high failure resistance of dentin in teeth is not fully understood. An interdisciplinary team led by scientists of Charite Universitaetsmedizin Berlin has now analyzed the complex structure of dentin. At the synchrotron sources BESSY II at HZB, Berlin, Germany, and the European Synchrotron Radiation Facility ESRF, Grenoble, France, they could reveal that the mineral particles are precompressed.

The internal stress works against crack propagation and increases resistance of the biostructure.

Engineers use internal stresses to strengthen materials for specific technical purposes. Now it seems that evolution has long ‘known’ about this trick, and has put it to use in our natural teeth. Unlike bones, which are made partly of living cells, human teeth are not able to repair damage. Their bulk is made of dentin, a bonelike material consisting of mineral nanoparticles. These mineral nanoparticles are embedded in collagen protein fibres, with which they are tightly connected. In every tooth, such fibers can be found, and they lie in layers, making teeth tough and damage resistant. Still, it was not well understood, how crack propagation in teeth can be stopped.

The press release goes on to describe the new research and the teams which investigated the role of the mineral nanoparticles with regard to compression and cracking,

Now researchers from Charite Julius-Wolff-Institute, Berlin have been working with partners from Materials Engineering Department of Technische Universitaets Berlin, MPI of Colloids and Interfaces, Potsdam and Technion – Israel Institute of Technology, Haifa, to examine these biostructures more closely. They performed Micro-beam in-situ stress experiments in the mySpot BESSY facility of HZB, Berlin, Germany and analyzed the local orientation of the mineral nanoparticles using the nano-imaging facility of the European Synchrotron Radiation Facility (ESRF) in Grenoble, France.

When the tiny collagen fibers shrink, the attached mineral particles become increasingly compressed, the science team found out. “Our group was able to use changes in humidity to demonstrate how stress appears in the mineral in the collagen fibers, Dr. Paul Zaslansky from Julius Wolff-Institute of Charite Berlin explains. “The compressed state helps to prevents cracks from developing and we found that compression takes place in such a way that cracks cannot easily reach the tooth inner parts, which could damage the sensitive pulp. In this manner, compression stress helps to prevent cracks from rushing through the tooth.

The scientists also examined what happens if the tight mineral-protein link is destroyed by heating: In that case, dentin in teeth becomes much weaker. We therefore believe that the balance of stresses between the particles and the protein is important for the extended survival of teeth in the mouth, Charite scientist Jean-Baptiste Forien says. Their results may explain why artificial tooth replacements usually do not work as well as healthy teeth do: they are simply too passive, lacking the mechanisms found in the natural tooth structures, and consequently fillings cannot sustain the stresses in the mouth as well as teeth do. “Our results might inspire the development of tougher ceramic structures for tooth repair or replacement, Zaslansky hopes.

Experiments took place as part of the DFG project “Biomimetic Materials Research: Functionality by Hierarchical Structuring of Materials (SPP1420).

Here’s a link to and a citation for the paper,

Compressive Residual Strains in Mineral Nanoparticles as a Possible Origin of Enhanced Crack Resistance in Human Tooth Dentin by Jean-Baptiste Forien, Claudia Fleck, Peter Cloetens, Georg Duda, Peter Fratzl, Emil Zolotoyabko, and Paul Zaslansky. Nano Lett., 2015, 15 (6), pp 3729–3734 DOI: 10.1021/acs.nanolett.5b00143 Publication Date (Web): May 26, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

Glass as a sponge

A glass sponge which can be found at the bottom of either the Indian and Pacific oceans is inspiring a group of physicists at the Max Planck Institute of Colloids and Interfaces according to a Feb. 25, 2014 news item on Azonano,

… Recently, Igor Zlotnikov and Peter Fratzl, who study biomaterials at the Max Planck Institute of Colloids and Interfaces in collaboration with the team of Peter Werner from the Max Planck Institute of Microstructure Physics, Emil Zolotoyabko from the Israeli Institute of Technology and Yannicke Dauphin from the Université P. & M. Curie, have discovered a mesoporous material in nature, namely in the glass sponge Monorhaphis chuni. The sponge lives on the bottom of the Indian and Pacific Oceans, and forms an approximately one-centimetre-thick glass rod to attach itself to the ocean’s floor. Over the course of its life, the rod can grow up to three meters in length. The glass filament, passing through the centre of this rod, is perforated with pores having a diameter of about five nanometres. Each pore is occupied by an egg-shaped protein molecule, called silicatein, connected to the protein molecules in adjacent pores through holes in the glass.

The Feb. 24, 2014 Max Planck Institute of Colloids and Interfaces news release, which originated the news item, explains the importance of nanoporous or mesoporous materials, natural and manufactured,

The amount of surface area often plays an important role in materials used in medicine and technology and normally, it should be as large as possible. It can accommodate, for instance, large quantities of pharmaceutical agents and release them gradually in the body. In chemistry, the efficiency of numerous processes is dependent on catalysts exhibiting a large surface on which reactions can occur. In sensors, for example, the sensitivity is strongly dependent on the amount of surface to which the detected molecules can attach. Porous structures are a good example for such materials.

Materials having pores measuring between 2 to 50 nanometres are particularly well suited for such purposes. Scientists refer to these as mesoporous structures, to distinguish them from structures that are microporous, having smaller pores, or macroporous, with larger pores.

Having discovered the glass sponge’s Monorhaphis chuni, ability to create a mesoporous material (a glass filament), the researchers attempted further studies, from the news release,

“Mesoporous glass structures are among the most studied materials. This makes it even more exiting to find them in nature,” says Igor Zlotnikov. “Presumably, this structure is not limited to M. chuni, but can also occur in other glass sponges.” However, not only does M. chuni produces a mesoporous material that is technologically relevant; the sponge sets standards in terms of size distribution and arrangement of the pores. In the sample that Igor Zlotnikov and his colleagues studied, all pores have the size of the inhabiting protein molecule and they are completely regularly arranged. Metaphorically speaking, the structure resembles egg cartons that are stacked one on top of another like pallets.

The researchers used two characterization techniques to gain an accurate picture of the internal architecture of the filament. First, they employed X-ray analysis at the BESSY II synchrotron facility in Berlin. Experiments with X-ray diffraction usually serve to identify the atomic periodic structure of crystals. However, Igor Zlotnikov’s team used a variant of this technology to reveal structural periodicity on a larger scale, namely, on the scale of the pores size and their spatial arrangement. The results were confirmed in cooperation with the team working with Peter Werner from the Max Planck Institute of Microstructure Physics using high resolution transmission electron microscopy. In addition to structural details, this technique allows researchers to make assertions about local chemical composition.

But what surprised the researchers even more than the periodicity of the structure that was revealed is the way in which M. chuni produces it: “It’s absolutely astonishing that nature and mankind converged on a similar manufacturing method independently”, says Peter Fratzl, Director at the Max Planck Institute of Colloids and Interfaces. To continue with the image of the egg cartons, the glass sponge first stacks one or maybe even several layers of eggs – that is, protein molecules – and then fills the gaps with cardboard, or in this case glass.

Here’s an image the researchers have provided to illustrate their ‘egg carton’ analogy,

 Pore distribution in the glass filament resembles stacked, pallet-like egg cartons. Each cavity is occupied by one protein molecule, called silicatein, measuring approximately five nanometres in size. © Igor Zlotnikov / MPI of Colloids and Interfaces


Pore distribution in the glass filament resembles stacked, pallet-like egg cartons. Each cavity is occupied by one protein molecule, called silicatein, measuring approximately five nanometres in size. © Igor Zlotnikov / MPI of Colloids and Interfaces

Even though humans have managed a similar engineering feat, it appears Nature has more successfully controlled sizes and mechanical properties (from the news release),

Since the protein molecules, which serve as a kind of a model for the surrounding glass structure, are all in the same size, the pores in the obtained material also have the same diameter and form a completely uniform structure. Achieving this precision via synthetic methods is difficult, even though the mesoporous glass is created in a very similar manner. Here, organic droplets around which the glass is produced determine the pore shape. Subsequently, the droplets are dissolved out of the nanostructure using a detergent – in principle, nothing other than a dishwashing liquid. However, scientists can’t adjust the size of the droplets as precisely as the biochemical apparatus of a living organism that controls the size of the proteins. Thus, the pore size in synthetic mesoporous materials varies, and the cavities don’t arrange themselves into a perfectly regular pattern.

“With silicatein or other proteins, it would be possible to produce mesoporous materials having a completely uniform pore size and a perfectly periodic arrangement”, says Igor Zlotnikov. “That would be very expensive.” Mimicking regularly structured materials similar to those found in M. chuni, for the time being, is not the goal of Max Planck researchers. They are currently investigating whether the mesoporous structure is as uniform over large regions of the glass filament as it is in the 100 micrometer section they analysed for the current publication. “Besides that, we focus on the relationship between the structure and the mechanical properties of the entire glass rod”, says Peter Fratzl. Also there, M. chuni sets standards in terms of structural optimization to enhance its mechanical behaviour.

Here’s a link to and a citation for the paper,

A Perfectly Periodic Three-Dimensional Protein/Silica Mesoporous Structure Produced by an Organism by Igor Zlotnikov, Peter Werner, Horst Blumtritt, Andreas Graff, Yannicke Dauphin, Emil Zolotoyabko, & Peter Fratzl. Advanced Materials. Article first published online: 12 DEC 2013 DOI: 10.1002/adma.201304696

© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.