Tag Archives: Igor Zlotnikov

Mother-of-pearl self-assembles from disorder into perfection

Courtesy: Mother-of-pearl Courtesy: Technische Universitaet (TU) Dresden

Mother-of-pearl (also known as nacre) research has been featured here a few times (links at the end of this post). This time it touches on self-assembly, which is the source of much interest and, on occasion, much concern in the field of nanotechnology.

In any case, the latest mother-of-pearl work comes from the Technische Universität (TU) Dresden (Technical University of Dresden), located in Germany. From a January 4, 2021 news item on phys.org,

In a new study published in Nature Physics, researchers from the B CUBE—Center for Molecular Bioengineering at TU Dresden and European Synchrotron Radiation Facility (ESRF) in Grenoble [Grance] describe, for the first time, that structural defects in self-assembling nacre attract and cancel each other out, eventually leading to a perfect periodic structure.

A January 4, 2021 Technische Universität (TU) Dresden press release (also on EurekAlert), which originated the news item, explains the reason for the ongoing interest in mother-of-pearl and reveals an unexpected turn in the research,

Mollusks build shells to protect their soft tissues from predators. Nacre, also known as the mother of pearl, has an intricate, highly regular structure that makes it an incredibly strong material. Depending on the species, nacres can reach tens of centimeters in length. No matter the size, each nacre is built from materials deposited by a multitude of single cells at multiple different locations at the same time. How exactly this highly periodic and uniform structure emerges from the initial disorder was unknown until now.

Nacre formation starts uncoordinated with the cells depositing the material simultaneously at different locations. Not surprisingly, the early nacre structure is not very regular. At this point, it is full of defects. “In the very beginning, the layered mineral-organic tissue is full of structural faults that propagate through a number of layers like a helix. In fact, they look like a spiral staircase, having either right-handed or left-handed orientation,” says Dr. Igor Zlotnikov, research group leader at the B CUBE – Center for Molecular Bioengineering at TU Dresden. “The role of these defects in forming such a periodic tissue has never been established. On the other hand, the mature nacre is defect-free, with a regular, uniform structure. How could perfection emerge from such disorder?”

The researchers from the Zlotnikov group collaborated with the European Synchrotron Radiation Facility (ESRF) in Grenoble to take a very detailed look at the internal structure of the early and mature nacre. Using synchrotron-based holographic X-ray nano-tomography the researchers could capture the growth of nacre over time. “Nacre is an extremely fine structure, having organic features below 50 nm in size. Beamline ID16A at the ESRF provided us with an unprecedented capability to visualize nacre in three-dimensions,” explains Dr. Zlotnikov. “The combination of electron dense and highly periodical inorganic platelets with delicate and slender organic interfaces makes nacre a challenging structure to image. Cryogenic imaging helped us to obtain the resolving power we needed,” explains Dr. ‘Alexandra] Pacureanu from the X-ray Nanoprobe group at the ESRF.

The analysis of data was quite a challenge. The researchers developed a segmentation algorithm using neural networks and trained it to separate different layers of nacre. In this way, they were able to follow what happens to the structural defects as nacre grows.

The behavior of structural defects in a growing nacre was surprising. Defects of opposite screw direction were attracted to each other from vast distances. The right-handed and left-handed defects moved through the structure, until they met, and cancelled each other out. These events led to a tissue-wide synchronization. Over time, it allowed the structure to develop into a perfectly regular and defect-free.

Periodic structures similar to nacre are produced by many different animal species. The researchers think that the newly discovered mechanism could drive not only the formation of nacre but also other biogenic structures.

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

Dynamics of topological defects and structural synchronization in a forming periodic tissue by Maksim Beliaev, Dana Zöllner, Alexandra Pacureanu, Paul Zaslansky & Igor Zlotnikov. Nature Physics (2021) First published online: 17 September 2020 Published: 04 January 2021

This paper is behind a paywall.

As promised here are the links for One tough mother, imitating mother-of-pearl for stronger ceramics (a March 14, 2014 posting) and Clues as to how mother of pearl is made (a December 15, 2015 posting).

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.