Tag Archives: mollusks

The nanoscale precision of pearls

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An October 21, 2021 news item on phys.org features a quote about nothingness and symmetry (Note: A link has been removed),

In research that could inform future high-performance nanomaterials, a University of Michigan-led team has uncovered for the first time how mollusks build ultradurable structures with a level of symmetry that outstrips everything else in the natural world, with the exception of individual atoms.

“We humans, with all our access to technology, can’t make something with a nanoscale architecture as intricate as a pearl,” said Robert Hovden, U-M assistant professor of materials science and engineering and an author on the paper. “So we can learn a lot by studying how pearls go from disordered nothingness to this remarkably symmetrical structure.” [emphasis mine]

The analysis was done in collaboration with researchers at the Australian National University, Lawrence Berkeley National Laboratory, Western Norway University [of Applied Sciences] and Cornell University.

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a. A Keshi pearl that has been sliced into pieces for study. b. A magnified cross-section of the pearl shows its transition from its disorderly center to thousands of layers of finely matched nacre. c. A magnification of the nacre layers shows their self-correction—when one layer is thicker, the next is thinner to compensate, and vice-versa. d, e: Atomic scale images of the nacre layers. f, g, h, i: Microscopy images detail the transitions between the pearl’s layers. Credit: University of Michigan

An October 21, 2021 University of Michigan news release (also on EurekAlert), which originated the news item, reveals a surprise,

Published in the Proceedings of the National Academy of Sciences [PNAS], the study found that a pearl’s symmetry becomes more and more precise as it builds, answering centuries-old questions about how the disorder at its center becomes a sort of perfection. 

Layers of nacre, the iridescent and extremely durable organic-inorganic composite that also makes up the shells of oysters and other mollusks, build on a shard of aragonite that surrounds an organic center. The layers, which make up more than 90% of a pearl’s volume, become progressively thinner and more closely matched as they build outward from the center.

Perhaps the most surprising finding is that mollusks maintain the symmetry of their pearls by adjusting the thickness of each layer of nacre. If one layer is thicker, the next tends to be thinner, and vice versa. The pearl pictured in the study contains 2,615 finely matched layers of nacre, deposited over 548 days.

“These thin, smooth layers of nacre look a little like bed sheets, with organic matter in between,” Hovden said. “There’s interaction between each layer, and we hypothesize that that interaction is what enables the system to correct as it goes along.”

The team also uncovered details about how the interaction between layers works. A mathematical analysis of the pearl’s layers show that they follow a phenomenon known as “1/f noise,” where a series of events that seem to be random are connected, with each new event influenced by the one before it. 1/f noise has been shown to govern a wide variety of natural and human-made processes including seismic activity, economic markets, electricity, physics and even classical music.

“When you roll dice, for example, every roll is completely independent and disconnected from every other roll. But 1/f noise is different in that each event is linked,” Hovden said. “We can’t predict it, but we can see a structure in the chaos. And within that structure are complex mechanisms that enable a pearl’s thousands of layers of nacre to coalesce toward order and precision.”

The team found that pearls lack true long-range order—the kind of carefully planned symmetry that keeps the hundreds of layers in brick buildings consistent. Instead, pearls exhibit medium-range order, maintaining symmetry for around 20 layers at a time. This is enough to maintain consistency and durability over the thousands of layers that make up a pearl.

The team gathered their observations by studying Akoya “keshi” pearls, produced by the Pinctada imbricata fucata oyster near the Eastern shoreline of Australia. They selected these particular pearls, which measure around 50 millimeters in diameter, because they form naturally, as opposed to bead-cultured pearls, which have an artificial center. Each pearl was cut with a diamond wire saw into sections measuring three to five millimeters in diameter, then polished and examined under an electron microscope.

Hovden says the study’s findings could help inform next-generation materials with precisely layered nanoscale architecture.

“When we build something like a brick building, we can build in periodicity through careful planning and measuring and templating,” he said. “Mollusks can achieve similar results on the nanoscale by using a different strategy. So we have a lot to learn from them, and that knowledge could help us make stronger, lighter materials in the future.”

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

The mesoscale order of nacreous pearls by Jiseok Gim, Alden Koch, Laura M. Otter, Benjamin H. Savitzky, Sveinung Erland, Lara A. Estroff, Dorrit E. Jacob, and Robert Hovden. PNAS vol. 118 no. 42 e2107477118 DOI: https://doi.org/10.1073/pnas.2107477118 Published in issue October 19, 2021 Published online October 18, 2021

This paper appears to be open access.

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

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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.

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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).

Ocean-inspired coatings for organic electronics

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An Oct. 19, 2016 news item on phys.org describes the advantages a new coating offers and the specific source of inspiration,

In a development beneficial for both industry and environment, UC Santa Barbara [University of California at Santa Barbara] researchers have created a high-quality coating for organic electronics that promises to decrease processing time as well as energy requirements.

“It’s faster, and it’s nontoxic,” said Kollbe Ahn, a research faculty member at UCSB’s Marine Science Institute and corresponding author of a paper published in Nano Letters.

In the manufacture of polymer (also known as “organic”) electronics—the technology behind flexible displays and solar cells—the material used to direct and move current is of supreme importance. Since defects reduce efficiency and functionality, special attention must be paid to quality, even down to the molecular level.

Often that can mean long processing times, or relatively inefficient processes. It can also mean the use of toxic substances. Alternatively, manufacturers can choose to speed up the process, which could cost energy or quality.

Fortunately, as it turns out, efficiency, performance and sustainability don’t always have to be traded against each other in the manufacture of these electronics. Looking no further than the campus beach, the UCSB researchers have found inspiration in the mollusks that live there. Mussels, which have perfected the art of clinging to virtually any surface in the intertidal zone, serve as the model for a molecularly smooth, self-assembled monolayer for high-mobility polymer field-effect transistors—in essence, a surface coating that can be used in the manufacture and processing of the conductive polymer that maintains its efficiency.

An Oct. 18, 2016 UCSB news release by Sonia Fernandez, which originated the news item, provides greater technical detail,

More specifically, according to Ahn, it was the mussel’s adhesion mechanism that stirred the researchers’ interest. “We’re inspired by the proteins at the interface between the plaque and substrate,” he said.

Before mussels attach themselves to the surfaces of rocks, pilings or other structures found in the inhospitable intertidal zone, they secrete proteins through the ventral grove of their feet, in an incremental fashion. In a step that enhances bonding performance, a thin priming layer of protein molecules is first generated as a bridge between the substrate and other adhesive proteins in the plaques that tip the byssus threads of their feet to overcome the barrier of water and other impurities.

That type of zwitterionic molecule — with both positive and negative charges — inspired by the mussel’s native proteins (polyampholytes), can self-assemble and form a sub-nano thin layer in water at ambient temperature in a few seconds. The defect-free monolayer provides a platform for conductive polymers in the appropriate direction on various dielectric surfaces.

Current methods to treat silicon surfaces (the most common dielectric surface), for the production of organic field-effect transistors, requires a batch processing method that is relatively impractical, said Ahn. Although heat can hasten this step, it involves the use of energy and increases the risk of defects.

With this bio-inspired coating mechanism, a continuous roll-to-roll dip coating method of producing organic electronic devices is possible, according to the researchers. It also avoids the use of toxic chemicals and their disposal, by replacing them with water.

“The environmental significance of this work is that these new bio-inspired primers allow for nanofabrication on silicone dioxide surfaces in the absence of organic solvents, high reaction temperatures and toxic reagents,” said co-author Roscoe Lindstadt, a graduate student researcher in UCSB chemistry professor Bruce Lipshutz’s lab. “In order for practitioners to switch to newer, more environmentally benign protocols, they need to be competitive with existing ones, and thankfully device performance is improved by using this ‘greener’ method.”

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

Molecularly Smooth Self-Assembled Monolayer for High-Mobility Organic Field-Effect Transistors by Saurabh Das, Byoung Hoon Lee, Roscoe T. H. Linstadt, Keila Cunha, Youli Li, Yair Kaufman, Zachary A. Levine, Bruce H. Lipshutz, Roberto D. Lins, Joan-Emma Shea, Alan J. Heeger, and B. Kollbe Ahn. Nano Lett., 2016, 16 (10), pp 6709–6715
DOI: 10.1021/acs.nanolett.6b03860 Publication Date (Web): September 27, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall but the scientists have made an illustration available,

An artist's concept of a zwitterionic molecule of the type secreted by mussels to prime surfaces for adhesion Photo Credit: Peter Allen

An artist’s concept of a zwitterionic molecule of the type secreted by mussels to prime surfaces for adhesion Photo Credit: Peter Allen

Clues as to how mother of pearl is made

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Iridescence seems to fascinate scientists and a team at Cornell University is no exception (from a Dec. 4, 2015 news item on Nanowerk),

Mother nature has a lot to teach us about how to make things.

With that in mind, Cornell researchers have uncovered the process by which mollusks manufacture nacre – commonly known as “mother of pearl.” Along with its iridescent beauty, this material found on the insides of seashells is incredibly strong. Knowing how it’s made could lead to new methods to synthesize a variety of new materials with as yet unguessed properties.

“We have all these high-tech facilities to make new materials, but just take a walk along the beach and see what’s being made,” said postdoctoral research associate Robert Hovden, M.S. ’10, Ph.D. ’14. “Nature is doing incredible nanoscience, and we need to dig into it.”

A Dec. 4, 2015 Cornell University news release by Bill Steele, which originated the news item, expands on the theme,

Using a high-resolution scanning transmission electron microscope (STEM), the researchers examined a cross section of the shell of a large Mediterranean mollusk called the noble pen shell or fan mussel (Pinna nobilis). To make the observations possible they had to develop a special sample preparation process. Using a diamond saw, they cut a thin slice through the shell, then in effect sanded it down with a thin film in which micron-sized bits of diamond were embedded, until they had a sample less than 30 nanometers thick, suitable for STEM observation. As in sanding wood, they moved from heavier grits for fast cutting to a fine final polish to make a surface free of scratches that might distort the STEM image.

Images with nanometer-scale resolution revealed that the organism builds nacre by depositing a series of layers of a material containing nanoparticles of calcium carbonate. Moving from the inside out, these particles are seen coming together in rows and fusing into flat crystals laminated between layers of organic material. (The layers are thinner than the wavelengths of visible light, causing the scattering that gives the material its iridescence.)

Exactly what happens at each step is a topic for future research. For now, the researchers said in their paper, “We cannot go back in time” to observe the process. But knowing that nanoparticles are involved is a valuable insight for materials scientists, Hovden said.

Here’s an image from the researchers,

Electron microscope image of a cross-section of a mollusk shell. The organism builds its shell from the inside out by depositing layers of calcium carbonate nanoparticles. As the particle density increases over time they fuse into large flat crystals embedded in layers of organic material to form nacre. Courtesy: Cornell University

Electron microscope image of a cross-section of a mollusk shell. The organism builds its shell from the inside out by depositing layers of calcium carbonate nanoparticles. As the particle density increases over time they fuse into large flat crystals embedded in layers of organic material to form nacre. Courtesy: Cornell University

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

Nanoscale assembly processes revealed in the nacroprismatic transition zone of Pinna nobilis mollusc shells by Robert Hovden, Stephan E. Wolf, Megan E. Holtz, Frédéric Marin, David A. Muller, & Lara A. Estroff. Nature Communications 6, Article number: 10097 doi:10.1038/ncomms10097 Published 03 December 2015

This is an open access paper.