Tag Archives: hydrophilic (attracting water)

Self-assembled molecular nanofibers that are stronger than steel

A January 26, 2021 news item on Nanowerk announces a promising discovery in ‘self-assembly research’ (Note: A link has been removed,

Self-assembly is ubiquitous in the natural world, serving as a route to form organized structures in every living organism. This phenomenon can be seen, for instance, when two strands of DNA — without any external prodding or guidance — join to form a double helix, or when large numbers of molecules combine to create membranes or other vital cellular structures. Everything goes to its rightful place without an unseen builder having to put all the pieces together, one at a time.

For the past couple of decades, scientists and engineers have been following nature’s lead, designing molecules that assemble themselves in water, with the goal of making nanostructures, primarily for biomedical applications such as drug delivery or tissue engineering.

“These small-molecule-based materials tend to degrade rather quickly,” explains Julia Ortony, assistant professor in [Massachusetts Institute of Technology] MIT’s Department of Materials Science and Engineering (DMSE), “and they’re chemically unstable, too. The whole structure falls apart when you remove the water, particularly when any kind of external force is applied.”

She and her team, however, have designed a new class of small molecules that spontaneously assemble into nanoribbons with unprecedented strength, retaining their structure outside of water. The results of this multi-year effort, which could inspire a broad range of applications, were described in Nature Nanotechnology (“Self-assembly of aramid amphiphiles into ultra-stable nanoribbons and aligned nanoribbon threads”) by Ortony and coauthors.

“This seminal work — which yielded anomalous mechanical properties through highly controlled self-assembly — should have a big impact on the field,” asserts Professor Tazuko Aida, deputy director for the RIKEN Center for Emergent Matter Science and professor of chemistry and biotechnology at the University of Tokyo, who was not involved in the research.

A January 26, 2021 MIT news release, which originated the news item, describe the work in more detail,

The material the MIT group constructed — or rather, allowed to construct itself — is modeled after a cell membrane. Its outer part is “hydrophilic,” which means it likes to be in water, whereas its inner part is “hydrophobic,” meaning it tries to avoid water. This configuration, Ortony comments, “provides a driving force for self-assembly,” as the molecules orient themselves to minimize interactions between the hydrophobic regions and water, consequently taking on a nanoscale shape.

The shape, in this case, is conferred by water, and ordinarily the whole structure would collapse when dried. But Ortony and her colleagues came up with a plan to keep that from happening. When molecules are loosely bound together, they move around quickly, analogous to a fluid; as the strength of intermolecular forces increases, motion slows and molecules assume a solid-like state. The idea, Ortony explains, “is to slow molecular motion through small modifications to the individual molecules, which can lead to a collective, and hopefully dramatic, change in the nanostructure’s properties.”

One way of slowing down molecules, notes Ty Christoff-Tempesta, a PhD student and first author of the paper, “is to have them cling to each other more strongly than in biological systems.” That can be accomplished when a dense network of strong hydrogen bonds join the molecules together. “That’s what gives a material like Kevlar — constructed of so-called ‘aramids’ — its chemical stability and strength,” states Christoff-Tempesta.

Ortony’s team incorporated that capability into their design of a molecule that has three main components: an outer portion that likes to interact with water, aramids in the middle for binding, and an inner part that has a strong aversion to water. The researchers tested dozens of molecules meeting these criteria before finding the design that led to long ribbons with nanometer-scale thickness. The authors then measured the nanoribbons’ strength and stiffness to understand the impact of including Kevlar-like interactions between molecules. They discovered that the nanoribbons were unexpectedly sturdy — stronger than steel, in fact. 

This finding led the authors to wonder if the nanoribbons could be bundled to produce stable macroscopic materials. Ortony’s group devised a strategy whereby aligned nanoribbons were pulled into long threads that could be dried and handled. Notably, Ortony’s team showed that the threads could hold 200 times their own weight and have extraordinarily high surface areas — 200 square meters per gram of material. “This high surface-to-mass ratio offers promise for miniaturizing technologies by performing more chemistry with less material,” explains Christoff-Tempesta. To this end, they have already developed nanoribbons whose surfaces are coated with molecules that can pull heavy metals, like lead or arsenic, out of contaminated water. Other efforts in the research group are aimed at using bundled nanoribbons in electronic devices and batteries.

Ortony, for her part, is still amazed that they’ve been able to achieve their original research goal of “tuning the internal state of matter to create exceptionally strong molecular nanostructures.” Things could easily have gone the other way; these materials might have proved to be disorganized, or their structures fragile, like their predecessors, only holding up in water. But, she says, “we were excited to see that our modifications to the molecular structure were indeed amplified by the collective behavior of molecules, creating nanostructures with extremely robust mechanical properties. The next step, figuring out the most important applications, will be exciting.”

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

Self-assembly of aramid amphiphiles into ultra-stable nanoribbons and aligned nanoribbon threads by Ty Christoff-Tempesta, Yukio Cho, Dae-Yoon Kim, Michela Geri, Guillaume Lamour, Andrew J. Lew, Xiaobing Zuo, William R. Lindemann & Julia H. Ortony. Nature Nanotechnology (2021) DOI: https://doi.org/10.1038/s41565-020-00840-w Published: 18 January 2021

This paper is behind a paywall.

Eye implants inspired by glasswing butterflies

Glasswinged butterfly. Greta oto. Credit: David Tiller/CC BY-SA 3.0

My jaw dropped on seeing this image and I still have trouble believing it’s real. (You can find more image of glasswinged butterflies here in an Cot. 25, 2014 posting on thearkinspace. com and there’s a video further down in the post.)

As for the research, an April 30, 2018 news item on phys.org announces work that could improve eye implants,

Inspired by tiny nanostructures on transparent butterfly wings, engineers at Caltech have developed a synthetic analogue for eye implants that makes them more effective and longer-lasting. A paper about the research was published in Nature Nanotechnology.

An April 30, 2018 California Institute of Technology (CalTech) news release (also on EurekAlert) by Robert Perkins, which originated the news item, goes into more detail,

Sections of the wings of a longtail glasswing butterfly are almost perfectly transparent. Three years ago, Caltech postdoctoral researcher Radwanul Hasan Siddique–at the time working on a dissertation involving a glasswing species at Karlsruhe Institute of Technology in Germany–discovered the reason why: the see-through sections of the wings are coated in tiny pillars, each about 100 nanometers in diameter and spaced about 150 nanometers apart. The size of these pillars–50 to 100 times smaller than the width of a human hair–gives them unusual optical properties. The pillars redirect the light that strikes the wings so that the rays pass through regardless of the original angle at which they hit the wings. As a result, there is almost no reflection of the light from the wing’s surface.

In effect, the pillars make the wings clearer than if they were made of just plain glass.

That redirection property, known as angle-independent antireflection, attracted the attention of Caltech’s Hyuck Choo. For the last few years Choo has been developing an eye implant that would improve the monitoring of intra-eye pressure in glaucoma patients. Glaucoma is the second leading cause of blindness worldwide. Though the exact mechanism by which the disease damages eyesight is still under study, the leading theory suggests that sudden spikes in the pressure inside the eye damages the optic nerve. Medication can reduce the increased eye pressure and prevent damage, but ideally it must be taken at the first signs of a spike in eye pressure.

“Right now, eye pressure is typically measured just a couple times a year in a doctor’s office. Glaucoma patients need a way to measure their eye pressure easily and regularly,” says Choo, assistant professor of electrical engineering in the Division of Engineering and Applied Science and a Heritage Medical Research Institute Investigator.

Choo has developed an eye implant shaped like a tiny drum, the width of a few strands of hair. When inserted into an eye, its surface flexes with increasing eye pressure, narrowing the depth of the cavity inside the drum. That depth can be measured by a handheld reader, giving a direct measurement of how much pressure the implant is under.

One weakness of the implant, however, has been that in order to get an accurate measurement, the optical reader has to be held almost perfectly perpendicular–at an angle of 90 degrees (plus or minus 5 degrees)–with respect to the surface of the implant. At other angles, the reader gives an incorrect measurement.

And that’s where glasswing butterflies come into the picture. Choo reasoned that the angle-independent optical property of the butterflies’ nanopillars could be used to ensure that light would always pass perpendicularly through the implant, making the implant angle-insensitive and providing an accurate reading regardless of how the reader is held.

He enlisted Siddique to work in his lab, and the two, working along with Caltech graduate student Vinayak Narasimhan, figured out a way to stud the eye implant with pillars approximately the same size and shape of those on the butterfly’s wings but made from silicon nitride, an inert compound often used in medical implants. Experimenting with various configurations of the size and placement of the pillars, the researchers were ultimately able to reduce the error in the eye implants’ readings threefold.

“The nanostructures unlock the potential of this implant, making it practical for glaucoma patients to test their own eye pressure every day,” Choo says.

The new surface also lends the implants a long-lasting, nontoxic anti-biofouling property.

In the body, cells tend to latch on to the surface of medical implants and, over time, gum them up. One way to avoid this phenomenon, called biofouling, is to coat medical implants with a chemical that discourages the cells from attaching. The problem is that such coatings eventually wear off.

The nanopillars created by Choo’s team, however, work in a different way. Unlike the butterfly’s nanopillars, the lab-made nanopillars are extremely hydrophilic, meaning that they attract water. Because of this, the implant, once in the eye, is soon encased in a coating of water. Cells slide off instead of gaining a foothold.

“Cells attach to an implant by binding with proteins that are adhered to the implant’s surface. The water, however, prevents those proteins from establishing a strong connection on this surface,” says Narasimhan. Early testing suggests that the nanopillar-equipped implant reduces biofouling tenfold compared to previous designs, thanks to this anti-biofouling property.

Being able to avoid biofouling is useful for any implant regardless of its location in the body. The team plans to explore what other medical implants could benefit from their new nanostructures, which can be inexpensively mass produced.

As if the still image wasn’t enough,

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

Multifunctional biophotonic nanostructures inspired by the longtail glasswing butterfly for medical devices by Vinayak Narasimhan, Radwanul Hasan Siddique, Jeong Oen Lee, Shailabh Kumar, Blaise Ndjamen, Juan Du, Natalie Hong, David Sretavan, & Hyuck Choo. Nature Nanotechnology (2018) doi:10.1038/s41565-018-0111-5 Published: 30 April 2018

This paper is behind a paywall.

ETA May 25, 2018:  I’m obsessed. Here’s one more glasswing image,

Caption: The clear wings make this South-American butterfly hard to see in flight, a succesfull defense mechanism. Credit: Eddy Van 3000 from in Flanders fields – Belgiquistan – United Tribes ov Europe Date: 7 October 2007, 14:35 his file is licensed under the Creative Commons Attribution-Share Alike 2.0 Generic license. [downloaded from https://commons.wikimedia.org/wiki/File:E3000_-_the_wings-become-windows_butterfly._(by-sa).jpg]