Forum for Science, Industry and Business

Sponsored by:     3M 
Search our Site:

 

Self-assembled superlattices create molecular machines with 'hinges' and 'gears'

07.04.2014

A combined computational and experimental study of self-assembled silver-based structures known as superlattices has revealed an unusual and unexpected behavior: arrays of gear-like molecular-scale machines that rotate in unison when pressure is applied to them.

Computational and experimental studies show that the superlattice structures, which are self-assembled from smaller clusters of silver nanoparticles and organic protecting molecules, form in layers with the hydrogen bonds between their components serving as "hinges" to facilitate the rotation. Movement of the "gears" is related to another unusual property of the material: increased pressure on the superlattice softens it, allowing subsequent compression to be done with significantly less force.


This video shows the motion of nanoparticles in neighboring layers of the superlattice as pressure is applied.

Credit: Courtesy of Uzi Landman

Materials containing the gear-like nanoparticles – each composed of nearly 500 atoms – might be useful for molecular-scale switching, sensing and even energy absorption. The complex superlattice structure is believed to be among the largest solids ever mapped in detail using a combined X-ray and computational techniques.

"As we squeeze on this material, it gets softer and softer and suddenly experiences a dramatic change," said Uzi Landman, a Regents' and F.E. Callaway professor in the School of Physics at the Georgia Institute of Technology. "When we look at the orientation of the microscopic structure of the crystal in the region of this transition, we see that something very unusual happens. The structures start to rotate with respect to one another, creating a molecular machine with some of the smallest moving elements ever observed."

The gears rotate as much as 23 degrees, and return to their original position when the pressure is released. Gears in alternating layers move in opposite directions, said Landman, who is director of the Center for Computational Materials Science at Georgia Tech.

Supported by the Air Force Office of Scientific Research and the Office of Basic Energy Sciences in the Department of Energy, the research was reported April 6 in the journal Nature Materials. Researchers from Georgia Tech and the University of Toledo collaborated on the project.

The research studied superlattice structures composed of clusters with cores of 44 silver atoms each. The silver clusters are protected by 30 ligand molecules of an organic material – mercaptobenzoic acid (p-MBA) – that include an acid group. The organic molecules are attached to the silver by sulfur atoms.

"It's not the individual atoms that form the superlattice," explained Landman. "You actually make the larger structure from clusters that are already crystallized. You can make an ordered array from those."

In solution, the clusters assemble themselves into the larger superlattice, guided by the hydrogen bonds, which can only form between the p-MBA molecules at certain angles.

"The self-assembly process is guided by the desire to form hydrogen bonds," Landman explained. "These bonds are directional and cannot vary significantly, which restricts the orientation that the molecules can have."

The superlattice was studied first using quantum-mechanical molecular dynamics simulations conducted in Landman's lab. The system was also studied experimentally by a research group headed by Terry Bigioni, an associate professor in the Department of Chemistry and Biochemistry at the University of Toledo.

The unusual behavior occurred as the superlattice was being compressed using hydrostatic techniques. After the structure had been compressed by about six percent of its volume, the pressure required for additional compression suddenly dropped significantly. The researchers discovered that the drop occurred when the nanocrystal components rotated, layer-by-layer, in opposite directions.

Just as the hydrogen bonds direct how the superlattice structure is formed, so also do they guide how the structure moves under pressure.

"The hydrogen bond likes to have directionality in its orientation," Landman explained. "When you press on the superlattice, it wants to maintain the hydrogen bonds. In the process of trying to maintain the hydrogen bonds, all the organic ligands bend the silver cores in one layer one way, and those in the next layer bend and rotate the other way."

When the nanoclusters move, the structure pivots about the hydrogen bonds, which act as "molecular hinges" to allow the rotation. The compression is possible at all, Landman noted, because the crystalline structure has about half of its space open.

The movement of the silver nanocrystallites could allow the superlattice material to serve as an energy-absorbing structure, converting force to mechanical motion. By changing the conductive properties of the silver superlattice, compressing the material could also allow it be used as molecular-scale sensors and switches.

The combined experimental and computation study makes the silver superlattice one of the most thoroughly studied materials in the world.

"We now have complete control over a unique material that by its composition has a diversity of molecules," Landman said. "It has metal, it has organic materials and it has a stiff metallic core surrounded by a soft material."

For the future, the researchers plan additional experiments to learn more about the unique properties of the superlattice system. The unique system shows how unusual properties can arise when nanometer-scale systems are combined with many other small-scale units.

"We make the small particles, and they are different because small is different," said Landman. "When you put them together, having more of them is different because that allows them to behave collectively, and that collective activity makes the difference."

###

In addition to those already mentioned, Georgia Tech co-authors include research scientist Bokwon Yoon – the paper's first author – and senior research scientists W. David Luedtke, Robert Barnett and Jianping Gao. Co-authors from the University of Toledo include Anil Desireddy and Brian E. Conn.

This research was supported by the Air Force Office of Scientific Research (AFOSR), and by the Office of Basic Energy Sciences of the U.S. Department of Energy (DOE) under Contract FG05-86ER45234. Any conclusions or opinions expressed are those of the authors and do not necessarily represent the official views of the AFOSR or the DOE.

CITATION: Bokwon Yoon, et al., "Hydrogen-bonded structure and mechanical chiral response of a silver nanoparticle superlattice." (Nature Materials, 2014). http://dx.doi.org/ 10.1038/NMAT3923.

John Toon | EurekAlert!
Further information:
http://www.gatech.edu

Further reports about: Energy Nature Technology acid bonds clusters pressure properties structure structures

More articles from Materials Sciences:

nachricht New gel-like coating beefs up the performance of lithium-sulfur batteries
22.03.2017 | Yale University

nachricht Pulverizing electronic waste is green, clean -- and cold
22.03.2017 | Rice University

All articles from Materials Sciences >>>

The most recent press releases about innovation >>>

Die letzten 5 Focus-News des innovations-reports im Überblick:

Im Focus: Giant Magnetic Fields in the Universe

Astronomers from Bonn and Tautenburg in Thuringia (Germany) used the 100-m radio telescope at Effelsberg to observe several galaxy clusters. At the edges of these large accumulations of dark matter, stellar systems (galaxies), hot gas, and charged particles, they found magnetic fields that are exceptionally ordered over distances of many million light years. This makes them the most extended magnetic fields in the universe known so far.

The results will be published on March 22 in the journal „Astronomy & Astrophysics“.

Galaxy clusters are the largest gravitationally bound structures in the universe. With a typical extent of about 10 million light years, i.e. 100 times the...

Im Focus: Tracing down linear ubiquitination

Researchers at the Goethe University Frankfurt, together with partners from the University of Tübingen in Germany and Queen Mary University as well as Francis Crick Institute from London (UK) have developed a novel technology to decipher the secret ubiquitin code.

Ubiquitin is a small protein that can be linked to other cellular proteins, thereby controlling and modulating their functions. The attachment occurs in many...

Im Focus: Perovskite edges can be tuned for optoelectronic performance

Layered 2D material improves efficiency for solar cells and LEDs

In the eternal search for next generation high-efficiency solar cells and LEDs, scientists at Los Alamos National Laboratory and their partners are creating...

Im Focus: Polymer-coated silicon nanosheets as alternative to graphene: A perfect team for nanoelectronics

Silicon nanosheets are thin, two-dimensional layers with exceptional optoelectronic properties very similar to those of graphene. Albeit, the nanosheets are less stable. Now researchers at the Technical University of Munich (TUM) have, for the first time ever, produced a composite material combining silicon nanosheets and a polymer that is both UV-resistant and easy to process. This brings the scientists a significant step closer to industrial applications like flexible displays and photosensors.

Silicon nanosheets are thin, two-dimensional layers with exceptional optoelectronic properties very similar to those of graphene. Albeit, the nanosheets are...

Im Focus: Researchers Imitate Molecular Crowding in Cells

Enzymes behave differently in a test tube compared with the molecular scrum of a living cell. Chemists from the University of Basel have now been able to simulate these confined natural conditions in artificial vesicles for the first time. As reported in the academic journal Small, the results are offering better insight into the development of nanoreactors and artificial organelles.

Enzymes behave differently in a test tube compared with the molecular scrum of a living cell. Chemists from the University of Basel have now been able to...

All Focus news of the innovation-report >>>

Anzeige

Anzeige

Event News

International Land Use Symposium ILUS 2017: Call for Abstracts and Registration open

20.03.2017 | Event News

CONNECT 2017: International congress on connective tissue

14.03.2017 | Event News

ICTM Conference: Turbine Construction between Big Data and Additive Manufacturing

07.03.2017 | Event News

 
Latest News

When Air is in Short Supply - Shedding light on plant stress reactions when oxygen runs short

23.03.2017 | Life Sciences

Researchers use light to remotely control curvature of plastics

23.03.2017 | Power and Electrical Engineering

Sea ice extent sinks to record lows at both poles

23.03.2017 | Earth Sciences

VideoLinks
B2B-VideoLinks
More VideoLinks >>>