Tag Archives: OIST

Nanomushroom sensors

Schematic illustration of cells (blue mountain-like shapes) on top of nanoscale mushroom-like structures with silicone dioxide stems and gold caps, which have the potential to detect cell proliferation in real-time. Courtesy: OIST

The nanomushroom sensors depicted in the above illustration and announced in a February 23, 2018 news item on Nanowerk probably aren’t edible but they certainly make up for that deficiency with other properties,

A small rectangle of pink glass, about the size of a postage stamp, sits on Professor Amy Shen’s desk. Despite its outwardly modest appearance, this little glass slide has the potential to revolutionize a wide range of processes, from monitoring food quality to diagnosing diseases.

The slide is made of a ‘nanoplasmonic’ material — its surface is coated in millions of gold nanostructures, each just a few billionths of a square meter in size. Plasmonic materials absorb and scatter light in interesting ways, giving them unique sensing properties. Nanoplasmonic materials have attracted the attention of biologists, chemists, physicists and material scientists, with possible uses in a diverse array of fields, such as biosensing, data storage, light generation and solar cells.

A February 23, 2018 Okinawa Institute of Science and Technology Graduate University (OIST) press release (also on EurekAlert), which originated the news item, provides more detail,

In several recent papers, Prof. Shen and colleagues at the Micro/Bio/Nanofluidics Unit at the Okinawa Institute of Science and Technology (OIST), described their creation of a new biosensing material that can be used to monitor processes in living cells.

“One of the major goals of nanoplasmonics is to search for better ways to monitor processes in living cells in real time,” says Prof. Shen. Capturing such information can reveal clues about cell behavior, but creating nanomaterials on which cells can survive for long periods of time yet don’t interfere with the cellular processes being measured is a challenge, she explains.

Counting Dividing Cells

One of the team’s new biosensors is made from a nanoplasmonic material that is able to accommodate a large number of cells on a single substrate and to monitor cell proliferation, a fundamental process involving cell growth and division, in real time. Seeing this process in action can reveal important insights into the health and functions of cells and tissues.

Researchers in OIST’s Micro/Bio/Nanofluidics Unit described the sensor in a study recently published in the journal Advanced Biosystems [citation and link follow this press release].

The most attractive feature of the material is that it allows cells to survive over long time periods. “Usually, when you put live cells on a nanomaterial, that material is toxic and it kills the cells,” says Dr. Nikhil Bhalla, a postdoctoral researcher at OIST and first author of the paper. “However, using our material, cells survived for over seven days.” The nanoplasmonic material is also highly sensitive: It can detect an increase in cells as small as 16 in 1000 cells.

The material looks just like an ordinary pieces of glass. However, the surface is coated in tiny nanoplasmonic mushroom-like structures, known as nanomushrooms, with stems of silicon dioxide and caps of gold. Together, these form a biosensor capable of detecting interactions at the molecular level.

The biosensor works by using the nanomushroom caps as optical antennae. When white light passes through the nanoplasmonic slide, the nanomushrooms absorb and scatter some of the light, changing its properties. The absorbance and scattering of light is determined by the size, shape and material of the nanomaterial and, more importantly, it is also affected by any medium in close proximity to the nanomushroom, such as cells that have been placed on the slide. By measuring how the light has changed once it emerges through the other side of the slide, the researchers can detect and monitor processes occurring on the sensor surface, such as cell division.

“Normally, you have to add labels, such as dyes or molecules, to cells, to be able to count dividing cells,” says Dr. Bhalla. “However, with our method, the nanomushrooms can sense them directly.”

Scaling Up

This work builds on a new method, developed by scientists at the Micro/Bio/Nanofluidics Unit at OIST, for fabricating nanomushroom biosensors. The technique was published in the journal ACS Applied Materials and Interfaces in December 2017.

Producing large-scale nanoplasmonic materials is challenging because it is difficult to ensure uniformity across the entire material surface. For this reason, biosensors for routine clinical examinations, such as disease testing, are still lacking.

In response to this problem, the OIST researchers developed a novel printing technique to create large-scale nanomushroom biosensors. With their method, they were able to develop a material consisting of approximately one million mushroom-like structures on a 2.5cm by 7.5cm silicon dioxide substrate.

“Our technique is like taking a stamp, covering it with ink made from biological molecules, and printing onto the nanoplasmonic slide,” says Shivani Sathish, a PhD student at OIST and co-author of the paper. The biological molecules increase the sensitivity of the material, meaning it can sense extremely low concentrations of substances, such as antibodies, and thus potentially detect diseases in their earliest stages.

“Using our method, it is possible to create a highly sensitive biosensor that can detect even single molecules,” says Dr. Bhalla, first author of the paper.

Plasmonic and nanoplasmonic sensors offer important tools for many fields, from electronics to food production to medicine. For example, in December 2017, second year Ph.D student Ainash Garifullina from the Unit developed a new plasmonic material for monitoring the quality of food products during the manufacturing process. The results were published in the journal Analytical Methods.

Prof. Shen and her unit say that, in the future, nanoplasmonic materials may even be integrated with emerging technologies, such as wireless systems in microfluidic devices, allowing users to take readings remotely and thereby minimizing the risk of contamination.

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

Large-Scale Nanophotonic Structures for Long-Term Monitoring of Cell Proliferation by Nikhil Bhalla, Shivani Sathish, Abhishek Sinha, and Amy Q. Shen. Advanced Biosystems Vol. 2 Issue 2 DOI: 10.1002/adbi.201700258 Version of Record online: 19 JAN 2018

© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

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

Probing specific gravity in real-time with graphene oxide plasmonics by Ainash Garifullina, Nikhil Bhalla, and Amy Q. Shen. Anal. Methods 2018, 10, 290-297 DOI: 10.1039/C7AY02423A first published [online] on 06 Dec 2017

This paper is open access provided you have registered for a free account.

Policing, detecting, and arresting pollution

The title for a May 13, 2015 news item on ScienceDaily was certainly eye-catching,

Nano-policing pollution

Pollutants emitted by factories and car exhausts affect humans who breathe in these harmful gases and also aggravate climate change up in the atmosphere. Being able to detect such emissions is a critically needed measure.

New research by the Nanoparticles by Design Unit at the Okinawa Institute of Science and Technology Graduate University (OIST), in collaboration with the Materials Center Leoben Austria and the Austrian Centre for Electron Microscopy and Nanoanalysis has developed an efficient way to improve methods for detecting polluting emissions using a sensor at the nanoscale. …

A May 13, 2015 OIST press release (also on EurekAlert) by Joykrit Mitra, which originated the news item, details the research (Note: A link has been removed),

The researchers used a copper oxide nanowire decorated with palladium nanoparticles to detect carbon monoxide, a common industrial pollutant.  The sensor was tested in conditions similar to ambient air since future devices developed from this method will need to operate in these conditions.

Copper oxide is a semiconductor and scientists use nanowires fabricated from it to search for potential application in the microelectronics industry. But in gas sensing applications, copper oxide was much less widely investigated compared to other metal oxide materials.

A semiconductor can be made to experience dramatic changes in its electrical properties when a small amount of foreign atoms are made to attach to its surface at high temperatures.  In this case, the copper oxide nanowire was made part of an electric circuit. The researchers detected carbon monoxide indirectly, by measuring the change in the resulting circuit’s electrical resistance in presence of the gas. They found that copper oxide nanowires decorated with palladium nanoparticles show a significantly greater increase in electrical resistance in the presence of carbon monoxide than the same type of nanowires without the nanoparticles.

The OIST Nanoparticles by Design Unit used a sophisticated technique that allowed them to first sift nanoparticles according to size, then deliver and deposit the palladium nanoparticles onto the surface of the nanowires in an evenly distributed manner. This even dispersion of size selected nanoparticles and the resulting nanoparticles-nanowire interactions are crucial to get an enhanced electrical response.  The OIST nanoparticle deposition system can be tailored to deposit multiple types of nanoparticles at the same time, segregated on distinct areas of the wafer where the nanowire sits. In other words, this system can be engineered to be able to detect multiple kinds of gases.  The next step is to detect different gases at the same time by using multiple sensor devices, with each device utilizing a different type of nanoparticle.

Compared to other options being explored in gas sensing which are bulky and difficult to miniaturize, nanowire gas sensors will be cheaper and potentially easier to mass produce.

The main energy cost in operating this kind of a sensor will be the high temperatures necessary to facilitate the chemical reactions for ensuring certain electrical response. In this study 350 degree centigrade was used.  However, different nanowire-nanoparticle material configurations are currently being investigated in order to lower the operating temperature of this system.

“I think nanoparticle-decorated nanowires have a huge potential for practical applications as it is possible to incorporate this type of technology into industrial devices,” said Stephan Steinhauer, a Japan Society for the Promotion of Science (JSPS) postdoctoral research fellow working under the supervision of Prof. Mukhles Sowwan at the OIST Nanoparticles by Design Unit.

The researchers have provided this image showing their work,

Palladium nanoparticles were deposited on the entire wafer in an evenly distributed fashion, as seen in the background.  They also attached on the surface of the copper oxide wire in the same evenly distributed manner, as seen in the foreground.   On the upper right is a top view of a single palladium nanoparticle photographed with a transmission electron microscope(TEM) which can only produce black and white images. The nanoparticle is made up of columns consisting of palladium atoms stacked on top of each other.  Courtesy OIST

Palladium nanoparticles were deposited on the entire wafer in an evenly distributed fashion, as seen in the background. They also attached on the surface of the copper oxide wire in the same evenly distributed manner, as seen in the foreground.
On the upper right is a top view of a single palladium nanoparticle photographed with a transmission electron microscope(TEM) which can only produce black and white images. The nanoparticle is made up of columns consisting of palladium atoms stacked on top of each other. Courtesy OIST

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

Single CuO nanowires decorated with size-selected Pd nanoparticles for CO sensing in humid atmosphere by Stephan Steinhauer, Vidyadhar Singh, Cathal Cassidy, Christian Gspan, Werner Grogger, Mukhles Sowwan, and Anton Köck. Nanotechnology 2015 Volume 26 Number 17 doi:10.1088/0957-4484/26/17/175502

This paper is behind a paywall.

Patenting a new method for controlling the size and composition of nanoparticles

A research team at the Okinawa Institute of Science and Technology Graduate University (OIST) in Japan has developed and patented a new more precise production technique for nanoparticles, specifically quantum dots. From a Jan. 5, 2014 news item on Nanowerk, (Note:  A link has been removed),

The Nanoparticles by Design Unit at the Okinawa Institute of Science and Technology Graduate University is constantly finding new ways to endow the tiniest of particles with more specific properties. They have developed methods to control the size and chemical composition of nanoparticles, and now they have found a way to control the degree of crystallinity, or the way that atoms align inside the nanoparticles. A nanoparticle’s crystallinity impacts its optical, magnetic, and electrical properties. Professor Mukhles Sowwan and the researchers in his unit Dr. Cathal Cassidy and Vidyadhar Singh have applied for a patent for their method, which describes exactly how to create semiconductor nanoparticles of varying crystallinity.

A Jan. 5, 2015 OIST news release, which originated the news item,  describes the researchers’ work in more detail,

“Most scientists and even companies nowadays are using nanoparticles not optimized for their applications or devices,” explains Sowwan. “We hope, at a certain time, we will optimize the nanoparticles for specific applications.” To start though, the researchers in the Nanoparticles by Design Unit must figure out how to control a few basic characteristics of nanoparticles, such as crystallinity. A crystalline nanoparticle will have all of its atoms aligned in neat rows, while an amorphous nanoparticle will have more disordered atoms. A polycrystalline structure has atoms aligned in groups, which are also known as grains. Crystallinity is responsible for profound differences between products made of the same material. For example, soot is amorphous carbon, or carbon without any crystal grains, while diamonds are crystalline carbon.

“It’s the first time to control the crystallinity and the number of crystallites of very small semiconductor nanoparticle,” Sowwan says, explaining that people have long known how to induce crystallinity in bulk semiconductor materials. But part of the reason why Sowwan can control certain characteristics is because of the experimental method he and his researchers use, based on a modified nanoparticle deposition system. One of the most important features of this system is the possibility to interact with or modify freshly formed semiconductor nanoparticles in flight before reaching a substrate. “That substrate is problematic,” explains Sowwan, “because it is always impacting the properties of the nanoparticle.” Following the steps described in the newly suggested method, nanoscientists expose these nanoparticles in flight to a beam of metal atoms. The metal atoms diffuse onto the surface of the nanoparticles and form metal nanoclusters, just a few nanometers wide, inducing crystallization in the product. The researchers can then selectively remove the metal nanoclusters with plasma cleaning, a fairly simple physical procedure, retaining only the intact semiconductor nanoparticles of desired crystallinity.

The new patent will credit this method to OIST.  “To use this method for commercial purposes, such as engineered nanoparticles in solar cells or for medical bio-imaging, the technology will have to be licensed from OIST,and academic researchers will have to credit us in their research.” Sowwan says this is one of many characteristics he would like to control in order to produce more specialized nanoparticles. At the end of the day, this is one new set of directions in the rulebook of how to customize a nanoparticle.

It’s not clear how much money, if any,  OIST will be charging should other researchers choose to avail themselves of this technology. At present, you can take a look at the patent application which makes for some very interesting reading,

Patent application number: WO 2014141662 A1, Metal Induced Crystallization of Semiconductor Quantum Dots via google

The present invention relates to metal induced crystallization of amorphous semiconductor, and in particular, to metal induced crystallization of amorphous semiconductor small dots and quantum dots.

Control of crystallinity and grain structure has been a central component of advanced materials engineering and metallurgy for centuries, ranging from forging of ancient Japanese katana or swords (Non-Patent Literature No. 1) to modern nano-engineered transistor gate electrodes (Non-patent Literature Nos. 2 and 3). …

My understanding is that this is a US patent.

Animating nanoparticles

It’s always good to find new tools for explaining/describing the nanoscale and this July 28, 2014 news item on Nanowerk, which highlights animation that simulates interactions between nanoparticles, helps to fill the bill,

Panagiotis Grammatikopoulos in the OIST [Okinawa Institute of Science and Technology] Nanoparticles by Design Unit simulates the interactions of particles that are too small to see, and too complicated to visualize. In order to study the particles’ behavior, he uses a technique called molecular dynamics. This means that every trillionth of a second, he calculates the location of each individual atom in the particle based on where it is and which forces apply. He uses a computer program to make the calculations, and then animates the motion of the atoms using visualization software. The resulting animation illuminates what happens, atom-by-atom, when two nanoparticles collide.

A July 25, 2014 OIST news release by Poncie Rutsch, which originated the news item, details the process Grammatikopoulos follows, (Note: A link has been removed)

Grammatikopoulos calls this a virtual experiment. He knows what the atoms in his starting nanoparticles look like. He knows their motion follows the laws of Newtonian physics. His colleagues have seen what the resulting particles look like after collision experiments.  Once his simulation is complete, Grammatikopoulos compares his end products with his colleagues to check his accuracy.

Grammatikopoulos most recently simulated how palladium nanoparticles interact, published in Scientific Reports on July 22, 2014. Palladium is an expensive but highly efficient catalyst that lowers the energy required to start many chemical reactions. Researchers can make palladium even more efficient by designing palladium nanoparticles, which use the same mass of palladium in tinier pieces, increasing surface area. The more surface area a catalyst has, the more effective it is, because there are more active sites where elements can meet and reactions can occur.

However, shrinking a material to only a few nanometers can change some of the properties of that material. For example, all nanoparticles melt at cooler temperatures than they would normally, which changes what happens when two particles collide. Ordinarily, two particles will collide and release a small amount of heat, but the particles remain more or less the same. But when two nanoparticles collide, sometimes the heat released melts the surface of the two particles, and they fuse together.

Grammatikopoulos simulated palladium nanoparticles colliding and fusing at different temperatures. He determined that each time the particles fused, their atoms would start to crystallize into orderly rows and planes. At higher temperatures, the particles fuse into one homogeneous structure. At lower temperatures, the products look like classic snowmen, with a few parts that had crystallized with different orientations.

“The simulation gives you an understanding of physical processes,” said Grammatikopoulos. Before his research, Grammatikopoulos could not explain why all the palladium nanoparticles his lab created had a crystalline structure. Furthermore, he noticed that many palladium nanoparticles grew protrusions, giving the particles a lumpy shape. “Since the protrusions stick out, they bond more easily with other molecules,” Grammatikopoulos explained. “I’m not sure yet if it’s beneficial, but it’s definitely affecting the catalytic properties.”

Here’s an image illustrating the process,

Grammatikopoulos simulated two palladium nanoparticles colliding at different temperatures. The hotter the temperature, the more homogenous the resulting product, and the further the atoms in the particle crystallize. Courtesy: OIST

The news release goes on to explain the impact this information could have,

This study establishes some ground rules and explains certain properties of palladium nanoparticles. Understanding these properties could help design other nanoparticles out of other materials that would rival palladium’s abilities as a catalyst.  Palladium plays a role in thousands of important reactions, from making drugs to creating new biofuels. For example, Prof. Mukhles Sowwan’s Nanoparticles by Design Unit and Prof. Igor Goryanin’s Biological Systems Unit at OIST are working with palladium-catalyzed reactions to improve the efficiency of microbial fuel cells. Better palladium nanoparticles will propel this research forward.

“We need to understand the basic science,” explained Sowwan, who is Grammatikopoulos’ advisor. Sowwan says that the field of nanoscience is only starting to move towards applying the research, because there is still so much to learn about the properties of nanoparticles. “If you build something without understanding the basics,” Sowwan said, “you will not be able to explain the results.”

The researchers have made videos available, here’s a video of palladium crystallization at 300K,

As per the information provided by OIST,

Published on Jul 24, 2014

Grammatikopoulos created this simulation of palladium nanoparticles colliding at 300 Kelvin, or about 27 degrees Celsius. The nanoparticles meet, then fuse, then crystallize in orderly planes.

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

Coalescence-induced crystallisation wave in Pd nanoparticles by Panagiotis Grammatikopoulos, Cathal Cassidy, Vidyadhar Singh, & Mukhles Sowwan. Scientific Reports 4, Article number: 5779 doi:10.1038/srep05779 Published 22 July 2014

This is an  open access paper.