Tag Archives: silicon nanoparticles

Seeing into silicon nanoparticles with ‘mining’ hardware

This was not the mining hardware I expected and it enters the picture after this paragraph which has been excerpted from a February 28, 2018 news item on Nanowerk,

For the first time, researchers developed a three-dimensional dynamic model of an interaction between light and nanoparticles. They used a supercomputer with graphic accelerators for calculations. Results showed that silicon particles exposed to short intense laser pulses lose their symmetry temporarily. Their optical properties become strongly heterogeneous. Such a change in properties depends on particle size, therefore it can be used for light control in ultrafast information processing nanoscale devices. …

A March 2, 2018 ITMO University (Russia) press release (also on EurekAlert), which originated the news item, provides more detail and a mention of ‘cryptocurrency mining’ hardware,

Improvement of computing devices today focuses on increasing information processing speeds. Nanophotonics is one of the sciences that can solve this problem by means of optical devices. Although optical signals can be transmitted and processed much faster than electronic ones, first, it is necessary to learn how to quickly control light on a small scale. For this purpose, one could use metal particles. They are efficient at localizing light, but weaken the signal, causing significant losses. However, dielectric and semiconducting materials, such as silicon, can be used instead of metal.

Silicon nanoparticles are now actively studied by researchers all around the world, including those at ITMO University. The long-term goal of such studies is to create ultrafast, compact optical signal modulators. They can serve as a basis for computers of the future. However, this technology will become feasible only once we understand how nanoparticles interact with light.

Silicon nanoparticles
Silicon nanoparticles

“When a laser pulse hits the particle, a lot of free electrons are formed inside,” explains Sergey Makarov, head of ITMO’s Laboratory of Hybrid Nanophotonics and Optoelectronics. “A region saturated with oppositely charged particles is created. It is usually called electron-hole plasma. Plasma changes optical properties of particles and, up until today, it was believed that it spreads over the whole particle simultaneously, so that the particle’s symmetry is preserved. We demonstrated that this is not entirely true and an even distribution of plasma inside particles is not the only possible scenario.”

Scientists found that the electromagnetic field caused by an interaction between light and particles has a more complex structure. This leads to a light distortion which varies with time. Therefore, the symmetry of particles is disturbed and optical properties become different throughout one particle.

“Using analytical and numerical methods, we were the first to look inside the particle and we proved that the processes taking place there are far more complicated than we thought,” says Konstantin Ladutenko, staff member of ITMO’s International Research Center of Nanophotonics and Metamaterials.  “Moreover, we found that by changing the particle size, we can affect its interaction with the light signal. This means we might be able to predict the signal path in an entire system of nanoparticles.”

In order to create a tool to study processes inside nanoparticles, scientists from ITMO University joined forces with colleagues from Jean Monnet University in France.

Sergey Makarov
Sergey Makarov

We developed analytical methods to determine the size range of the particles and their refractive index which would make a change in optical properties likely. Afterwards, we used powerful computational methods to monitor processes inside particles. Our colleagues performed calculations on a computer with graphics accelerators. Such computers are often used for cryptocurrency mining [emphasis mine]. However, we decided to enrich humanity with new knowledge, rather than enrich ourselves. Besides, bitcoin rate had just started to go down then,” adds Konstantin.

Devices based on these nanoparticles may become basic elements of optical computers, just as transistors are basic elements of electronics today. They will make it possible to distribute and redirect or branch the signal.

“Such asymmetric structures have a variety of applications, but we are focusing on ultra-fast signal processing,” continues Sergey.We now have a powerful theoretical tool which will help us develop light management systems that will operate on a small scale – in terms of both time and space”.

Here’s a little more about ITMO University from its Wikipedia entry (Note: Links have been removed),

ITMO University (Russian: Университет ИТМО) is a large state university in Saint Petersburg and is one of Russia’s National Research Universities.[1] ITMO University is one of 15 Russian universities that were selected to participate in Russian Academic Excellence Project 5-100[2] by the government of the Russian Federation to improve their international competitiveness among the world’s leading research and educational centers.[3]

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

Photogenerated Free Carrier-Induced Symmetry Breaking in Spherical Silicon Nanoparticle by Anton Rudenko, Konstantin Ladutenko, Sergey Makarov, and Tatiana E. Itina.Advanced Optical Materials Vol. 6 Issue 5 DOI: 10.1002/adom.201701153 Version of Record online: 29 JAN 2018

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

This paper is behind a paywall.

Nanomedicine and an enhanced uptake of nanoparticles

It’s nice to know that a step forward has been taken with regard to improving uptake in  nanoparticle-based drug delivery (see my April 27, 2016 posting titled: How many nanoparticle-based drugs does it take to kill a cancer tumour? More than 1% for insight into the difficulties of f nanoparticle-based drug delivery systems).

Here’s the latest move forward in a March 8, 2017 news item on Nanowerk (Note: A link has been removed),

Nanotechnology has become a growing part of medical research in recent years, with scientists feverishly working to see if tiny particles could revolutionize the world of drug delivery.

But many questions remain about how to effectively transport those particles and associated drugs to cells.
In an article published today in Scientific Reports (“Enhanced cellular uptake of size-separated lipophilic silicon nanoparticles”), FSU Associate Professor of Biological Science Steven Lenhert takes a step forward in the understanding of nanoparticles and how they can best be used to deliver drugs.

After conducting a series of experiments, Lenhert and his colleagues found that it may be possible to boost the efficacy of medicine entering target cells via a nanoparticle.

A March 8, 2017 Florida State University news release by Kathleen Haughney, which originated the news item, provides more detail about the research (an international collaboration involving the University of Toronto [Canada] and the Karlsruhe Institute of Technology [Germany]),

“We can enhance how cells take them up and make more drugs more potent,” Lenhert said.

Initially, Lenhert and his colleagues from the University of Toronto and the Karlsruhe Institute of Technology  wanted to see what happened when they encapsulated silicon nanoparticles in liposomes — or small spherical sacs of molecules — and delivered them to HeLa cells, a standard cancer cell model.

The initial goal was to test the toxicity of silicon-based nanoparticles and get a better understanding of its biological activity.

Silicon is a non-toxic substance and has well-known optical properties that allow their nanostructures to appear fluorescent under an infrared camera, where tissue would be nearly transparent. Scientists believe it has enormous potential as a delivery agent for drugs as well as in medical imaging.

But there are still questions about how silicon behaves at such a small size.

“Nanoparticles change properties as they get smaller, so scientists want to understand the biological activity,” Lenhert said. “For example, how does shape and size affect toxicity?”

Scientists found that 10 out of 18 types of the particles, ranging from 1.5 nanometers to 6 nanometers, were significantly more toxic than crude mixtures of the material.

At first, scientists believed this could be a setback, but they then discovered the reason for the toxicity levels. The more toxic fragments also had enhanced cellular uptake.

That information is more valuable long term, Lenhert said, because it means they could potentially alter nanoparticles to enhance the potency of a given therapeutic.

The work also paves the way for researchers to screen libraries of nanoparticles to see how cells react.

“This is an essential step toward the discovery of novel nanotechnology based therapeutics,” Lenhert said. “There’s big potential here for new therapeutics, but we need to be able to test everything first.”

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

Enhanced cellular uptake of size-separated lipophilic silicon nanoparticles by Aubrey E. Kusi-Appiah, Melanie L. Mastronardi, Chenxi Qian, Kenneth K. Chen, Lida Ghazanfari, Plengchart Prommapan, Christian Kübel, Geoffrey A. Ozin, & Steven Lenhert. Scientific Reports 7, Article number: 43731 (2017) doi:10.1038/srep43731 Published online: 08 March 2017

This paper is open access.

The Swiss come to a better understanding of nanomaterials

Just to keep things interesting, after the report suggesting most of the information that the OECD (Organization for Economic Cooperation and Development) has on nanomaterials is of little value for determining risk (see my April 5, 2017 posting for more) the Swiss government has released a report where they claim an improved understanding of nanomaterials than they previously had due to further research into the matter. From an April 6, 2017 news item on Nanowerk,

In the past six years, the [Swiss] National Research Programme “Opportunities and Risks of Nanomaterials” (NRP 64) intensively studied the development, use, behaviour and degradation of engineered nanomaterials, including their impact on humans and on the environment.

Twenty-three research projects on biomedicine, the environment, energy, construction materials and food demonstrated the enormous potential of engineered nanoparticles for numerous applications in industry and medicine. Thanks to these projects we now know a great deal more about the risks associated with nanomaterials and are therefore able to more accurately determine where and how they can be safely used.

An April 6, 2017 Swiss National Science Foundation press release, which originated the news item, expands on the theme,

“One of the specified criteria in the programme was that every project had to examine both the opportunities and the risks, and in some cases this was a major challenge for the researchers,” explains Peter Gehr, President of the NRP 64 Steering Committee.

One development that is nearing industrial application concerns a building material strengthened with nanocellulose that can be used to produce a strong but lightweight insulation material. Successful research was also carried out in the area of energy, where the aim was to find a way to make lithium-ion batteries safer and more efficient.

Promising outlook for nanomedicine

A great deal of potential is predicted for the field of nanomedicine. Nine of the 23 projects in NRP 64 focused on biomedical applications of nanoparticles. These include their use for drug delivery, for example in the fight against viruses, or as immune modulators in a vaccine against asthma. Another promising application concerns the use of nanomagnets for filtering out harmful metallic substances from the blood. One of the projects demonstrated that certain nanoparticles can penetrate the placenta barrier, which points to potential new therapy options. The potential of cartilage and bone substitute materials based on nanocellulose or nanofibres was also studied.

The examination of potential health risks was the focus of NRP 64. A number of projects examined what happens when nanoparticles are inhaled, while two focused on ingestion. One of these investigated whether the human gut is able to absorb iron more efficiently if it is administered in the form of iron nanoparticles in a food additive, while the other studied silicon nanoparticles as they occur in powdered condiments. It was ascertained that further studies will be required in order to determine the doses that can be used without risking an inflammatory reaction in the gut.

What happens to engineered nanomaterials in the environment?

The aim of the seven projects focusing on environmental impact was to gain a better understanding of the toxicity of nanomaterials and their degradability, stability and accumulation in the environment and in biological systems. Here, the research teams monitored how engineered nanoparticles disseminate along their lifecycle, and where they end up or how they can be discarded.

One of the projects established that 95 per cent of silver nanoparticles that are washed out of textiles are collected in sewage treatment plants, while the remaining particles end up in sewage sludge, which in Switzerland is incinerated. In another project a measurement device was developed to determine how aquatic microorganisms react when they come into contact with nanoparticles.

Applying results and making them available to industry

“The findings of the NRP 64 projects form the basis for a safe application of nanomaterials,” says Christoph Studer from the Federal Office of Public Health. “It has become apparent that regulatory instruments such as testing guidelines will have to be adapted at both national and international level.” Studer has been closely monitoring the research programme in his capacity as the Swiss government’s representative in NRP 64. In this context, the precautionary matrix developed by the government is an important instrument by means of which companies can systematically assess the risks associated with the use of nanomaterials in their production processes.

The importance of standardised characterisation and evaluation of engineered nanomaterials was highlighted by the close cooperation among researchers in the programme. “The research network that was built up in the framework of NRP 64 is functioning smoothly and needs to be further nurtured,” says Professor Bernd Nowack from Empa, who headed one of the 23 projects.

The results of NRP 64 show that new key technologies such as the use of nanomaterials need to be closely monitored through basic research due to the lack of data on its long-term effects. As Peter Gehr points out, “We now know a lot more about the risks of nanomaterials and how to keep them under control. However, we need to conduct additional research to learn what happens when humans and the environment are exposed to engineered nanoparticles over longer periods, or what happens a long time after a one-off exposure.”

You can find out more about the Opportunities and Risks of Nanomaterials; National Research Programme (NRP 64) here.

Small, soft, and electrically functional: an injectable biomaterial

This development could be looked at as a form of synthetic biology without the genetic engineering. From a July 1, 2016 news item on ScienceDaily,

Ideally, injectable or implantable medical devices should not only be small and electrically functional, they should be soft, like the body tissues with which they interact. Scientists from two UChicago labs set out to see if they could design a material with all three of those properties.

The material they came up with, published online June 27, 2016, in Nature Materials, forms the basis of an ingenious light-activated injectable device that could eventually be used to stimulate nerve cells and manipulate the behavior of muscles and organs.

“Most traditional materials for implants are very rigid and bulky, especially if you want to do electrical stimulation,” said Bozhi Tian, an assistant professor in chemistry whose lab collaborated with that of neuroscientist Francisco Bezanilla on the research.

The new material, in contrast, is soft and tiny — particles just a few micrometers in diameter (far less than the width of a human hair) that disperse easily in a saline solution so they can be injected. The particles also degrade naturally inside the body after a few months, so no surgery would be needed to remove them.

A July 1, 2016 University of Chicago news release (also on EurekAlert) by , which originated the news item, provides more detail,

Each particle is built of two types of silicon that together form a structure full of nano-scale pores, like a tiny sponge. And like a sponge, it is squishy — a hundred to a thousand times less rigid than the familiar crystalline silicon used in transistors and solar cells. “It is comparable to the rigidity of the collagen fibers in our bodies,” said Yuanwen Jiang, Tian’s graduate student. “So we’re creating a material that matches the rigidity of real tissue.”

The material constitutes half of an electrical device that creates itself spontaneously when one of the silicon particles is injected into a cell culture, or, eventually, a human body. The particle attaches to a cell, making an interface with the cell’s plasma membrane. Those two elements together — cell membrane plus particle — form a unit that generates current when light is shined on the silicon particle.

“You don’t need to inject the entire device; you just need to inject one component,” João L. Carvalho-de-Souza , Bezanilla’s postdoc said. “This single particle connection with the cell membrane allows sufficient generation of current that could be used to stimulate the cell and change its activity. After you achieve your therapeutic goal, the material degrades naturally. And if you want to do therapy again, you do another injection.”

The scientists built the particles using a process they call nano-casting. They fabricate a silicon dioxide mold composed of tiny channels — “nano-wires” — about seven nanometers in diameter (less than 10,000 times smaller than the width of a human hair) connected by much smaller “micro-bridges.” Into the mold they inject silane gas, which fills the pores and channels and decomposes into silicon.

And this is where things get particularly cunning. The scientists exploit the fact the smaller an object is, the more the atoms on its surface dominate its reactions to what is around it. The micro-bridges are minute, so most of their atoms are on the surface. These interact with oxygen that is present in the silicon dioxide mold, creating micro-bridges made of oxidized silicon gleaned from materials at hand. The much larger nano-wires have proportionately fewer surface atoms, are much less interactive, and remain mostly pure silicon. [I have a note regarding ‘micro’ and ‘nano’ later in this posting.]

“This is the beauty of nanoscience,” Jiang said. “It allows you to engineer chemical compositions just by manipulating the size of things.”

Web-like nanostructure

Finally, the mold is dissolved. What remains is a web-like structure of silicon nano-wires connected by micro-bridges of oxidized silicon that can absorb water and help increase the structure’s softness. The pure silicon retains its ability to absorb light.

Transmission electron microscopy image shows an ordered nanowire array. The 100-nanometer scale bar is 1,000 times narrower than a hair. Courtesy of Tian Lab

Transmission electron microscopy image shows an ordered nanowire array. The 100-nanometer scale bar is 1,000 times narrower than a hair. Courtesy of
Tian Lab

The scientists have added the particles onto neurons in culture in the lab, shone light on the particles, and seen current flow into the neurons which activates the cells. The next step is to see what happens in living animals. They are particularly interested in stimulating nerves in the peripheral nervous system that connect to organs. These nerves are relatively close to the surface of the body, so near-infra-red wavelength light can reach them through the skin.

Tian imagines using the light-activated devices to engineer human tissue and create artificial organs to replace damaged ones. Currently, scientists can make engineered organs with the correct form but not the ideal function.

To get a lab-built organ to function properly, they will need to be able to manipulate individual cells in the engineered tissue. The injectable device would allow a scientist to do that, tweaking an individual cell using a tightly focused beam of light like a mechanic reaching into an engine and turning a single bolt. The possibility of doing this kind of synthetic biology without genetic engineering [emphasis mine] is enticing.

“No one wants their genetics to be altered,” Tian said. “It can be risky. There’s a need for a non-genetic system that can still manipulate cell behavior. This could be that kind of system.”

Tian’s graduate student Yuanwen Jiang did the material development and characterization on the project. The biological part of the collaboration was done in the lab of Francisco Bezanilla, the Lillian Eichelberger Cannon Professor of Biochemistry and Molecular Biology, by postdoc João L. Carvalho-de-Souza. They were, said Tian, the “heroes” of the work.

I was a little puzzled about the use of the word ‘micro’ in a context suggesting it was smaller than something measured at the nanoscale. Dr. Tian very kindly cleared up my confusion with this response in a July 4, 2016 email,

In fact, the definition of ‘micro’ and ’nano’ have been quite ambiguous in literature. For example, microporous materials (e.g., zeolite) usually refer to materials with pore sizes of less than 2 nm — this is defined based on IUPAC [International Union of Pure and Applied Chemistry] definition (http://goldbook.iupac.org/M03853.html). We used ‘micro-bridges’ because they come from the ‘micropores’ in the original template.

Thank you Dr. Tian for that very clear reply and Steve Koppes for forwarding my request to Dr. Tian!

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

Heterogeneous silicon mesostructures for lipid-supported bioelectric interfaces by Yuanwen Jiang, João L. Carvalho-de-Souza, Raymond C. S. Wong, Zhiqiang Luo, Dieter Isheim, Xiaobing Zuo, Alan W. Nicholls, Il Woong Jung, Jiping Yue, Di-Jia Liu, Yucai Wang, Vincent De Andrade, Xianghui Xiao, Luizetta Navrazhnykh, Dara E. Weiss, Xiaoyang Wu, David N. Seidman, Francisco Bezanilla, & Bozhi Tian. Nature Materials (2016)  doi:10.1038/nmat4673 Published online 27 June 2016

This paper is behind a paywall.

I gather animal testing will be the next step as they continue to develop this exciting technology. Good luck!

Smallest known reference material issued

I betray some of my occupational origins with this comment; a reference material is not necessarily a reference book. A Sept. 25, 2014, news item on Nanowerk clarifies the use of the term reference material in relationship to the US National Institute of Standards and technology while describing a new set designed for use at the nanoscale,

If it’s true that good things come in small packages, then the National Institute of Standards and Technology (NIST) can now make anyone working with nanoparticles very happy. NIST recently issued Reference Material (RM) 8027, the smallest known reference material ever created for validating measurements of these man-made, ultrafine particles between 1 and 100 nanometers in size.

RM 8027 consists of five hermetically sealed ampoules containing one milliliter of silicon nanoparticles—all certified to be close to 2 nanometers in diameter—suspended in toluene.

A Sept. 24, 2014 NIST news release (also on EurekAlert but dated Sept. 25, 2014), which originated the news item, provides a more detailed description and purchasing instructions

To yield the appropriate sizes for the new RM, the nanocrystals are etched from a silicon wafer, separated using ultrasound and then stabilized within an organic shell. Particle size and chemical composition are determined by dynamic light scattering, analytical centrifugation, electron microscopy and inductively coupled plasma mass spectrometry (ICP-MS), a powerful technique that can measure elements at concentrations as low as several parts per billion.

“For anyone working with nanomaterials at dimensions 5 nanometers or less, our well-characterized nanoparticles can ensure confidence that their measurements are accurate,” says NIST research chemist Vytas Reipa, leader of the team that developed and qualified RM 8027.

Silicon nanoparticles such as those in RM 8027 are being studied as alternative semiconductor materials for next-generation photovoltaic solar cells and solid-state lighting, and as a replacement for carbon in the cathodes of lithium batteries. Another potential application comes from the fact that silicon crystals at dimensions of 5 nanometers or less fluoresce under ultraviolet light. Because of this property, silicon nanoparticles may one day serve as easily detectable “tags” for tracking nanosized substances in biological, environmental or other dynamic systems.

RM 8027 maybe ordered from the NIST Standard Reference Materials Program by phone, (301) 975-2200; by fax, (301) 948-3730; or online at http://www.nist.gov/srm.

NIST has provided an illustration,

Caption: A structural model of a typical silicon nanocrystal (yellow) was stabilized within an organic shell of cyclohexane (blue). Credit: NIST

Caption: A structural model of a typical silicon nanocrystal (yellow) was stabilized within an organic shell of cyclohexane (blue).
Credit: NIST

NIST also supplied this image,

Caption: This is a high-resolution transmission electron microscope photograph of a single silicon nanoparticle. Credit: NIST

Caption: This is a high-resolution transmission electron microscope photograph of a single silicon nanoparticle. Credit: NIST

As is common with the images that scientists actually use in their work, the colour palette is gray.