Tag Archives: Russia

The birth of carbon nanotubes (CNTs): a history

There is a comprehensive history of the carbon nanotube stretching back to prehistory and forward to recent times in a June 3, 2016 Nanowerk Spotlight article by C.K. Nisha and Yashwant Mahajan of the Center of Knowledge Management of Nanoscience & Technology (CKMNT) in India. The authors provide an introduction explaining the importance of CNTs,

Carbon nanotubes (CNTs) have been acknowledged as the material of the 21st century. They possess unique combination of extraordinary mechanical, electronic, transport, electrical and optical, properties and nanoscale sizes making them suitable for a variety of applications ranging from engineering, electronics, optoelectronics, photonics, space, defence industry, medicine, molecular and biological systems and so on and so forth. Worldwide demand for CNTs is increasing at a rapid pace as applications for the material are being matured.

According to MarketsandMarkets (M&M), the global market for carbon nanotubes in 2015 was worth about $2.26 billion1; an increase of 45% from 2009 (i.e. ~ $ 1.24 billion). This was due to the growing potential of CNTs in electronics, plastics and energy storage applications and the projected market of CNTs is expected to be around $ 5.64 billion in 2020.

In view of the scientific and technological potential of CNTs, it is of immense importance to know who should be credited for their discovery. In the present article, we have made an attempt to give a glimpse into the discovery and early history of this fascinating material for our readers. Thousands of papers are being published every year on CNTs or related areas and most of these papers give credit for the discovery of CNTs to Sumio Iijima of NEC Corporation, Japan, who, in 1991, published a ground-breaking paper in Nature reporting the discovery of multi-walled carbon nanotubes (MWCNTs)2. This paper has been cited over 27,105 times in the literature (as on January 12, 2016, based on Scopus database). This discovery by Iijima has triggered an avalanche of scientific publications and catapulted CNTs onto the global scientific stage.

Nisha and Mahajan then prepare to take us back in time,

In a guest editorial for the journal Carbon, Marc Monthioux and Vladimir L. Kuznetsov3 have tried to clear the air by describing the chronological events that led to the discovery of carbon nanotubes. As one delves deeper into the history of carbon nanotubes, it becomes more apparent that the origin of CNTs could be even pre-historic in nature.

Recently, Ponomarchuk et al from Russia have reported the presence micro and nano carbon tubes in igneous rocks formed about 250 million years ago4-7. They suggested the possibility of formation of carbon nanotubes during the magmatic processes. It is presumed that the migration of hydrocarbon fluids through the residual melt of the rock groundmass created gas-saturated areas (mostly CH4, CO2, CO) in which condensation and decomposition of hydrocarbon in presence of metal elements resulted in the formation of micro and sub-micron carbon tubes.

Another most compelling evidence of pre-historic naturally occurring carbon nanotubes (MWCNTs) is based on the TEM studies carried out by Esquivel and Murr8 that analyzed 10,000-year-old Greenland ice core samples and it was suggested that probably they could have been formed during combustion of natural gas/methane during natural processes.

However, the validity of this evidence is questionable owing to the lack of clear high-resolution TEM images, high-quality diffraction patterns or Raman spectroscopy data. In addition, [an]other interesting possibility is that the carbon nanotubes could have been directly formed by the transformation of naturally occurring C60 fullerenes in nature without the assistance of man, given the right conditions prevail. Suchanek et al.,9 have actually demonstrated this thesis, under the laboratory environment, by transforming C60 fullerenes into CNTs under hydrothermal conditions.

There is a large body of evidence in literature about the existence of naturally occurring fullerenes in nature, e.g., coal, carboneous rocks, interstellar media, etc. Since the above experiments were conducted under the simulated geological environment, their results imply that CNTs may form in natural hydrothermal environment.

This hypothesis was further corroborated by Velasco-Santos and co-workers10, when they reported the presence of CNTs in a coal–petroleum mix obtained from an actual oil well, identified by the PEMEX (the Mexican Petroleum Company) as P1, which is located in Mexico’s southeast shore. TEM studies revealed that the coal-petroleum mix contained predominantly end-capped CNTs that are nearly 2 µm long with outer diameter varying between few to several tenths of nanometers.

There’s another study supporting the notion that carbon nanotubes may be formed naturally,

In yet another study, researchers from Germany11 have synthesized carbon nanotubes using igneous rock from Mount Etna lava as both support and catalyst. The naturally occurring iron oxide particles present in Etna lava rock make it an ideal material for growing and immobilizing nanocarbons.

When a mixture of ethylene and hydrogen were passed over the pulverized rocks reduced in a hydrogen atmosphere at 700°C, the iron particles catalyzed the decomposition of ethylene to elemental carbon, which gets deposited on the lava rock in the form of tiny tubes and fibers.
This study showed that if a carbon source is available, CNTs/CNFs can grow on a mineral at moderate temperatures, which directs towards the possibilities of carbon nanotube formation in active suboceanic volcanos or even in interstellar space where methane, atomic hydrogen, carbon oxides, and metallic iron are present.

This fascinating and informative piece was originally published in the January 2016 edition of Nanotech Insights (CKMNT newsletter; scroll down) and can be found there although it may be more easily accessible as the June 3, 2016 Nanowerk Spotlight article where it extends over five (Nanowerk) pages and has a number of embedded images along with an extensive list of references at the end.


Combining chitosan, agarose, and protein gelatine with clay nanotubes to create scaffolds for tissue engineering

Russian scientists have published work on clay nanotube-bipolymer composite scaffolds according to an April 29, 2016 news item on ScienceDaily,

Scientists combined three biopolymers, chitosan and agarose (polysaccharides), and a protein gelatine, as the materials to produce tissue engineering scaffolds and demonstrated the enhancement of mechanical strength (doubled pick load), higher water uptake and thermal properties in chitosan-gelatine-agarose hydrogels doped with halloysite [a clay mineral and a naturally occurring nanotube].

An April 29, 2016 Kazan Federal University (Russia) press release on EurekAlert, which originated the news item, provides more detail and context,

The fabrication of a prototype tissue having functional properties close to the natural ones is crucial for effective transplantation. Tissue engineering scaffolds are typically used as supports which allow cells to form tissue-like structures essentially required for the correct functioning of the cells under the conditions close to the three-dimensional tissue.

Chitosan, a natural biodegradable and chemically versatile biopolymer, has been effectively used in antibacterial, antifungal, anti-tumour and immunostimulating formulations. To overcome the disadvantages of pure chitosan scaffolds such as mechanical fragility and low biological resistance, chitosan scaffolds are typically doped with other supporting compounds which allow for mechanical strengthening, thus yielding ?omposite biologically resistant scaffolds.

Agarose is a galactose-based backbone polysaccharide isolated from red algae, having remarkable mechanical properties which are useful in the design of tissue engineering scaffolds.

Gelatine is formed from collagen by hydrolysis (breaking the triple-helix structure into single-strand molecules) and has a number of advantages over its precursor. It is less immunogenic compared with collagen and it retains informational signal sequences promoting cell adhesion, migration, differentiation and proliferation.

The surface irregularities of the scaffold pores due to the insoluble nanosized components promote the best adhesion of the cells on scaffold materials, while the nanoparticle fillers increase the composites’ strength. Thus, researchers doped halloysite nanotubes into a chitosan-agarose-gelatine matrix to design the implantable 3D cell scaffolds.

The resulting scaffolds demonstrate the shape memory upon deformation and have the porous structure suitable for cell adhesion and proliferation which is essential for artificial tissue fabrication. Macroscopic observations have confirmed that all the samples of scaffolds exhibited the sponge-like behaviour with the shape memory and shape reconstitution after deformation both in wet and dry states.

The swelling experiments indicated that the addition of halloysite can greatly improve the hydrophilicity and wetting of composite scaffolds. The incorporation of halloysite nanotubes into the scaffolds increases the water uptake and subsequently improves the biocompatibility. The intrinsic properties of halloysite nanotubes can be used for further improving the biocompatibility of scaffolds by the loading and sustained release of different bioactive compounds. This opens the prospect for fabrication of scaffolds with defined properties for directed differentiation of cells on matrixes due to gradual release of differentiation factors.

Experiments on two types of human cancer cells (A549 and Hep3B) show that in vitro cell adhesion and proliferation on the nanocomposites occur without changes in viability and cytoskeleton formation.

Further in vivo biocompatibility and biodegradability evaluation in rats has confirmed that the scaffolds promote the formation of novel blood vessels around the implantation sites. The scaffolds show excellent resorption within six weeks after implantation in rats. Neo-vascularization observed in newly formed connective tissue placed near the scaffold allows for the complete restoration of blood flow.

The results obtained indicate that the halloysite doped scaffolds are biocompatible as demonstrated both in vitro and in vivo. In addition, they confirm the great potential of chitosan-agarose-gelatine nanocomposite porous scaffolds doped with halloysite in tissue engineering with potential for sustained nanotube drug delivery.

For anyone interested about drug delivery and nanoparticles, there’s some interesting research profiled in my April 27, 2016 posting which describes how very few nanoparticles are actually delivered to specific sites.

Getting back to the regular program, here’s a link to and a citation for the paper on scaffolds and clay nanotubes,

Clay nanotube–biopolymer composite scaffolds for tissue engineering by Ekaterina A. Naumenko, Ivan D. Guryanov, Raghuvara Yendluri, Yuri M. Lvova, and Rawil F. Fakhrullin. Nanoscale, 2016,8, 7257-7271 DOI: 10.1039/C6NR00641H First published online 01 Mar 2016

This paper is behind a paywall.

Greece and Russia agree to cooperate on quantum and nanotechnology research

I don’t often get a chance to feature Greece here but an April 4, 2016 news item on tornos news (and also on ANAmpa: Athens News Agency [and] Macedonian Press Agency) provides an opportunity,

Greece’s Alternate Minister for Research and Innovation Costas Fotakis and Russian Federation Deputy Minister for Education and Science Ludmila Ogorodova on Friday [April 1, 2016] signed an agreement for cooperation between the two countries in specialist new technologies, such as quantum technology, nanotechnology and related areas.

According to an announcement, the agreement covers four innovative applications in quantum nano-electronics, nanophotonics, quantum information-communication and metamaterials. It extends an invitation to research and technology centres, universities and even public and private research companies to submit proposals in the area of quantum technologies by the end of next June. It envisages financing of up to one million euros in each of the four proposed areas, for programmes to be implemented over 24-36 months.

In spite of the difficult conditions created by the economic crisis, Greece has research centres that have achieved international acclaim and excellence in the emerging field of quantum technology,

So it seems Greece is supplying the quantum expertise and Russia the nanotechnology expertise. It’s a bit surprising that Anatoly Chubais isn’t mentioned since every reference that I’ve ever seen to Russian nanotechnology includes his name as the head of Russia’s state-funded RUSNANO (Russian Nanotechnology Corporation).

Plastic memristors for neural networks

There is a very nice explanation of memristors and computing systems from the Moscow Institute of Physics and Technology (MIPT). First their announcement, from a Jan. 27, 2016 news item on ScienceDaily,

A group of scientists has created a neural network based on polymeric memristors — devices that can potentially be used to build fundamentally new computers. These developments will primarily help in creating technologies for machine vision, hearing, and other machine sensory systems, and also for intelligent control systems in various fields of applications, including autonomous robots.

The authors of the new study focused on a promising area in the field of memristive neural networks – polymer-based memristors – and discovered that creating even the simplest perceptron is not that easy. In fact, it is so difficult that up until the publication of their paper in the journal Organic Electronics, there were no reports of any successful experiments (using organic materials). The experiments conducted at the Nano-, Bio-, Information and Cognitive Sciences and Technologies (NBIC) centre at the Kurchatov Institute by a joint team of Russian and Italian scientists demonstrated that it is possible to create very simple polyaniline-based neural networks. Furthermore, these networks are able to learn and perform specified logical operations.

A Jan. 27, 2016 MIPT press release on EurekAlert, which originated the news item, offers an explanation of memristors and a description of the research,

A memristor is an electric element similar to a conventional resistor. The difference between a memristor and a traditional element is that the electric resistance in a memristor is dependent on the charge passing through it, therefore it constantly changes its properties under the influence of an external signal: a memristor has a memory and at the same time is also able to change data encoded by its resistance state! In this sense, a memristor is similar to a synapse – a connection between two neurons in the brain that is able, with a high level of plasticity, to modify the efficiency of signal transmission between neurons under the influence of the transmission itself. A memristor enables scientists to build a “true” neural network, and the physical properties of memristors mean that at the very minimum they can be made as small as conventional chips.

Some estimates indicate that the size of a memristor can be reduced up to ten nanometers, and the technologies used in the manufacture of the experimental prototypes could, in theory, be scaled up to the level of mass production. However, as this is “in theory”, it does not mean that chips of a fundamentally new structure with neural networks will be available on the market any time soon, even in the next five years.

The plastic polyaniline was not chosen by chance. Previous studies demonstrated that it can be used to create individual memristors, so the scientists did not have to go through many different materials. Using a polyaniline solution, a glass substrate, and chromium electrodes, they created a prototype with dimensions that, at present, are much larger than those typically used in conventional microelectronics: the strip of the structure was approximately one millimeter wide (they decided to avoid miniaturization for the moment). All of the memristors were tested for their electrical characteristics: it was found that the current-voltage characteristic of the devices is in fact non-linear, which is in line with expectations. The memristors were then connected to a single neuromorphic network.

A current-voltage characteristic (or IV curve) is a graph where the horizontal axis represents voltage and the vertical axis the current. In conventional resistance, the IV curve is a straight line; in strict accordance with Ohm’s Law, current is proportional to voltage. For a memristor, however, it is not just the voltage that is important, but the change in voltage: if you begin to gradually increase the voltage supplied to the memristor, it will increase the current passing through it not in a linear fashion, but with a sharp bend in the graph and at a certain point its resistance will fall sharply.

Then if you begin to reduce the voltage, the memristor will remain in its conducting state for some time, after which it will change its properties rather sharply again to decrease its conductivity. Experimental samples with a voltage increase of 0.5V hardly allowed any current to pass through (around a few tenths of a microamp), but when the voltage was reduced by the same amount, the ammeter registered a figure of 5 microamps. Microamps are of course very small units, but in this case it is the contrast that is most significant: 0.1 μA to 5 μA is a difference of fifty times! This is more than enough to make a clear distinction between the two signals.

After checking the basic properties of individual memristors, the physicists conducted experiments to train the neural network. The training (it is a generally accepted term and is therefore written without inverted commas) involves applying electric pulses at random to the inputs of a perceptron. If a certain combination of electric pulses is applied to the inputs of a perceptron (e.g. a logic one and a logic zero at two inputs) and the perceptron gives the wrong answer, a special correcting pulse is applied to it, and after a certain number of repetitions all the internal parameters of the device (namely memristive resistance) reconfigure themselves, i.e. they are “trained” to give the correct answer.

The scientists demonstrated that after about a dozen attempts their new memristive network is capable of performing NAND logical operations, and then it is also able to learn to perform NOR operations. Since it is an operator or a conventional computer that is used to check for the correct answer, this method is called the supervised learning method.

Needless to say, an elementary perceptron of macroscopic dimensions with a characteristic reaction time of tenths or hundredths of a second is not an element that is ready for commercial production. However, as the researchers themselves note, their creation was made using inexpensive materials, and the reaction time will decrease as the size decreases: the first prototype was intentionally enlarged to make the work easier; it is physically possible to manufacture more compact chips. In addition, polyaniline can be used in attempts to make a three-dimensional structure by placing the memristors on top of one another in a multi-tiered structure (e.g. in the form of random intersections of thin polymer fibers), whereas modern silicon microelectronic systems, due to a number of technological limitations, are two-dimensional. The transition to the third dimension would potentially offer many new opportunities.

The press release goes to explain what the researchers mean when they mention a fundamentally different computer,

The common classification of computers is based either on their casing (desktop/laptop/tablet), or on the type of operating system used (Windows/MacOS/Linux). However, this is only a very simple classification from a user perspective, whereas specialists normally use an entirely different approach – an approach that is based on the principle of organizing computer operations. The computers that we are used to, whether they be tablets, desktop computers, or even on-board computers on spacecraft, are all devices with von Neumann architecture; without going into too much detail, they are devices based on independent processors, random access memory (RAM), and read only memory (ROM).

The memory stores the code of a program that is to be executed. A program is a set of instructions that command certain operations to be performed with data. Data are also stored in the memory* and are retrieved from it (and also written to it) in accordance with the program; the program’s instructions are performed by the processor. There may be several processors, they can work in parallel, data can be stored in a variety of ways – but there is always a fundamental division between the processor and the memory. Even if the computer is integrated into one single chip, it will still have separate elements for processing information and separate units for storing data. At present, all modern microelectronic systems are based on this particular principle and this is partly the reason why most people are not even aware that there may be other types of computer systems – without processors and memory.

*) if physically different elements are used to store data and store a program, the computer is said to be built using Harvard architecture. This method is used in certain microcontrollers, and in small specialized computing devices. The chip that controls the function of a refrigerator, lift, or car engine (in all these cases a “conventional” computer would be redundant) is a microcontroller. However, neither Harvard, nor von Neumann architectures allow the processing and storage of information to be combined into a single element of a computer system.

However, such systems do exist. Furthermore, if you look at the brain itself as a computer system (this is purely hypothetical at the moment: it is not yet known whether the function of the brain is reducible to computations), then you will see that it is not at all built like a computer with von Neumann architecture. Neural networks do not have a specialized computer or separate memory cells. Information is stored and processed in each and every neuron, one element of the computer system, and the human brain has approximately 100 billion of these elements. In addition, almost all of them are able to work in parallel (simultaneously), which is why the brain is able to process information with great efficiency and at such high speed. Artificial neural networks that are currently implemented on von Neumann computers only emulate these processes: emulation, i.e. step by step imitation of functions inevitably leads to a decrease in speed and an increase in energy consumption. In many cases this is not so critical, but in certain cases it can be.

Devices that do not simply imitate the function of neural networks, but are fundamentally the same could be used for a variety of tasks. Most importantly, neural networks are capable of pattern recognition; they are used as a basis for recognising handwritten text for example, or signature verification. When a certain pattern needs to be recognised and classified, such as a sound, an image, or characteristic changes on a graph, neural networks are actively used and it is in these fields where gaining an advantage in terms of speed and energy consumption is critical. In a control system for an autonomous flying robot every milliwatt-hour and every millisecond counts, just in the same way that a real-time system to process data from a collider detector cannot take too long to “think” about highlighting particle tracks that may be of interest to scientists from among a large number of other recorded events.

Bravo to the writer!

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

Hardware elementary perceptron based on polyaniline memristive devices by V.A. Demin. V. V. Erokhin, A.V. Emelyanov, S. Battistoni, G. Baldi, S. Iannotta, P.K. Kashkarov, M.V. Kovalchuk. Organic Electronics Volume 25, October 2015, Pages 16–20 doi:10.1016/j.orgel.2015.06.015

This paper is behind a paywall.

A Russia-China high technology investment fund announced

My Sept. 12, 2014 posting mentioned a proposed joint China-Russia nanotechnology investment fund which has now been realized (and changed somewhat). From a Jan. 19, 2016 news item on sputniknews.com,

Russia’s Rusnano nanotechnology company has established a $500-million joint investment fund with the Chinese Zhongrong International Trust, Rusnano CEO Anatoly Chubais said Tuesday.

The agreement between the companies was signed by Chubais and Zhongrong International Trust Chairman Fang Tao, the statement by Rusnano confirmed.

“Zhongrong is one of the largest financial institutes in the Asia-Pacific region that specializes in private equity and financing of large-scale innovative projects… Our partnership is aimed at the creation of new competitive products with the prospect of their launch both in Russia and China, as well as worldwide,” Chubais said, as quoted by Rusnano’s press center.

A Jan. 19, 2016 RUSNANO press release, which originated the news item, provides more details abut the deal and about RUSNANO (Note: A link has been removed),

At the first stage, the RUSNANO Zhongrong United Investment Fund will have $500 mln of capital under management. The Partners of the Fund, RUSNANO Group and Zhongrong Trust International Co., LTD. (Zhongrong), will provide their equity investments in equal portions and establish a joint management company.

The Fund’s investment focus will be concentrated on projects in the growth stage aimed at application, development, and transfer of high technologies (related to electric power industry (including RES), oil and gas industry, as well as microelectronics and biotechnologies) to Russia. It is envisaged that investments into the projects and project companies will be effected on the territory of Russia (not less than 70 %), China, and other countries.

RUSNANO was founded as an open joint stock company in March 2011, through reorganization of state corporation Russian Corporation of Nanotechnologies. RUSNANO is instrumental in realizing government policies for nanoindustry growth, investing in financially effective high-technology projects that guarantee the development of new manufacturing within the Russian Federation. The company invests in nanotechnology companies directly and through investment funds. Its primary investment focus is in electronics, optoelectronics and telecommunications, healthcare and biotechnology, metallurgy and metalwork, energy, mechanical engineering and instrument making, construction and industrial materials, and chemicals and petrochemicals. The Government of the Russian Federation owns 100 percent of the shares in RUSNANO.

Work to establish nanotechnology infrastructure and carry out educational programs is fulfilled by RUSNANO’s Fund for Infrastructure and Educational Programs, which was also established during the reorganization of the Russian Corporation of Nanotechnologies.

Management of the investment assets of RUSNANO are carried out by a limited liability company established in December 2013, RUSNANO Asset Management. Anatoly Chubais is chairman of its Executive Board.

Presumably, the amount is in US dollars (USD). In 2014 when I first stumbled across an English language media announcement about this fund, China was considering ways to make its own currency (Renmibis) an international standard (mentioned in the Sept. 12, 2014 posting). Of course, China’s recent stock market collapse (a Jan. 18, 2016 CNN news article by Andrew Stevens with
Jessie Jiang and Shen Lu provides more details and insight into the collapse) must have been a setback for those currency plans but it’s interesting to see China has pushed ahead with this investment fund.

Ceramic firefighting foam: better at extinguishing fires and nontoxic

A Dec. 14, 2015 news item on Nanowerk announces a new ceramic firefighting foam developed in Russia,

A team of chemists from ITMO University, in collaboration with research company SOPOT, has developed a novel type of firefighting foam based on inorganic silica nanoparticles. The new foam beats existing analogues in fire extinguishing capacity, thermal and mechanical stability and biocompatibility.

A Dec. 14, 2015 ITMO University press release on EurekAlert, which originated the news item, provides more details,

Fighting large-scale fires usually involves firefighting foams based on synthetic substances, such as prefluorinated surfactants, that, despite their effectiveness, are extremely toxic for living organisms. Complete biodegradation of such foams can last for more than 200 years [emphasis mine], with residues quickly penetrating deep into soil and surface water. This leads to the the accumulation of toxic elements in living organisms, such as plants, animals and men. Many countries have declined the use of such fire extinguishing agents or opted for reducing the production of such substances despite the absence of any decent alternatives.

A group of scientists from the International Laboratory of Advanced Materials and Technologies (SCAMT) at ITMO University in Saint Petersburg and research company SOPOT devised a foam, which was awarded full biodegradability and whose fire extinguishing capacity is higher than that of any existing analogue currently in use by fire fighters. After the fire is extinguished, the substance actively absorbs water, softens and falls apart into bioinert silica particles. And even when the foam accidentally enters living organisms, it does not not pose any danger to them.

“Our foam is based on silica nanoparticles, which create a polymer network when exposed to air,” says Alexander Vinogradov, deputy head of the SCAMT laboratory. “Such a network embraces and adheres to the burning object and momentarily cools it down. At the same time, the foam itself hardens. The inorganic origin of this polymer network allows it to resist temperatures above 1000 degrees Celsius, which ensures gigantic stability from the aggressive environment in the midst of a raging fire.”

“Most existing foams are made of organic materials and quickly deteriorate when temperature approaches 300 degrees Celsius. In our case, the foam creates a hard frame that not only puts out the fire, but also protects the object from re-ignition. With ordinary foams, re-ignition occurs within seconds after flame is applied to the object again.”

The scientists conducted a series of large-scale experiments of the hardening foam, including the imitation of an actual forest fire. The foam was used to create a flame retardant belt that was supposed stop the spread of the fire. The tests demonstrated that the foam easily localizes the forest fire seat and can stay active during the whole fire season.

“The flame retardant belt made of our foam will prevent the spread of any forest fire, regardless of its strength and level of complexity,” says Gennady Kuprin, head of SOPOT. “We can localize the fire and be sure that the adjacent territories will be safe. This is crucial to organize evacuation works during forest fires, where 9 of 10 people die in our and other countries.”

The standard firefighting foam can take up to 200 years before completely degrading? I hope this new foam is all they say it is and that they can get it to market. In the meantime, here’s a link to and a citation for the researchers’ paper,

Silica foams for fire prevention and firefighting by Alexander V. Vinogradov, Denis Kuprin, Iosif Abduragimov, Gennadii Kuprin, Evgeniy Serebriyakov, and Vladimir V. Vinogradov. ACS Appl. Mater. Interfaces, DOI: 10.1021/acsami.5b08653
Publication Date (Web): October 22, 2015

Copyright © 2015 American Chemical Society

This is paper is behind a paywall. But, the researchers have made an image of the foam available,

Caption: This is an electronic microscope image of hybrid silica foam. Credit: ITMO University

Caption: This is an electronic microscope image of hybrid silica foam. Credit: ITMO University

For anyone curious about SOPOT, here’s more from the company’s About page,

  “NPO Sopot” was founded in 1994 in St. Petersburg. Its creation was preceded by many years of scientific research and experimental design work done in person at the head of the firm basis of the Ministry of Defence and the Ministry of Internal Affairs of Russia, as well as, with the participation and cooperation with representatives of several institutions of the defense industry (the Sukhoi Design Bureau, Institute TRANSMASH, Academy. Zhukovsky etc.), the Ministry of Civil aviation, Fire Prevention Russian Interior Ministry, the Russian Interior Ministry VIPTSH

General Director of JSC “NPO” Sopot “Gennady Kuprin. Winner of the National Industry Award” Bison-2006 “, the grand prize Emergencies Ministry in 2005 and 2006., Awarded the” Golden Shield of the Russian economy, “international diploma” European quality “member of the International Academy of Patronage, the World Academy of Integrated Security.

Russians offer nanotechnology report at Paris Climate talks

Sadly I cannot find the report presented by the Russians  at the Paris Climate Talks (also known as World Climate Change Conference 2015 [COP21]) but did find this reference to it in a Dec. 7, 2015 article in the New York Times,

One of the surprises of the Paris climate talks was the sudden interest by Russia in appearing as a player in the efforts to reel in greenhouse gases.

The second part occurred on Monday, when an event was added to the schedule of news briefings: “Russia Proposes a New Approach to Climate Change.”

And so Russia did, putting forth a plan — and a report — that in the end seemed largely geared toward promoting a government-funded business, run by a prominent politician.

The Russian Times (rt.com) published a Nov. 30, 2015 article detailing President Vladimir Putin’s address to the conference attendees,

“We have gone beyond the target fixed by the Kyoto Protocol for the period from 1991 to 2012. Russia not only prevented the growth of greenhouse gas emission, by also significantly reduced it,” Putin said.

“Nearly 40 billion tons of carbon dioxide equivalent weren’t released into the atmosphere. As a comparison, the total emissions of all countries in 2012 reached 46 billion tons.”

Russia is planning to keep progressing by bringing breakthrough technologies into practice, “including nanotechnology,” Putin continued saying the country is also open to exchange and share the findings.

Apart from that, Putin has also promised Russia will reduce its polluting emissions by 70 percent by 2030 as compared to base level in 1990.

A Dec. 8, 2015 article by Jasper Nikki De La Cruz for The Science Times provides more detail about the Russian report/proposal (Note: A link has been removed),

Russia proposes a “New Approach” when it comes to dealing with climate change. The proposal focuses on efforts to reduce emissions involving five materials: steel, cement, aluminum, plastic and paper. The proposal is not on the reduction of the production of these materials but rather making these materials lighter, stronger and more efficient. With this approach, nanotechnology is put into the spotlight as the primary technology in making this proposal possible in real-world applications.

Rusnano is a company that is dedicated to nanotechnology. They received $10B of funding from the Russian government. They are pegged to be the frontrunner in research and application of nanotechnology in the production of the mentioned materials.

“Carbon nanotubes have been shown to toughen aluminum, make plastics conductive, extend the life of lithium-ion batteries,” Anatoly B. Chubais, Rusnano founder, said. “So all that is true. Tangentially, that can then lower CO2 emissions, I suppose.”

James Tour, a scientist at Rice University, commented for the New York Times Dec. 7, 2015 article on this suggestion that greater use of carbon nanotubes could reduce emissions,

A report laying out the materials thesis rested heavily on contentions about the use of carbon nanotubes. For a moment that puzzled James M. Tour, a professor of chemistry and materials science at Rice University and an expert on nanomaterials, who was asked about the proposal.

“Carbon nanotubes have been shown to toughen aluminum, make plastics conductive, extend the life of lithium-ion batteries,” he said in an email. “So all that is true. Tangentially, that can then lower CO2 emissions, I suppose.”

But, he added, “All of the above was well known long before Rusnano came around.”

Reporters, too, were confused. When one asked whether the announcement was “a distraction from real action,” Mr. Chubais said the proposal was a means to the same end.

I don’t find the Russian proposal all that outlandish although the emphasis on carbon nanotubes seems a bit outsized (pun intended). In any event, there’s certainly a role for emerging technologies to play in the attempts to change our lifestyles and ameliorate climate change.

A new nanoparticle—layered* like an onion

The new nanoparticle comes courtesy of an international collaboration (US, China, Sweden, and Russia. A Nov. 10, 2015 University of Buffalo news release (also on EurekAlert) by Charlotte Hu describes the particle and its properties,

A new, onion-like nanoparticle could open new frontiers in biomaging, solar energy harvesting and light-based security techniques.

The particle’s innovation lies in its layers: a coating of organic dye, a neodymium-containing shell, and a core that incorporates ytterbium and thulium. Together, these strata convert invisible near-infrared light to higher energy blue and UV light with record-high efficiency, a trick that could improve the performance of technologies ranging from deep-tissue imaging and light-induced therapy to security inks used for printing money.

Here’s an artist’s representation of the new nanoparticle,

An artist’s rendering shows the layers of a new, onion-like nanoparticle whose specially crafted layers enable it to efficiently convert invisible near-infrared light to higher energy blue and UV light. Credit: Kaiheng Wei Courtesy: University of Buffalo

An artist’s rendering shows the layers of a new, onion-like nanoparticle whose specially crafted layers enable it to efficiently convert invisible near-infrared light to higher energy blue and UV light. Credit: Kaiheng Wei Courtesy: University of Buffalo

The news release goes on to describe technology in more detail,

When it comes to bioimaging, near-infrared light could be used to activate the light-emitting nanoparticles deep inside the body, providing high-contrast images of areas of interest. In the realm of security, nanoparticle-infused inks could be incorporated into currency designs; such ink would be invisible to the naked eye, but glow blue when hit by a low-energy laser pulse — a trait very difficult for counterfeiters to reproduce.

“It opens up multiple possibilities for the future,” says Tymish Ohulchanskyy, deputy director of photomedicine and research associate professor at the Institute for Lasers, Photonics, and Biophotonics (ILPB) at the University at Buffalo.

“By creating special layers that help transfer energy efficiently from the surface of the particle to the core, which emits blue and UV light, our design helps overcome some of the long-standing obstacles that previous technologies faced,” says Guanying Chen, professor of chemistry at Harbin Institute of Technology [China] and ILPB research associate professor.

“Our particle is about 100 times more efficient at ‘upconverting’ light than similar nanoparticles created in the past, making it much more practical,” says Jossana Damasco, a UB chemistry PhD student who played a key role in the project.

The research was published online in Nano Letters on Oct. 21 and led by the Institute for Lasers, Photonics, and Biophotonics at UB, and the Harbin Institute of Technology in China, with contributions from the Royal Institute of Technology in Sweden; Tomsk State University in Russia; and the University of Massachusetts Medical School.

The study’s senior author was Paras Prasad, ILPB executive director and SUNY [State University of New York] Distinguished Professor in chemistry, physics, medicine and electrical engineering at UB.

Peeling back the layers

Converting low-energy light to light of higher energies isn’t easy to do. The process involves capturing two or more tiny packets of light called “photons” from a low-energy light source, and combining their energy to form a single, higher-energy photon.

The onionesque nanoparticle performs this task beautifully. Each of its three layers fulfills a unique function:

  • The outermost layer is a coating of organic dye. This dye is adept at absorbing photons from low-energy near-infrared light sources. It acts as an “antenna” for the nanoparticle, harvesting light and transferring energy inside, Ohulchanskyy says.
  • The next layer is a neodymium-containing shell. This layer acts as a bridge, transferring energy from the dye to the particle’s light-emitting core.
  • Inside the light-emitting core, ytterbium and thulium ions work in concert. The ytterbium ions draw energy into the core and pass the energy on to the thulium ions, which have special properties that enable them to absorb the energy of three, four or five photons at once, and then emit a single higher-energy photon of blue and UV light.

So why not just use the core? Why add the dye and neodymium layer at all?

As Ohulchanskyy and Chen explain, the core itself is inefficient in absorbing photons from the outside world. That’s where the dye comes in.

Once you add the dye, the neodymium-containing layer is necessary for transferring energy efficiently from dye to core. Ohulchanskyy uses the analogy of a staircase to explain why this is: When molecules or ions in a material absorb a photon, they enter an “excited” state from which they can transfer energy to other molecules or ions. The most efficient transfer occurs between molecules or ions whose excited states require a similar amount of energy to obtain, but the dye and ytterbium ions have excited states with very different energies. So the team added neodymium — whose excited state is in between that of the dye and thulium’s — to act as a bridge between the two, creating a “staircase” for the energy to travel down to reach emitting thulium ions.

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

Energy-Cascaded Upconversion in an Organic Dye-Sensitized Core/Shell Fluoride Nanocrystal by Guanying Chen, Jossana Damasco, Hailong Qiu, Wei Shao, Tymish Y. Ohulchanskyy, Rashid R. Valiev, Xiang Wu, Gang Han, Yan Wang, Chunhui Yang, Hans Ågren, and Paras N. Prasad. Nano Lett., 2015, 15 (11), pp 7400–7407 DOI: 10.1021/acs.nanolett.5b02830 Publication Date (Web): October 21, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

Finally, there is a Nov. 11, 2015 article about the research by Jake Wilkinson for Azonano. He provides additional details such as this measurement,

Measuring approximately 50nm in diameter, the new nanoparticle features three differently designed layers. …

*’ayered’ changed to ‘layered’ on Nov. 11, 2015.

Global overview of nano-enabled food and agriculture regulation

First off, this post features an open access paper summarizing global regulation of nanotechnology in agriculture and food production. From a Sept. 11, 2015 news item on Nanowerk,

An overview of regulatory solutions worldwide on the use of nanotechnology in food and feed production shows a differing approach: only the EU and Switzerland have nano-specific provisions incorporated in existing legislation, whereas other countries count on non-legally binding guidance and standards for industry. Collaboration among countries across the globe is required to share information and ensure protection for people and the environment, according to the paper …

A Sept. 11, 2015 European Commission Joint Research Centre press release (also on EurekAlert*), which originated the news item, summarizes the paper in more detail (Note: Links have been removed),

The paper “Regulatory aspects of nanotechnology in the agri/feed/food sector in EU and non-EU countries” reviews how potential risks or the safety of nanotechnology are managed in different countries around the world and recognises that this may have implication on the international market of nano-enabled agricultural and food products.

Nanotechnology offers substantial prospects for the development of innovative products and applications in many industrial sectors, including agricultural production, animal feed and treatment, food processing and food contact materials. While some applications are already marketed, many other nano-enabled products are currently under research and development, and may enter the market in the near future. Expected benefits of such products include increased efficacy of agrochemicals through nano-encapsulation, enhanced bioavailability of nutrients or more secure packaging material through microbial nanoparticles.

As with any other regulated product, applicants applying for market approval have to demonstrate the safe use of such new products without posing undue safety risks to the consumer and the environment. Some countries have been more active than others in examining the appropriateness of their regulatory frameworks for dealing with the safety of nanotechnologies. As a consequence, different approaches have been adopted in regulating nano-based products in the agri/feed/food sector.

The analysis shows that the EU along with Switzerland are the only ones which have introduced binding nanomaterial definitions and/or specific provisions for some nanotechnology applications. An example would be the EU labelling requirements for food ingredients in the form of ‘engineered nanomaterials’. Other regions in the world regulate nanomaterials more implicitly mainly by building on non-legally binding guidance and standards for industry.

The overview of existing legislation and guidances published as an open access article in the Journal Regulatory Toxicology and Pharmacology is based on information gathered by the JRC, RIKILT-Wageningen and the European Food Safety Agency (EFSA) through literature research and a dedicated survey.

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

Regulatory aspects of nanotechnology in the agri/feed/food sector in EU and non-EU countries by Valeria Amenta, Karin Aschberger, , Maria Arena, Hans Bouwmeester, Filipa Botelho Moniz, Puck Brandhoff, Stefania Gottardo, Hans J.P. Marvin, Agnieszka Mech, Laia Quiros Pesudo, Hubert Rauscher, Reinhilde Schoonjans, Maria Vittoria Vettori, Stefan Weigel, Ruud J. Peters. Regulatory Toxicology and Pharmacology Volume 73, Issue 1, October 2015, Pages 463–476 doi:10.1016/j.yrtph.2015.06.016

This is the most inclusive overview I’ve seen yet. The authors cover Asian countries, South America, Africa, and the MIddle East, as well as, the usual suspects in Europe and North America.

Given I’m a Canadian blogger I feel obliged to include their summary of the Canadian situation (Note: Links have been removed),

4.2. Canada

The Canadian Food Inspection Agency (CFIA) and Public Health Agency of Canada (PHAC), who have recently joined the Health Portfolio of Health Canada, are responsible for food regulation in Canada. No specific regulation for nanotechnology-based food products is available but such products are regulated under the existing legislative and regulatory frameworks.11 In October 2011 Health Canada published a “Policy Statement on Health Canada’s Working Definition for Nanomaterials” (Health Canada, 2011), the document provides a (working) definition of NM which is focused, similarly to the US definition, on the nanoscale dimensions, or on the nanoscale properties/phenomena of the material (see Annex I). For what concerns general chemicals regulation in Canada, the New Substances (NS) program must ensure that new substances, including substances that are at the nano-scale (i.e. NMs), are assessed in order to determine their toxicological profile ( Environment Canada, 2014). The approach applied involves a pre-manufacture and pre-import notification and assessment process. In 2014, the New Substances program published a guidance aimed at increasing clarity on which NMs are subject to assessment in Canada ( Environment Canada, 2014).

Canadian and US regulatory agencies are working towards harmonising the regulatory approaches for NMs under the US-Canada Regulatory Cooperation Council (RCC) Nanotechnology Initiative.12 Canada and the US recently published a Joint Forward Plan where findings and lessons learnt from the RCC Nanotechnology Initiative are discussed (Canada–United States Regulatory Cooperation Council (RCC) 2014).

Based on their summary of the Canadian situation, with which I am familiar, they’ve done a good job of summarizing. Here are a few of the countries whose regulatory instruments have not been mentioned here before (Note: Links have been removed),

In Turkey a national or regional policy for the responsible development of nanotechnology is under development (OECD, 2013b). Nanotechnology is considered as a strategic technological field and at present 32 nanotechnology research centres are working in this field. Turkey participates as an observer in the EFSA Nano Network (Section 3.6) along with other EU candidate countries Former Yugoslav Republic of Macedonia, and Montenegro (EFSA, 2012). The Inventory and Control of Chemicals Regulation entered into force in Turkey in 2008, which represents a scale-down version of the REACH Regulation (Bergeson et al. 2010). Moreover, the Ministry of Environment and Urban Planning published a Turkish version of CLP Regulation (known as SEA in Turkish) to enter into force as of 1st June 2016 (Intertek).

The Russian legislation on food safety is based on regulatory documents such as the Sanitary Rules and Regulations (“SanPiN”), but also on national standards (known as “GOST”) and technical regulations (Office of Agricultural Affairs of the USDA, 2009). The Russian policy on nanotechnology in the industrial sector has been defined in some national programmes (e.g. Nanotechnology Industry Development Program) and a Russian Corporation of Nanotechnologies was established in 2007.15 As reported by FAO/WHO (FAO/WHO, 2013), 17 documents which deal with the risk assessment of NMs in the food sector were released within such federal programs. Safe reference levels on nanoparticles impact on the human body were developed and implemented in the sanitary regulation for the nanoforms of silver and titanium dioxide and, single wall carbon nanotubes (FAO/WHO, 2013).

Other countries included in this overview are Brazil, India, Japan, China, Malaysia, Iran, Thailand, Taiwan, Australia, New Zealand, US, South Africa, South Korea, Switzerland, and the countries of the European Union.

*EurekAlert link added Sept. 14, 2015.