Tag Archives: Russia

International news bits: Israel and Germany and Cuba and Iran

I have three news bits today.


From a Nov. 14, 2016 posting by Lynn L. Bergeson and Carla N. Hutton for The National Law Review (Note: A link has been removed),

The German Federal Ministry of Education and Research (BMBF) recently published an English version of its Action Plan Nanotechnology 2020. Based on the success of the Action Plan Nanotechnology over the previous ten years, the federal government will continue the Action Plan Nanotechnology for the next five years.  Action Plan Nanotechnology 2020 is geared towards the priorities of the federal government’s new “High-Tech Strategy” (HTS), which has as its objective the solution of societal challenges by promoting research.  According to Action Plan Nanotechnology 2020, the results of a number of research projects “have shown that nanomaterials are not per se linked with a risk for people and the environment due to their nanoscale properties.”  Instead, this is influenced more by structure, chemical composition, and other factors, and is thus dependent on the respective material and its application.

A Nov. 16, 2016 posting on Out-Law.com provides mores detail about the plan (Note: A link has been removed),

Eight ministries have been responsible for producing a joint plan on nanotechnology every five years since 2006, the Ministry said. The ministries develop a common approach that pools strategies for action and fields of application for nanotechnology, it [Germany’s Federal Ministry of Education and Research] said.

The German public sector currently spends more than €600 million a year on nanotechnology related developments, and 2,200 organisations from industry, services, research and associations are registered in the Ministry’s nanotechnology competence map, the report said.

“There are currently also some 1,100 companies in Germany engaged [in] the use of nanotechnology in the fields of research and development as well as the marketing of commercial products and services. The proportion of SMEs [small to medium enterprises?] is around 75%,” it said.

Nanotechnology-based product innovations play “an increasingly important role in many areas of life, such as health and nutrition, the workplace, mobility and energy production”, and the plan “thus pursues the objective of continuing to exploit the opportunities and potential of nanotechnology in Germany, without disregarding any potential risks to humans and the environment.”, the Ministry said.

Technology law expert Florian von Baum of Pinsent Masons, the law firm behind Out-Law.com said: “The action plan aims to achieve and secure Germany’s critical lead in the still new nanotechnology field and to recognise and use the full potential of nanotechnology while taking into account possible risks and dangers of this new technology.”


“With the rapid pace of development and the new applications that emerge every day, the government needs to ensure that the dangers and risks are sufficiently recognised and considered. Nanotechnology will provide great and long-awaited breakthroughs in health and ecological areas, but ethical, legal and socio-economic issues must be assessed and evaluated at all stages of the innovation chain,” von Baum said.

You can find Germany’s Action Plan Nanotechnology 2020 here, all 64 pp.of it.

Israel and Germany

A Nov. 16, 2016 article by Shoshanna Solomon for The Times of Israel announces a new joint (Israel-Germany) nanotechnology fund,

Tsrael and Germany have set up a new three-year, €30 million plan to promote joint nanotechnology initiatives and are calling on companies and entities in both countries to submit proposals for funding for projects in this field.

“Nanotech is the industry of the future in global hi-tech and Israel has set a goal of becoming a leader of this field, while cooperating with leading European countries,” Ilan Peled, manager of Technological Infrastructure Arena at the Israel Innovation Authority, said in a statement announcing the plan.

In the past decade nanotechnology, seen by many as the tech field of the future, has focused mainly on research. Now, however, Israel’s Innovation Authority, which has set up the joint program with Germany, believes the next decade will focus on the application of this research into products — and countries are keen to set up the right ecosystem that will draw companies operating in this field to them.

Over the last decade, the country has focused on creating a “robust research foundation that can support a large industry,” the authority said, with six academic research institutes that are among the world’s most advanced.

In addition, the authority said, there are about 200 new startups that were established over the last decade in the field, many in the development stage.

I know it’s been over 70 years since the events of World War II but this does seem like an unexpected coupling. It is heartening to see that people can resolve the unimaginable within the space of a few generations.

Iran and Cuba

A Nov. 16, 2016 Mehr News Agency press release announces a new laboratory in Cuba,

Iran is ready to build a laboratory center equipped with nanotechnology in one of nano institutes in Cuba, Iran’s VP for Science and Technology Sorena Sattari said Tuesday [Nov. 15, 2016].

Sorena Sattari, Vice-President for Science and Technology, made the remark in a meeting with Fidel Castro Diaz-Balart, scientific adviser to the Cuban president, in Tehran on Tuesday [November 15, 2016], adding that Iran is also ready to present Cuba with a gifted package including educational services related to how to operate the equipment at the lab.

During the meeting, Sattari noted Iran’s various technological achievements including exports of biotechnological medicine to Russia, the extensive nanotechnology plans for high school and university students as well as companies, the presence of about 160 companies active in the field of nanotechnology and the country’s achievements in the field of water treatment.

“We have sealed good nano agreements with Cuba, and are ready to develop our technological cooperation with this country in the field of vaccines and recombinant drugs,” he said.

Sattari maintained that the biggest e-commerce company in the Middle East is situated in Iran, adding “the company which was only established six years ago now sales over $3.5 million in a day, and is even bigger than similar companies in Russia.”

The Cuban official, for his part, welcomed any kind of cooperation with Iran, and thanked the Islamic Republic for its generous proposal on establishing a nanotechnology laboratory in his country.

This coupling is not quite so unexpected as Iran has been cozying up to all kinds of countries in its drive to establish itself as a nanotechnology leader.

A computer that intuitively predicts a molecule’s chemical properties

First, we have emotional artificial intelligence from MIT (Massachusetts Institute of Technology) with their Kismet [emotive AI] project and now we have intuitive computers according to an Oct. 14, 2016 news item on Nanowerk,

Scientists from Moscow Institute of Physics and Technology (MIPT)’s Research Center for Molecular Mechanisms of Aging and Age-Related Diseases together with Inria research center, Grenoble, France have developed a software package called Knodle to determine an atom’s hybridization, bond orders and functional groups’ annotation in molecules. The program streamlines one of the stages of developing new drugs.

An Oct. 14, 2016 Moscow Institute of Physics and Technology press release (also on EurekAlert), which originated the news item, expands on the theme,

Imagine that you were to develop a new drug. Designing a drug with predetermined properties is called drug-design. Once a drug has entered the human body, it needs to take effect on the cause of a disease. On a molecular level this is a malfunction of some proteins and their encoding genes. In drug-design these are called targets. If a drug is antiviral, it must somehow prevent the incorporation of viral DNA into human DNA. In this case the target is viral protein. The structure of the incorporating protein is known, and we also even know which area is the most important – the active site. If we insert a molecular “plug” then the viral protein will not be able to incorporate itself into the human genome and the virus will die. It boils down to this: you find the “plug” – you have your drug.

But how can we find the molecules required? Researchers use an enormous database of substances for this. There are special programs capable of finding a needle in a haystack; they use quantum chemistry approximations to predict the place and force of attraction between a molecular “plug” and a protein. However, databases only store the shape of a substance; information about atom and bond states is also needed for an accurate prediction. Determining these states is what Knodle does. With the help of the new technology, the search area can be reduced from hundreds of thousands to just a hundred. These one hundred can then be tested to find drugs such as Reltagravir – which has actively been used for HIV prevention since 2011.

From science lessons at school everyone is used to seeing organic substances as letters with sticks (substance structure), knowing that in actual fact there are no sticks. Every stick is a bond between electrons which obeys the laws of quantum chemistry. In the case of one simple molecule, like the one in the diagram [diagram follows], the experienced chemist intuitively knows the hybridizations of every atom (the number of neighboring atoms which it is connected to) and after a few hours looking at reference books, he or she can reestablish all the bonds. They can do this because they have seen hundreds and hundreds of similar substances and know that if oxygen is “sticking out like this”, it almost certainly has a double bond. In their research, Maria Kadukova, a MIPT student, and Sergei Grudinin, a researcher from Inria research center located in Grenoble, France, decided to pass on this intuition to a computer by using machine learning.

Compare “A solid hollow object with a handle, opening at the top and an elongation at the side, at the end of which there is another opening” and “A vessel for the preparation of tea”. Both of them describe a teapot rather well, but the latter is simpler and more believable. The same is true for machine learning, the best algorithm for learning is the simplest. This is why the researchers chose to use a nonlinear support vector machines (SVM), a method which has proven itself in recognizing handwritten text and images. On the input it was given the positions of neighboring atoms and on the output collected hybridization.

Good learning needs a lot of examples and the scientists did this using 7605 substances with known structures and atom states. “This is the key advantage of the program we have developed, learning from a larger database gives better predictions. Knodle is now one step ahead of similar programs: it has a margin of error of 3.9%, while for the closest competitor this figure is 4.7%”, explains Maria Kadukova. And that is not the only benefit. The software package can easily be modified for a specific problem. For example, Knodle does not currently work with substances containing metals, because those kind of substances are rather rare. But if it turns out that a drug for Alzheimer’s is much more effective if it has metal, the only thing needed to adapt the program is a database with metallic substances. We are now left to wonder what new drug will be found to treat a previously incurable disease.

Scientists from MIPT's Research Center for Molecular Mechanisms of Aging and Age-Related Diseases together with Inria research center, Grenoble, France have developed a software package called Knodle to determine an atom's hybridization, bond orders and functional groups' annotation in molecules. The program streamlines one of the stages of developing new drugs. Credit: MIPT Press Office

Scientists from MIPT’s Research Center for Molecular Mechanisms of Aging and Age-Related Diseases together with Inria research center, Grenoble, France have developed a software package called Knodle to determine an atom’s hybridization, bond orders and functional groups’ annotation in molecules. The program streamlines one of the stages of developing new drugs. Credit: MIPT Press Office

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

Knodle: A Support Vector Machines-Based Automatic Perception of Organic Molecules from 3D Coordinates by Maria Kadukova and Sergei Grudinin. J. Chem. Inf. Model., 2016, 56 (8), pp 1410–1419 DOI: 10.1021/acs.jcim.5b00512 Publication Date (Web): July 13, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

Mechanism behind interaction of silver nanoparticles with the cells of the immune system

Scientists have come to a better understanding of the mechanism affecting silver nanoparticle toxicity according to an Aug. 30, 2016 news item on Nanowerk (Note: A link has been removed),

A senior fellow at the Faculty of Chemistry, MSU (Lomonosov Moscow State University), Vladimir Bochenkov together with his colleagues from Denmark succeeded in deciphering the mechanism of interaction of silver nanoparticles with the cells of the immune system. The study is published in the journal Nature Communications (“Dynamic protein coronas revealed as a modulator of silver nanoparticle sulphidation in vitro”).

‘Currently, a large number of products are containing silver nanoparticles: antibacterial drugs, toothpaste, polishes, paints, filters, packaging, medical and textile items. The functioning of these products lies in the capacity of silver to dissolve under oxidation and form ions Ag+ with germicidal properties. At the same time there are research data in vitro, showing the silver nanoparticles toxicity for various organs, including the liver, brain and lungs. In this regard, it is essential to study the processes occurring with silver nanoparticles in biological environments, and the factors affecting their toxicity,’ says Vladimir Bochenkov.

Caption: Increased intensity of the electric field near the silver nanoparticle surface in the excitation of plasmon resonance. Credit: Vladimir Bochenkov

Caption: Increased intensity of the electric field near the silver nanoparticle surface in the excitation of plasmon resonance. Credit: Vladimir Bochenkov

An Aug. 30, 2016 MSU press release on EurekAlert, which originated the news item, provides more information about the research,

The study is devoted to the protein corona — a layer of adsorbed protein molecules, which is formed on the surface of the silver nanoparticles during their contact with the biological environment, for example in blood. Protein crown masks nanoparticles and largely determines their fate: the speed of the elimination from the body, the ability to penetrate to a particular cell type, the distribution between the organs, etc.

According to the latest research, the protein corona consists of two layers: a rigid hard corona — protein molecules tightly bound with silver nanoparticles, and soft corona, consisting of weakly bound protein molecules in a dynamic equilibrium with the solution. Hitherto soft corona has been studied very little because of the experimental difficulties: the weakly bound nanoparticles separated from the protein solution easily desorbed (leave a particle remaining in the solution), leaving only the rigid corona on the nanoparticle surface.

The size of the studied silver nanoparticles was of 50-88 nm, and the diameter of the proteins that made up the crown — 3-7 nm. Scientists managed to study the silver nanoparticles with the protein corona in situ, not removing them from the biological environment. Due to the localized surface plasmon resonance used for probing the environment near the surface of the silver nanoparticles, the functions of the soft corona have been primarily investigated.

‘In the work we showed that the corona may affect the ability of the nanoparticles to dissolve to silver cations Ag+, which determine the toxic effect. In the absence of a soft corona (quickly sharing the medium protein layer with the environment) silver cations are associated with the sulfur-containing amino acids in serum medium, particularly cysteine and methionine, and precipitate as nanocrystals Ag2S in the hard corona,’ says Vladimir Bochenkov.

Ag2S (silver sulfide) famously easily forms on the silver surface even on the air in the presence of the hydrogen sulfide traces. Sulfur is also part of many biomolecules contained in the body, provoking the silver to react and be converted into sulfide. Forming of the nano-crystals Ag2S due to low solubility reduces the bioavailability of the Ag+ ions, reducing the toxicity of silver nanoparticles to null. With a sufficient amount of amino acid sulfur sources available for reaction, all the potentially toxic silver is converted into the nontoxic insoluble sulfide. Scientists have shown that what happens in the absence of a soft corona.

In the presence of a soft corona, the Ag2S silver sulfide nanocrystals are formed in smaller quantities or not formed at all. Scientists attribute this to the fact that the weakly bound protein molecules transfer the Ag+ ions from nanoparticles into the solution, thereby leaving the sulfide not crystallized. Thus, the soft corona proteins are ‘vehicles’ for the silver ions.

This effect, scientists believe, be taken into account when analyzing the stability of silver nanoparticles in a protein environment, and in interpreting the results of the toxicity studies. Studies of the cells viability of the immune system (J774 murine line macrophages) confirmed the reduction in cell toxicity of silver nanoparticles at the sulfidation (in the absence of a soft corona).

Vladimir Bochenkov’s challenge was to simulate the plasmon resonance spectra of the studied systems and to create the theoretical model that allowed quantitative determination of silver sulfide content in situ around nanoparticles, following the change in the absorption bands in the experimental spectra. Since the frequency of the plasmon resonance is sensitive to a change in dielectric constant near the nanoparticle surface, changes in the absorption spectra contain information about the amount of silver sulfide formed.

Knowledge of the mechanisms of formation and dynamics of the behavior of the protein corona, information about its composition and structure are extremely important for understanding the toxicity and hazards of nanoparticles for the human body. In prospect the protein corona formation can be used to deliver drugs in the body, including the treatment of cancer. For this purpose it will be enough to pick such a content of the protein corona, which enables silver nanoparticles penetrate only in the cancer cell and kill it.

Here’s a link to and a citation for the paper describing this fascinating work,

Dynamic protein coronas revealed as a modulator of silver nanoparticle sulphidation in vitro by Teodora Miclăuş, Christiane Beer, Jacques Chevallier, Carsten Scavenius, Vladimir E. Bochenkov, Jan J. Enghild, & Duncan S. Sutherland. Nature Communications 7,
Article number: 11770 doi:10.1038/ncomms11770 Published  09 June 2016

This paper is open access.

Deriving graphene-like films from salt

This research comes from Russia (mostly). A July 29, 2016 news item on ScienceDaily describes a graphene-like structure derived from salt,

Researchers from Moscow Institute of Physics and Technology (MIPT), Skolkovo Institute of Science and Technology (Skoltech), the Technological Institute for Superhard and Novel Carbon Materials (TISNCM), the National University of Science and Technology MISiS (Russia), and Rice University (USA) used computer simulations to find how thin a slab of salt has to be in order for it to break up into graphene-like layers. Based on the computer simulation, they derived the equation for the number of layers in a crystal that will produce ultrathin films with applications in nanoelectronics. …

Caption: Transition from a cubic arrangement into several hexagonal layers. Credit: authors of the study

Caption: Transition from a cubic arrangement into several hexagonal layers. Credit: authors of the study

A July 29, 2016 Moscow Institute of Physics and Technology press release on EurekAlert, which originated the news item,  provides more technical detail,

From 3D to 2D

Unique monoatomic thickness of graphene makes it an attractive and useful material. Its crystal lattice resembles a honeycombs, as the bonds between the constituent atoms form regular hexagons. Graphene is a single layer of a three-dimensional graphite crystal and its properties (as well as properties of any 2D crystal) are radically different from its 3D counterpart. Since the discovery of graphene, a large amount of research has been directed at new two-dimensional materials with intriguing properties. Ultrathin films have unusual properties that might be useful for applications such as nano- and microelectronics.

Previous theoretical studies suggested that films with a cubic structure and ionic bonding could spontaneously convert to a layered hexagonal graphitic structure in what is known as graphitisation. For some substances, this conversion has been experimentally observed. It was predicted that rock salt NaCl can be one of the compounds with graphitisation tendencies. Graphitisation of cubic compounds could produce new and promising structures for applications in nanoelectronics. However, no theory has been developed that would account for this process in the case of an arbitrary cubic compound and make predictions about its conversion into graphene-like salt layers.

For graphitisation to occur, the crystal layers need to be reduced along the main diagonal of the cubic structure. This will result in one crystal surface being made of sodium ions Na? and the other of chloride ions Cl?. It is important to note that positive and negative ions (i.e. Na? and Cl?)–and not neutral atoms–occupy the lattice points of the structure. This generates charges of opposite signs on the two surfaces. As long as the surfaces are remote from each other, all charges cancel out, and the salt slab shows a preference for a cubic structure. However, if the film is made sufficiently thin, this gives rise to a large dipole moment due to the opposite charges of the two crystal surfaces. The structure seeks to get rid of the dipole moment, which increases the energy of the system. To make the surfaces charge-neutral, the crystal undergoes a rearrangement of atoms.

Experiment vs model

To study how graphitisation tendencies vary depending on the compound, the researchers examined 16 binary compounds with the general formula AB, where A stands for one of the four alkali metals lithium Li, sodium Na, potassium K, and rubidium Rb. These are highly reactive elements found in Group 1 of the periodic table. The B in the formula stands for any of the four halogens fluorine F, chlorine Cl, bromine Br, and iodine I. These elements are in Group 17 of the periodic table and readily react with alkali metals.

All compounds in this study come in a number of different structures, also known as crystal lattices or phases. If atmospheric pressure is increased to 300,000 times its normal value, an another phase (B2) of NaCl (represented by the yellow portion of the diagram) becomes more stable, effecting a change in the crystal lattice. To test their choice of methods and parameters, the researchers simulated two crystal lattices and calculated the pressure that corresponds to the phase transition between them. Their predictions agree with experimental data.

Just how thin should it be?

The compounds within the scope of this study can all have a hexagonal, “graphitic”, G phase (the red in the diagram) that is unstable in 3D bulk but becomes the most stable structure for ultrathin (2D or quasi-2D) films. The researchers identified the relationship between the surface energy of a film and the number of layers in it for both cubic and hexagonal structures. They graphed this relationship by plotting two lines with different slopes for each of the compounds studied. Each pair of lines associated with one compound has a common point that corresponds to the critical slab thickness that makes conversion from a cubic to a hexagonal structure energetically favourable. For example, the critical number of layers was found to be close to 11 for all sodium salts and between 19 and 27 for lithium salts.

Based on this data, the researchers established a relationship between the critical number of layers and two parameters that determine the strength of the ionic bonds in various compounds. The first parameter indicates the size of an ion of a given metal–its ionic radius. The second parameter is called electronegativity and is a measure of the ? atom’s ability to attract the electrons of element B. Higher electronegativity means more powerful attraction of electrons by the atom, a more pronounced ionic nature of the bond, a larger surface dipole, and a lower critical slab thickness.

And there’s more

Pavel Sorokin, Dr. habil., [sic] is head of the Laboratory of New Materials Simulation at TISNCM. He explains the importance of the study, ‘This work has already attracted our colleagues from Israel and Japan. If they confirm our findings experimentally, this phenomenon [of graphitisation] will provide a viable route to the synthesis of ultrathin films with potential applications in nanoelectronics.’

The scientists intend to broaden the scope of their studies by examining other compounds. They believe that ultrathin films of different composition might also undergo spontaneous graphitisation, yielding new layered structures with properties that are even more intriguing.

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

Ionic Graphitization of Ultrathin Films of Ionic Compounds by A. G. Kvashnin, E. Y. Pashkin, B. I. Yakobson, and P. B. Sorokin. J. Phys. Chem. Lett., 2016, 7 (14), pp 2659–2663 DOI: 10.1021/acs.jpclett.6b01214 Publication Date (Web): June 23, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

Ageing population could drive progress in nanotechnology and robotics

A couple of theoreticians are proposing a generational gap as being a key source of conflict and technological process in the near future. From a July 27, 2016 news item on Nanotechnology Now,

The UN estimates that the number of people aged 65 and older will have reached almost a billion by 2030. The proportion of those aged over 80 will grow at particularly high rates, and their numbers are expected to reach 200 million by 2030 and triple that forty years later.

Due to a combination of an ageing population and declining birthrates, the demographic structure of most countries will change towards lower proportions of children and young people. As a result, the global division will no longer be between first- and third-world nations [also called developed and developing nations], but between old and young ones.

A July 25, 2016 National Research University Higher School of Economics [Russia] press release (also on EurekAlert), which originated the news item, expands on the theme,

According to the report of Senior Research Fellow of the HSE [Higher School of Economics] Laboratory for Monitoring the Risks of Socio-Political Destabilization Leonid Grinin and Senior Research Fellow of the International Centre for Education, Social and Humanitarian Studies Anton Grinin “Global Population Ageing and the Threat of Political Risks in the Light of Radical Technological Innovation in the Coming Decades.”, an increase in the number of older people will:

  • encourage societies facing workforce shortages to seek solutions to improve older people’s employability by helping them stay healthy, fit and full of energy for much longer than today;
  • encourage societies to focus more on rehabilitation of people with disabilities and provide them with new technology to support their employment;
  • encourage the development of labour-saving technologies, such as robotics, to assist caregivers;
  • lead to breakthroughs in medicine. Indeed, medical services will be the first to enter a new phase of technological revolution, radically changing the structure of production and people’s lives. Such a breakthrough will be associated what the authors call MANBRIC, i.e. a technological paradigm based on medicine, additive, nano- and bio- technologies, robotic, IT, and cognitive technologies;
  • boost government spending on healthcare, which today accounts for at least 10% of global GDP and can vary vastly across countries, e.g. reaching 17% in the U.S.;
  • promote the development of peripheral countries through higher spending on health care, leading to the emergence of a middle class, poverty reduction, literacy, and a better quality of life;
  • increase the demand for innovation and its financing from accumulated funds such as pensions and public allocations to medical and social needs;
  • lead to higher investment in supporting the health of ageing populations and the growing middle class.

Longevity Comes at a Cost

A confrontation between generations in the labor market and the weakening of democracy are the key risks associated with longer life expectancy.

Longer life spans and a lower proportion of young people in society may lead to the predominance of ‘third age’ voters. Politicians will need to tailor their messages to older and perhaps more conservative electorates. According to the researchers, “democracy can transform into a form of gerontocracy which may be hard to overcome; under such circumstances, competition for voters may lead to a crisis of democratic governance.”

A conflict between generations is another potential risk. As the retirement age increases, older employees will stay in the workforce longer – a situation which may hinder younger people’s careers and slow down technological progress.

A tendency towards gerontocracy has been particularly noticeable in Western Europe and the U.S., where democratic traditions are the strongest, but ethnic and cultural imbalances are increasingly visible. As a result, the U.S. may face confrontation between its younger Latinos and older white populations, and Europe may experience tensions between older white Christians and younger Muslims. Hence, globalization will inevitably cause such conflicts to transcend national borders and become global challenges.

I was not able to find the report mentioned in this release but I certainly would have liked to have looked at it. This redraws the conflict map in some interesting ways.

Researchers from Canada and Russia find metal-organic-frameworks in nature

To date, these ‘natural’ metal-organic-frameworks have been found only in Siberian coal mines. From an Aug, 5, 2016 news item on ScienceDaily,

One of the hottest new materials is a class of porous solids known as metal-organic frameworks, or MOFs. These human-made materials were introduced in the 1990s, and researchers around the world are working on ways to use them as molecular sponges for applications such as hydrogen storage, carbon sequestration, or photovoltaics.

Now, a surprising discovery by scientists in Canada and Russia reveals that MOFs also exist in nature — albeit in the form of rare minerals found so far only in Siberian coal mines.

The finding, published in the journal Science Advances, “completely changes the normal view of these highly popular materials as solely artificial, ‘designer’ solids,” says senior author Tomislav Friščić, an associate professor of chemistry at McGill University in Montreal. “This raises the possibility that there might be other, more abundant, MOF minerals out there.”

Caption: Individual crystals of synthetic zhemchuzhnikovite, prepared by Igor Huskić, McGill University. Credit: Igor Huskić, Friščić Research Group, McGill University

Caption: Individual crystals of synthetic zhemchuzhnikovite, prepared by Igor Huskić, McGill University. Credit: Igor Huskić, Friščić Research Group, McGill University

An Aug, 8, 2016 McGill University news release (also on EurekAlert but dated Aug. 5, 2016), which originated the news item, expands on the theme,

The twisting path to the discovery began six years ago, when Friščić came across a mention of the minerals stepanovite and zhemchuzhnikovite in a Canadian mineralogy journal. The crystal structure of the minerals, found in Russia between the 1940s and 1960s, hadn’t been fully determined. But the Russian mineralogists who discovered them had analyzed their chemical composition and the basic parameters of their structures, using a technique known as X-ray powder diffraction. To Friščić, those parameters hinted that the minerals could be structurally similar to a type of man-made MOF.

His curiosity piqued, Friščić began looking for samples of the rare minerals, reaching out to experts, museums and vendors in Russia and elsewhere. After a promising lead with a mining museum in Saint Petersburg failed to pan out, Igor Huskić, a graduate student in the Friščić research group at McGill turned his attention to synthesizing analogues of the minerals in the lab – and succeeded. But a major journal last year declined to publish the team’s work, in part because the original description of the minerals had been reported in a somewhat obscure Russian mineralogical journal.

Then, the McGill chemists caught a break: with the help of a crystallographer colleague in Venezuela, they connected with two prominent Russian mineralogists: Sergey Krivovichev, a professor at Saint Petersburg State University, and Prof. Igor Pekov of Lomonosov Moscow State University.

Krivovichev and Pekov were able to obtain the original samples of the two rare minerals, which had been found decades earlier in a coal mine deep beneath the Siberian permafrost. The Russian experts were also able to determine the crystal structures of the minerals. These findings confirmed the McGill researchers’ initial results from their lab synthesis.

Stepanovite and zhemchuzhnikovite have the elaborate, honeycomb-like structure of MOFs, characterized at the molecular level by large voids. The two minerals aren’t, however, representative of the hottest varieties of MOFs — those that are being developed for use in hydrogen-fueled cars or to capture waste carbon dioxide.

As a result, Friščić and his collaborators are now broadening their research to determine if other, more abundant minerals have porous structures that could make them suitable for uses such as hydrogen storage or even drug delivery.

In any event, the discovery of MOF structures in the two rare minerals already is “paradigm-changing” Friščić says. If scientists had been able to determine those structures in the 1960s, he notes, the development of MOF materials “might have been accelerated by 30 years.”

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

Minerals with metal-organic framework structures by Igor Huskić, Igor V. Pekov, Sergey V. Krivovichev, and Tomislav Friščić. Science Advances  05 Aug 2016: Vol. 2, no. 8, e1600621 DOI: 10.1126/sciadv.1600621

This paper appears to be open access.

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).